JP2023104975A - Coloring composition, color filter, solid-state image sensor, and liquid crystal display device - Google Patents

Abstract

To provide a coloring composition capable of obtaining a photosensitive coloring composition having an appropriate viscosity and satisfactory viscosity stability (dispersion stability), which can form a film having less foreign matter generation, less residue, and suppressed surface roughness.SOLUTION: The coloring composition contains organic pigment (A) and resin type dispersant (B). The organic pigment (A) includes one or more selected from zinc phthalocyanine pigment (A1) and aluminum phthalocyanine pigment (A2). The content of organic pigment (A) is 40 to 90% by mass in 100% by mass of the non-volatile content of the coloring composition. The resin type dispersant (B) contains an aromatic carboxylic acid structure, and a resin type dispersant (B1) having a vinyl polymer moiety which has a (meth) acryloyl group.SELECTED DRAWING: Figure 1

Description

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

Color filters used in solid-state imaging devices, liquid crystal display devices, and the like form fine patterns of photosensitive coloring compositions by photolithography. Solid-state imaging devices and liquid crystal display devices are required to have higher image quality and higher definition, and further improvements are required, and color filters are also required to be further miniaturized.

Patent Literature 1 discloses a coloring composition containing a block-structured dispersant.

JP-A-2002-31713

However, conventional coloring compositions tend to have a high viscosity and poor storage stability, so that they have a short self-life and tend to generate foreign matter in the coating. Furthermore, the photosensitive coloring composition containing the coloring composition has a problem that a residue tends to be generated after development by a photolithography method, and a problem that the film surface has a large surface roughness.

The present invention has moderate viscosity and good viscosity stability (dispersion stability), less generation of foreign matter, less residue, and a photosensitive coloring composition capable of forming a film with suppressed surface roughness. It is intended to provide a coloring composition that is obtained.

The photosensitive coloring composition of the present invention comprises an organic pigment (A), a resin-type dispersant (B), a binder resin (C) (excluding resins having a maleimide structure), and a polymerizable compound ( D) and a photosensitive coloring composition containing a photopolymerization initiator (E),
The organic pigment (A) contains one or more selected from zinc phthalocyanine pigment (A1) and aluminum phthalocyanine pigment (A2),
The content of the organic pigment (A) is 40 to 90% by mass in the non-volatile content of 100% by mass of the photosensitive coloring composition,
The resin-type dispersant (B) includes a resin-type dispersant (B1) having an aromatic carboxylic acid structure and a vinyl polymer moiety having a (meth)acryloyl group, and a resin-type dispersant (B3) having a basic group. including
In 100 parts by mass of the resin type dispersant (B), 34 to 100 parts by mass of the resin type dispersant (B1) is included, and 0.5 part of the binder resin (C) is added to 100 parts by mass of the resin type dispersant (B). Contains up to 50 parts by mass.

According to the above-described present invention, a photosensitizer capable of forming a film having moderate viscosity and good viscosity stability (dispersion stability), generating less foreign matter, less residue, and having suppressed surface roughness. It is possible to provide a coloring composition, a color filter, and a solid-state imaging device from which a natural coloring composition can be obtained.

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

Terms used herein are defined. "(meth)acryloyl", "(meth)acrylic", "
(Meth)acrylic acid", "(meth)acrylate", or "(meth)acrylamide", respectively, unless otherwise specified, "acryloyl and / or methacryloyl", "acrylic and / or methacrylic ”, “acrylic acid and/or methacrylic acid”, “acrylates and/or methacrylates”, or “acrylamide and/or methacrylamide”. References herein to "C.I." mean Color Index (C.I.). Colorants include pigments and dyes. A monomer is an ethylenically unsaturated group-containing monomer.

The coloring composition of the present invention is a coloring composition containing an organic pigment (A) and a resin type dispersant (B),
The organic pigment (A) contains one or more selected from zinc phthalocyanine pigment (A1) and aluminum phthalocyanine pigment (A2),
The content of the organic pigment (A) is 40 to 90% by mass in the non-volatile content of 100% by mass of the coloring composition,
The resin type dispersant (B) contains a resin type dispersant (B1) having a vinyl polymer moiety having an aromatic carboxylic acid structure and a (meth)acryloyl group.

<Organic Pigment (A)>
The organic pigment (A) contains one or more selected from zinc phthalocyanine pigment (A1) and aluminum phthalocyanine pigment (A2).
The zinc phthalocyanine pigment (A1) and aluminum phthalocyanine pigment (A2) preferably contain a halogen atom such as chlorine or bromine as a substituent. As the zinc phthalocyanine pigment (A1) and the aluminum phthalocyanine pigment (A2), for example, pigments described in JP-A-2004-70342 and JP-A-2017-111398 can be used.
The organic pigment (A) can be used in combination with a yellow pigment (a) to adjust the color tone of the film.

(Yellow pigment (a))
Yellow pigments are organic pigments such as 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 are preferred.

The coloring composition can contain inorganic pigments and dyes.
Inorganic pigments include, for example, titanium oxide, barium sulfate, zinc oxide, 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.

<Dye>
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 an acid dye having an acid group such as sulfonic acid or carboxylic acid, and in the case of a direct dye, an inorganic salt of an acid dye; an acid dye, a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, or salt-forming compounds with primary amine compounds; and salt-forming compounds such as resin components having these amino groups and acid dyes. 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.

Examples of basic dyes include organic acids, perchloric acid, and salt-forming compounds with these metal salts. 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.

<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. Examples of the method for the refinement treatment include wet grinding, dry grinding, dissolution precipitation, and the like. Among these, a salt milling treatment by a kneader method, which is one type of wet grinding, and the like are preferable. The average primary particle size of the organic pigment after refining is preferably 10 to 80 nm, more preferably 15 to 70 nm. Appropriate particle size improves the dispersibility and the contrast ratio of the film. The average primary particle size is the average value of about 20 particles arbitrarily selected from an enlarged image of a TEM (transmission electron microscope). When the particle has a vertical axis length and a horizontal axis length, the vertical axis length is used.

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, barium 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 pigment, 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 pigment.

When salt milling the pigment, a resin may be added as necessary. The type of resin used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like can be used. The resins used are preferably solid at room temperature, water-insoluble, and more preferably partially soluble in the above organic solvents. The amount of the resin used is preferably in the range of 5 to 200 parts by mass with respect to 100 parts by mass of the pigment.

<Resin Dispersant (B)>
The resin type dispersant (B) contains a resin type dispersant (B1) having a vinyl polymer moiety having an aromatic carboxylic acid structure and a (meth)acryloyl group.
The aromatic carboxylic acid structure adsorbs to the zinc phthalocyanine pigment (A1) and the aluminum phthalocyanine pigment (A2), and adheres to them to a high degree. In addition, the (meth)acryloyl group in the vinyl polymer portion can impart photocurability to the vinyl polymer portion, which is a relaxation portion with other materials. Normally, when preparing a photosensitive coloring composition, if the organic pigment (A) is blended at a high concentration, the blending amount of the binder resin is relatively reduced, and the film-forming properties may be reduced. The resin-type dispersant (B) is photocurable, contributes to film formation, and is less susceptible to deterioration in developability and the like. Further, when a color filter containing the zinc phthalocyanine pigment (A1) or the aluminum phthalocyanine pigment (A2) is heated in the post-baking process or the subsequent heat treatment process, the pigment may aggregate and crystal foreign matter may be generated. By using the resin-type dispersant (B1), aggregation due to thermal motion of the pigment particles can be suppressed, so heat resistance is improved, and deposition of crystal foreign matter can be prevented.

(Resin type dispersant (B1))
The resin-type dispersant (B1) is a dispersant having an aromatic carboxylic acid structure and a vinyl polymer moiety having a (meth)acryloyl group. The resin-type dispersant (B1) is, for example, (1) an acid anhydride group in one or more acid anhydrides selected from the group of tetracarboxylic acid anhydrides and tricarboxylic acid anhydrides, and a vinyl polymer synthesized separately. A method of synthesizing by reacting with the hydroxyl group of (2) a method of reacting an acid anhydride group in the acid anhydride with a hydroxyl group-containing thiol, and then polymerizing a monomer starting from the thiol group of the thiol to form a vinyl polymer moiety; mentioned. The resin-type dispersant (B1) is, in other words, a dispersant comprising a polyester portion having a carboxyl group and a vinyl polymer portion B obtained by polymerizing a monomer, and having a (meth)acryloyl group in the vinyl polymer portion. is. Resin-type dispersants (B1) include, for example, comb-type dispersants described in JP-A-2011-157416.

Tetracarboxylic dianhydrides are, for example, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1, 2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 3,5,6 -tricarboxynorbornane-2-acetic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 5-(2,5-dioxotetrahydrofural)-3-methyl-3-cyclohexene-1 ,2-dicarboxylic dianhydride, aliphatic tetracarboxylic dianhydride such as bicyclo[2,2,2]-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, pyro Melitic dianhydride, ethylene glycol dianhydride trimellitic ester, propylene glycol dianhydride trimellitic ester, butylene glycol dianhydride trimellitic ester, 3,3′,4,4′-benzophenonetetracarboxylic dianhydride , 3,3′,4,4′-biphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride 3,3′,4,4′-Biphenylethertetracarboxylic dianhydride, 3,3′,4,4′-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3′,4,4′ -tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylsulfide dianhydride, 4, 4'-bis(3,4-dicarboxyphenoxy)diphenylsulfone dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'- Perfluoroisopropylidene diphthalic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, bis(phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) acid) dianhydride, m-phenylene-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4'-diphenyl ether dianhydride, bis(triphenylphthalic acid)-4,4 '-diphenylmethane dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl]fluorene dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic dianhydride or 3,4-dicarboxy-1,2,3,4-tetrahydro-6-methyl-1- aromatic tetracarboxylic dianhydrides such as naphthalenesuccinic dianhydride; Among these, aromatic tetracarboxylic dianhydrides are preferable, and tetracarboxylic dianhydrides having two or more aromatic rings are more preferable in view of excellent adsorption to the colorant.

Tricarboxylic anhydrides include, for example, benzenetricarboxylic anhydride (1,2,3-benzenetricarboxylic anhydride, trimellitic anhydride [1,2,4-benzenetricarboxylic anhydride], etc.), naphthalenetricarboxylic acid Anhydrides (1,2,4-naphthalenetricarboxylic anhydride, 1,4,5-naphthalenetricarboxylic anhydride, 2,3,6-naphthalenetricarboxylic anhydride, 1,2,8-naphthalenetricarboxylic anhydride etc.), 3,4,4′-benzophenonetricarboxylic anhydride, 3,4,4′-biphenylethertricarboxylic anhydride, 3,4,4′-biphenyltricarboxylic anhydride, 2,3,2′- biphenyltricarboxylic anhydride, 3,4,4'-biphenylmethanetricarboxylic anhydride, 3,4,4'-biphenylsulfonetricarboxylic anhydride and the like. Among these, trimellitic anhydride is more preferable.

((Meth)acryloyl group-containing vinyl polymer moiety)
The (meth)acryloyl group-containing vinyl polymer portion can be synthesized by reacting the hydroxyl group of the vinyl polymer portion with the isocyanate group in the isocyanate group-containing monomer. As a result, photocurability is obtained at the vinyl polymer portion which is the relaxation portion.

Examples of isocyanate group-containing monomers include 2-methacryloyloxyethyl isocyanate, 2-acryloyloxyethyl isocyanate, 1,1-bis(acryloyloxymethyl)ethyl isocyanate and the like.

The hydroxyl-containing thiol is preferably a compound having two hydroxyl groups and one thiol group. As such, hydroxyl group-containing thiols include, for example, 1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, 3-mercapto-1,2-propanediol (thioglycerin), 2- mercapto-1,2-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol, 1-mercapto-2,2-propanediol, 2-mercaptoethyl-2-methyl-1,3-propanediol, 2-mercaptoethyl-2-ethyl-1,3-propanediol, and the like.

The monomer used for synthesizing the vinyl polymer moiety includes, for example, at least one thermally crosslinkable functional group selected from the group consisting of hydroxyl group, oxetane group, t-butyl group and blocked isocyanate group, and a carboxyl group-containing monomer. and other monomers.

Hydroxyl-containing monomers include, for example, 2-hydroxyethyl (meth)acrylate, 2 (or 3)-hydroxypropyl (meth)acrylate, 2 (or 3 or 4)-hydroxybutyl (meth)acrylate and cyclohexanedimethanol mono hydroxyalkyl (meth)acrylates such as (meth)acrylates and alkyl-α-hydroxyalkyl acrylates such as ethyl-α-hydroxymethyl acrylate;
(Meth)acrylamide-based monomers having a hydroxyl group include, for example, N-(2-hydroxyethyl)(meth)acrylamide, N-(2-hydroxypropyl)(meth)acrylamide, N-(2-hydroxybutyl) ( N-(hydroxyalkyl)(meth)acrylamides such as meth)acrylamide;
Vinyl ether monomers having a hydroxyl group, such as hydroxyalkyl vinyl ethers such as 2-hydroxyethyl vinyl ether, 2-(or 3-) hydroxypropyl vinyl ether, 2-(or 3- or 4-) hydroxybutyl vinyl ether;
As allyl ether monomers having a hydroxyl group, hydroxyalkyls such as 2-hydroxyethyl allyl ether, 2-(or 3-) hydroxypropyl allyl ether, 2-(or 3- or 4-) hydroxybutyl allyl ether Allyl ethers are mentioned.

Examples of the oxetane group-containing monomer include (vinyloxyalkyl)alkyloxetane, (meth)acryloyloxyalkyloxetane, [(meth)acryloyloxyalkyl]alkyloxetane and the like. Among these, (3-ethyloxetan-3-yl)methyl methacrylate is preferred.

Examples of monomers having a t-butyl group include t-butyl methacrylate and t-butyl acrylate.

Examples of blocked isocyanate group-containing monomers include 2-(0-[1'-methylpropylideneamino]carboxyamino)ethyl methacrylate, 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate, and the like. mentioned.

The amount of the thermally crosslinkable functional group-containing monomer used is preferably 5 to 90% by mass, more preferably 20 to 60% by mass, based on the total amount of monomers. When used in an appropriate amount, the solvent resistance of the film is further improved.

Carboxyl group-containing monomers include, for example, (meth)acrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid and the like. Among these, (meth)acrylic acid is preferred.

Other monomers include (meth)acrylic acid esters, nitrogen-containing group monomers, and vinyl monomers. (Meth) acrylic acid esters, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate and other (meth)acrylic acid alkyl esters; cyclohexyl (meth)acrylate, tertiarybutylcyclohexyl (meth)acrylate, Alicyclic (meth)acrylates such as dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and isobornyl (meth)acrylate; phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate ) acrylates, aromatic (meth)acrylates such as phenoxydiethylene glycol (meth)acrylate; heterocyclic (meth)acrylates such as tetrahydrofurfuryl (meth)acrylate, and 3-methyl-3-oxetanyl (meth)acrylate; Alkoxypolyalkylene glycol (meth)acrylates such as methoxypolypropylene glycol (meth)acrylate and ethoxypolyethylene glycol (meth)acrylate;

Nitrogen-containing group monomers include, for example, (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, N-substituted (meth)acrylamides such as acryloylmorpholine; amino group-containing (meth)acrylates such as N,N-dimethylaminoethyl (meth)acrylate and N,N-diethylaminoethyl (meth)acrylate; meth)acrylonitrile, etc. Nitriles of.

Vinyl monomers include, for example, styrenes such as styrene and α-methylstyrene; vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether and isobutyl vinyl ether; Examples include fatty acid vinyls.

(Resin type dispersant (B2))
The resin-type dispersant (B) can be used in combination with the resin-type dispersant (B2). The resin-type dispersant (B2) is a dispersant having an aromatic carboxylic acid structure and a vinyl polymer moiety (but not having a (meth)acryloyl group). The resin-type dispersant (B2) has a structure obtained by removing the (meth)acryloyl group from the resin-type dispersant (B1). Examples of the resin-type dispersant (B2) include comb-type dispersants described in Japanese Patent No. 4,396,777 and Japanese Patent No. 5,181,664. By using the resin-type dispersant (B1) and the resin-type dispersant (B2) together, the photocurability of the film can be appropriately adjusted.

(Resin type dispersant (B3))
The resin-type dispersant (B) can be used in combination with a resin-type dispersant (B3) having a basic group. Basic groups include, for example, tertiary amino groups, quaternary ammonium bases, nitrogen-containing heterocycles, and the like. Examples of the resin skeleton include acrylic resins and urethane resins.

(Other dispersants)
The resin-type dispersant (B) can be used in combination with dispersants other than those described above.
Other dispersants include, for example, urethane dispersants such as polyurethane, polycarboxylic acid esters such as polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid (partial) amine salt, polycarboxylic acid ammonium salt, polycarboxylic acid Alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, modified products thereof, amides formed by the reaction of poly(lower alkyleneimine) with polyesters having free carboxyl groups and its salts, (meth)acrylic acid-styrene copolymer, (meth)acrylic acid-(meth)acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinyl Water-soluble resins such as pyrrolidone, water-soluble polymer compounds, polyesters, modified polyacrylates, ethylene oxide/propylene oxide addition compounds, phosphoric acid esters and the like can be mentioned.

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

The amount of the resin type dispersant (B) used is preferably 3 to 200% by mass, more preferably 5 to 100% by mass, based on 100 parts by mass of the organic pigment (A). When used in an appropriate amount, the film formability is further improved.

<Dye derivative (b)>
The coloring composition can contain a dye derivative (b). When the dye derivative (b) is used in dispersing the organic pigment (A), the dispersion stability of the coloring composition is further improved.
The dye derivative is preferably a known dye derivative having an acidic group, a basic group, a neutral group, or the like in an organic dye residue. Examples of dye derivatives include compounds having an acidic substituent such as a sulfo group, a carboxyl group, and a phosphoric acid group, amine salts thereof, compounds having a basic substituent such as a sulfonamide group or a terminal tertiary amino group, phenyl and compounds having a neutral substituent such as a phthalimidoalkyl group. Since the resin-type dispersant used in combination has an acidic group, a dye derivative having a basic group is preferred.
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. .

<Binder resin (C)>
The coloring composition can contain a binder resin (C). This makes it easier to form a coating.
The amount of the binder resin (C) used is preferably 0.5 to 50 parts by weight, more preferably 1 to 40 parts by weight, based on 100 parts by weight of the resin type dispersant (B).
The binder resin (C) preferably has a transmittance of 80% or more, more preferably 95% or more, in the entire wavelength range of 400 to 700 nm. This does not deteriorate the color tone of the coloring agent used.
The binder resin (C) can be classified into thermoplastic resin, thermosetting resin, and active energy ray-curable resin according to its main curing method. The active energy ray-curable resin is a resin obtained by imparting active energy ray-curable properties to a thermoplastic resin or a thermosetting resin. Further, the binder resin (C) is preferably an alkali-soluble resin having developability. Alkali-solubility is for imparting development solubility in the alkali development step in producing a color filter, and an acidic group is required. In this specification, the binder resin (C) is preferably an active energy ray-curable alkali-soluble resin.

Binder resin can be used individually or in combination of 2 or more types.

The content of the binder resin is preferably 20 to 400 parts by mass, more preferably 50 to 250 parts by mass, with respect to 100 parts by mass of the colorant. When contained in an appropriate amount, a film can be easily formed, and good color characteristics can be easily obtained.

<Thermoplastic resin>
Thermoplastic resins include, for example, acrylic resins, butyral resins, styrene-maleic acid copolymers, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, polyvinyl acetate, polyurethane resins, Examples include polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins.
The alkali-soluble resin is preferably a thermoplastic resin having an acidic group. Examples of acidic groups include carboxyl groups and sulfone groups. The alkali-soluble 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 having acidic groups are preferred in terms of developability, heat resistance and transparency, and acrylic resins having acidic groups are more preferred.

<Alkali-soluble resin>
The alkali-soluble resin imparts developing solubility to the coating film formed from the photosensitive coloring composition when the color filter is produced by photolithography.

The mass average molecular weight (Mw) of the alkali-soluble resin is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, even more preferably 4,000 to 20,000. Moreover, the value of Mw/Mn is preferably 10 or less. An appropriate Mw further improves the solubility in alkali development.
The acid value of the alkali-soluble resin is preferably 50-200 mgKOH/g, more preferably 70-180, even more preferably 90-170. If it has a moderate acid value, the alkali developability is further improved.

<Active energy ray-curable alkali-soluble resin>
The active energy ray-curable alkali-soluble resin preferably has an ethylenically unsaturated group. Ethylenically unsaturated groups can be introduced, for example, by the following methods (i) and (ii). When the active energy ray-curable alkali-soluble resin is used, the film is three-dimensionally crosslinked, thereby increasing the crosslink density and improving chemical resistance.

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

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

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

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

A monomer and a polybasic acid anhydride can be used individually or in combination of 2 or more types, respectively.

As a method similar to method (i), for example, a carboxyl group-containing monomer and other monomers are synthesized to produce a polymer. Next, there is a method of adding an epoxy group-containing monomer to a part of the carboxyl groups of the polymer to obtain an alkali-soluble resin.

[Method (ii)]
In method (ii), for example, a hydroxyl group-containing monomer, a carboxyl group-containing monomer, and other monomers are polymerized to produce a polymer. Next, a method of reacting the hydroxyl group of the polymer with the isocyanate group of the isocyanate group-containing monomer can be mentioned. Other monomers include, for example, other monomers already exemplified, maleimide, and phosphate ester group-containing monomers. Examples of the hydroxyl group-containing monomer and the carboxyl group-containing monomer include the monomers already exemplified.

Maleimides are, 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-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl- N-substituted maleimides such as 6-maleimidohexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, 9-maleimidoacridine, and the like.

The phosphate group-containing monomer is, for example, a monomer obtained by reacting an acid group of a hydroxyl group-containing monomer with a phosphate esterifying agent such as phosphorus pentoxide or polyphosphoric acid.

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

<Alkali-soluble resin not having active energy ray curability>
For the coloring composition, an active energy ray-curable alkali-soluble resin and an active energy ray-curable alkali-soluble resin can be used in combination in order to adjust the degree of curing of the film.

<Thermosetting compound>
When a thermoplastic resin is used as the binder resin, the coloring composition preferably uses a thermosetting compound in combination. As a result, when a color filter is produced, the heat resistance is improved because the crosslinking density is improved in the heating step after the film is patterned by photolithography. In addition, since the colorant (A) is less likely to aggregate in the heating step, the contrast ratio is further improved.

A thermosetting compound is a low-molecular-weight compound or polymer (thermosetting resin) and is not limited by molecular weight.
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.

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

The content of the epoxy compound is preferably 0.5 to 300 parts by mass, more preferably 1.0 to 50 parts by mass, based on 100 parts by mass of the colorant (A). When blended in an appropriate amount, the heat resistance and pattern shape of the film are further improved.

(oxetane compound)
An oxetane compound is a compound having an oxetane group. Examples of the oxetane compound include monofunctional oxetane compounds, bifunctional oxetane compounds, and trifunctional or higher oxetane compounds.

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

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

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

The content of the oxetane compound is preferably 0.5 to 50 parts by mass, more preferably 1 to 40 parts by mass. If it is contained in an appropriate amount, the solvent resistance of the film will be further improved.

(melamine compound)
A melamine compound is a compound having a melamine ring structure. Melamine compounds include low-molecular-weight compounds and high-molecular-weight compounds. The melamine compound used herein is preferably a compound in which a methylol group or an ether group is bonded to a melamine ring. The average number of bonds of methylol groups and/or ether groups per melamine ring is preferably 5.0 or more. If it has an appropriate number of bonds, the solvent resistance of the film is further improved, and the contrast ratio is less likely to decrease.

(curing agent)
A curing agent may be included herein to aid in curing the thermosetting compound. Curing agents include, for example, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like.
Amine compounds include (for example, dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine amines, etc.), quaternary ammonium salt compounds (e.g., triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (e.g., dimethylamine, etc.), imidazole derivatives bicyclic amidine compounds and their salts (e.g., imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, etc. ), phosphorus compounds (e.g., triphenylphosphine, etc.), S-triazine derivatives (e.g., 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine/isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine/isocyanuric acid adduct, etc.).

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

The photosensitive coloring composition of the specification preferably contains a coloring composition, a polymerizable compound (D), and a photopolymerization initiator (E).

<Polymerizable compound (D)>
The polymerizable compound (D) includes monomers and oligomers that form a transparent resin by curing with ultraviolet light, heat, or the like.

Polymerizable compound (D), for example, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (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 , phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethyleneglycol (meth)acrylate, trimethylolpropane PO-modified tri(meth)acrylate, trimethylolpropane EO-modified tri(meth)acrylate, isocyanuric acid EO-modified di(meth)acrylate , isocyanuric acid EO-modified tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,6-hexanediol diglycidyl ether di(meth)acrylate , bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodecanyl (meth) acrylate , Methylolated melamine (meth)acrylic acid esters, epoxy (meth)acrylates, various acrylic acid esters and methacrylic acid esters such as urethane acrylate, (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.

These commercially available products are KAYARAD R-128H, R526, PEG400DA, MAND, NPGDA, R-167, HX-220, R-551, R712, R-604, R-684, GPO-303 manufactured by Nippon Kayaku Co., Ltd. , TMPTA, DPHA, DPEA-12, DPHA-2C, D-310, D-330, DPCA-20, DPCA-30, DPCA-60, DPCA-120, and Aronix M-303, M- 305, M-306, M-309, M-310, M-321, M-325, M-350, M-360, M-313, M-315, M-400, M-402, M-403, M-404, M-405, M-406, M-450, M-452, M-408, M-211B, M-101A, Viscoat #310HP, #335HP, #700, #295 manufactured by Osaka Organic Co., Ltd., #330, #360, #GPT, #400, #405, NK Ester A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., and the like.

(Polymerizable compound having acid group)
The polymerizable compound (D) can contain a polymerizable compound having an acid group. Examples of acid groups include sulfonic acid groups, carboxyl groups, and phosphoric acid groups.

Polymerizable compounds having an acid group include, for example, esters of free hydroxyl group-containing poly(meth)acrylates of polyhydric alcohol and (meth)acrylic acid, and dicarboxylic acids; Examples include esterified products with meth)acrylates. Specific examples include monohydroxyoligoacrylates or monohydroxyoligomethacrylates such as trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate. and free carboxyl group-containing monoesters with dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, and phthalic acid; propane-1,2,3-tricarboxylic acid (tricarballylic acid), butane-1,2,4 - Tricarboxylic acids such as tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid, 2-hydroxyethyl acrylate, 2- Monohydroxy monoacrylates such as hydroxyethyl methacrylate, 2-hydroxypropyl acrylate and 2-hydroxypropyl methacrylate, or free carboxyl group-containing oligoesters with monohydroxy monomethacrylates, and the like can be mentioned.

Commercially available products thereof include Viscoat #2500P manufactured by Osaka Organic Co., Ltd., and Aronix M-5300, M-5400, M-5700, M-510, M-520 manufactured by Toagosei Co., Ltd., and the like.

(Polymerizable compound having urethane bond)
The polymerizable compound (D) can contain a polymerizable compound having an ethylenically unsaturated group and a urethane bond. The polymerizable compound is, for example, a polyfunctional urethane acrylate obtained by reacting a (meth)acrylate having a hydroxyl group with a polyfunctional isocyanate, or reacting a polyfunctional isocyanate with an alcohol and further reacting a (meth)acrylate having a hydroxyl group. and polyfunctional urethane acrylates obtained by

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

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

A polymerizable compound can be used individually or in combination of 2 or more types.

The amount of the polymerizable compound (D) is 1 to 1 in the non-volatile content of 100% by mass of the photosensitive coloring composition
50% by mass is preferred, and 2 to 40 parts by mass is more preferred. 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.

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

(Oxime ester compound)
In oxime ester-based compounds, absorption of ultraviolet rays 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 concentration of the coloring agent in the photosensitive coloring composition is high, the ultraviolet transmittance of the film may be low and the degree of curing of the film may be low.

Oxime ester compounds, for example, JP-A-2007-210991, JP-A-2009-179619, JP-A-2010-037223, JP-A-2010-215575, JP-A-2011-020998, etc. and an oxime ester photopolymerization initiator.

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 contained in an appropriate amount, the photocurability and developability are further improved.

<Sensitizer (H)>
The photosensitive coloring composition can further 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, and 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, acyl 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. Specifically, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4′-bis( dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, 3,6-dibenzoyl-N - Ethylcarbazole and the like are 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, based on 100 parts by mass of the photopolymerization initiator. When contained in an appropriate amount, curability and developability are further improved.

<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 light irradiation, thereby 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 the tapered shape of the cross section of the film after development are improved, and wrinkles are less likely to occur on the surface of the film.

<Polymerization inhibitor>
The photosensitive coloring composition can contain a polymerization inhibitor. As a result, exposure by diffracted light from the mask is suppressed during exposure by photolithography, making it easier to obtain a good pattern 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 parts by mass based on 100% by mass of the non-volatile content of the photosensitive coloring composition. 0.01 to 0.4 parts by mass is preferred. When contained in an appropriate amount, it is possible to suppress the linearity of the cross section of the film after development and wrinkles on the surface.

<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.

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

Moreover, the total content of the photopolymerization initiator and the ultraviolet absorber is preferably 1 to 20% by mass based on 100% by mass of the non-volatile matter 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.

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.

Ultraviolet absorbers can be used alone or in combination of two or more.

I supplemented it.
The content of the ultraviolet absorber is preferably 5 to 70% by weight based on the total 100% by weight of the photopolymerization initiator and the ultraviolet absorber. A good pattern shape can be easily obtained when it is contained in an appropriate amount. In addition, suppose that content of a sensitizer is included in content of a photoinitiator when a photosensitive coloring composition contains a sensitizer.

Moreover, the total content of the photopolymerization initiator and the ultraviolet absorber is preferably 1 to 20% by mass based on 100% by mass of the non-volatile matter of the photosensitive coloring composition. When contained in an appropriate amount, the adhesion of the film to the substrate is further improved, making it easier to obtain good sensitivity.

<Antioxidant (L)>
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. . In particular, when the colorant concentration of 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, hindered amine-based, phosphorus-based, sulfur-based, and hydroxylamine-based compounds. Among these, hindered phenol-based compounds, hindered amine-based compounds, phosphorus-based compounds, and sulfur-based compounds are preferred from the viewpoint of achieving both transmittance and sensitivity of the coating. In this specification, the antioxidant is preferably a compound containing no halogen atom.

Hindered phenol compounds include, for example, 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H ,5H)-trione, 1,1,3-tris-(2′-methyl-4′-hydroxy-5′-t-butylphenyl)-butane, 4,4′-butylidene-bis-(2-t- butyl-5-methylphenol), 3-(3,5-di-t-butyl-4-hydroxyphenyl)stearylpropionate, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxy phenyl)propionate, 3,9-bis[2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl]-2,4,8,10 -tetraoxaspiro[5.5]undecane, 1,3,5-tris(3,5-di-t-butyl-4-hydroxyphenylmethyl)-2,4,6-trimethylbenzene, 1,3,5 -tris(3-hydroxy-4-t-butyl-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2,2′-methylenebis (6-t-butyl-4-ethylphenol), 2,2′ thiodiethylbis-(3,5-di-t-butyl-4-hydroxyphenyl)-propionate, N,N-hexamethylenebis(3, 5-di-t-butyl-4-hydroxy-hydrocinnamamide), i-octyl 3-(3,5-di-t-butyl-4-hydroxyphenyl) propionate, 4,6-bis(dodecylthiomethyl )-o-cresol, calcium salt of 3,5-di-t-butyl-4-hydroxybenzylphosphonic acid monoethyl ester, 4,6-bis(octylthiomethyl)-o-cresol, bis[3-(3 -methyl-4-hydroxy-5-t-butylphenyl)propionic acid]ethylenebisoxybisethylene, 1,6-hexanediol bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate , 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, 2,2′-thio-bis-(6 -t-butyl-4-methylphenol), 2,5-di-t-amyl-hydroquinone, 2,6-di-t-butyl-4-nonylphenol, 2,2′-isobutylidene-bis-(4,6 -dimethyl-phenol), 2,2′-methylene-bis-(6-(1-methyl-cyclohexyl)-p-cresol), 2,4-dimethyl-6-(1-methyl-cyclohexyl)-phenol, etc. mentioned.

Hindered amine compounds include, for example, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, tetrakis(2,2,6,6-tetramethyl -4-piperidyl) 1,2,3,4-butane tetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl) -4-piperidyl) sebacate, bis(1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 2, 2,6,6-tetramethyl-4-piperidyl methacrylate, a polycondensate of dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine, poly[ [6-[(1,1,3,3-tetramethylbutyl)amino]-s-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidyl)imino] -hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imino]], 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol and 3,5,5 -ester of trimethylhexanoic acid, N,N'-4,7-tetrakis[4,6-bis{N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino}- 1,3,5-triazin-2-yl]-4,7-diazadecane-1,10-diamine, bis(2,2,6,6-tetramethyl-1-(octyloxy)-4-decanedioate piperidinyl) ester, reaction product of 1,1-dimethylethyl hydroperoxide and octane, bis(1,2,2,6,6-pentamethyl-4-pyliperidyl)[[3,5-bis(1,1 dimethylethyl )-4-hydroxyphenyl]methyl]butylmalonate methyl 1,2,2,6,6-pentamethyl-4-pyriperidyl sebacate, poly[[6-morpholino-s-triazine-2,4-diyl] -[(2,2,6,6-tetramethyl-4-piperidyl)imino]-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imino]], 2,2,6 ,6-tetramethyl-4-piperidyl-C12-21 and C18 unsaturated fatty acid esters, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,6-hexamethylenediamine , 2-methyl-2-(2,2,6,6-tetramethyl-4-piperidyl)amino-N-(2,2,6,6-tetramethyl-4-piperidyl)propionamide and the like.

Phosphorus compounds include, for example, di(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite, distearylpentaerythritol diphosphite, 2,2′-methylenebis(4,6-di -t-butylphenyl)2-ethylhexylphosphite, tris(2,4-di-t-butylphenyl)phosphite, tris(nonylphenyl)phosphite, tetra(C12-C15alkyl)-4,4'-isopropyl redene diphenyl diphosphite, diphenyl mono(2-ethylhexyl) phosphite, diphenyl isodecyl phosphite, tris(isodecyl) phosphite, triphenyl phosphite, tetrakis(2,4-di-t-butylphenyl)-4, 4-biphenyldiphosphonate, tris(tridecyl)phosphite, phenylisooctylphosphite, phenylisodecylphosphite, phenyldi(tridecyl)phosphite, diphenylisooctylphosphite, diphenyltridecylphosphite, 4,4' isopropyl Redenediphenol alkyl phosphite, trisnonylphenyl phosphite, trisdinonylphenyl phosphite, tris(biphenyl)phosphite, di(2,4-di-t-butylphenyl)pentaerythritol diphosphite, di(nonylphenyl) ) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, tetratridecyl 4,4′-butylidenebis(3-methyl-6-t-butylphenol) diphosphite, hexatridecyl 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl)butane triphosphite, 3,5-di-t-butyl-4-hydroxybenzylphosphite diethyl ester, sodium bis(4-t-butylphenyl)phosphite Phyto, sodium-2,2-methylene-bis(4,6-di-t-butylphenyl)-phosphite, 1,3-bis(diphenoxyphosphonyloxy)-benzene, ethyl bis(2,4 -di-tert-butyl-6-methylphenyl) and the like.

Sulfur compounds include, for example, 2,2-bis{[3-(dodecylthio)-1-oxopropoxy]methyl}propane-1,3-diylbis[3-(dodecylthio)propionate], 3,3′-thiobis ditridecyl propionate, 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,4-bis[(octylthio)methyl]-o-cresol, 2,4-bis[(laurylthio)methyl]-o-cresol and the like.

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

The content of the antioxidant is 0.5 to 5.0% by mass in 100% by mass of the non-volatile content of the photosensitive coloring composition, and if it is contained in an appropriate amount, the sensitivity and the transmittance and spectral characteristics of the coating are further improved. .

<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, anionic surfactants, and the like.

Examples of silicone-based surfactants include chain polymers having siloxane bonds and modified siloxane polymers in which organic groups are introduced into side chains or terminals.

A fluorosurfactant is a compound having a fluorocarbon chain.

Nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyethylene myrister ether, polyoxyethylene octyldodecyl Ethers, polyoxyalkylene alkyl ethers, polyoxyphenylene distyrenated phenyl ethers, polyoxyethylene tribenzylphenyl ethers, polyoxyethylene polyoxypropylene glycols, polyoxyalkylene alkenyl ethers, polyoxyethylene nonylphenyl ethers, polyoxyethylene alkyls Ether phosphate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, sorbitan tristearate, sorbitan monooleate, sorbitan trioleate, sorbitan sesquioleate, polyoxyethylene sorbitan monolaurate Polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan triisostearate, polyoxyethylene sorbitate tetraoleate , glycerol monostearate, glycerol monooleate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol monooleate, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkylamine, alkylalkanol Amides, alkyl imidazolines and the like can be mentioned.

Examples of cationic surfactants include alkylamine salts, alkyl quaternary ammonium salts such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride and cetyltrimethylammonium chloride, and their ethylene oxide adducts.

Anionic surfactants include, for example, polyoxyethylene alkyl ether sulfates, sodium dodecylbenzenesulfonate, alkali salts of styrene-acrylic acid copolymers, sodium alkylnaphthalenesulfonates, sodium alkyldiphenylether disulfonates, and monoethanol lauryl sulfate. amine, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate, and the like.

Amphoteric surfactants include, for example, lauramidopropyl betaine, lauryl betaine, cocamidopropyl betaine, stearyl betaine, alkylbetaines such as alkyldimethylaminoacetic acid betaine, and alkylamine oxides such as lauryldimethylamine oxide.

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

The content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the non-volatile content of 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% by mass with respect to 100 parts by mass of the colorant.

<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.

<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.

Ester solvents include, for example, methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyric acid. Butyl, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, γ-butyrolactone and the like.

Ether solvents include, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl. Ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl Ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl-n-propyl ether, anisole, phenetol, methylanisole and the like.

Ether ester solvents include, for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3- ethyl ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate , ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate, dipropylene glycol diacetate and the like.

Ketone solvents are, for example, 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, and isophorone.

Examples of alcohol solvents include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, 1,3-butylene glycol, glycerin and the like.

Examples of aromatic hydrocarbon solvents include benzene, toluene, xylene and mesitylene.

Amide solvents include, for example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone 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.

<Method for producing a photosensitive coloring composition>
The photosensitive coloring composition is subjected to dispersion treatment using, for example, an organic pigment (A) and a resin-type dispersant (B) to prepare a pigment dispersion (also referred to as a coloring composition). The coloring composition can further contain a binder resin (C). A photosensitive coloring composition can be prepared by mixing a coloring composition with a polymerizable compound (D) and a photopolymerization initiator (E). Incidentally, the binder resin may be blended when producing the photosensitive coloring composition.

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.

<Dispersed particle size of pigment>
The average dispersed particle size of the pigment in the coloring composition or photosensitive coloring composition is preferably 30 to 200 nm, more preferably 40 to 120 nm. Within this range, the coloring composition tends to have an appropriate viscosity, and the dispersion stability is further improved. Moreover, the photosensitive coloring composition has high sensitivity and can increase the development speed. Therefore, it is easy to produce a high-quality color filter.

For the average dispersed particle diameter, Nikkiso Co., Ltd.'s Microtrac UPA-EX150 that employs the dynamic light scattering method (FFT power spectrum method) is used, the particle permeability is the absorption mode, the particle shape is aspherical, and D50 is the average diameter. can be measured as As the diluting solvent for measurement, the solvent used for preparing the pigment dispersion is used. Further, it is preferable to measure a sample that has been treated with ultrasonic waves in advance, immediately after sample preparation, because it is easy to obtain results with little variation.

<Removal of coarse particles>
The photosensitive coloring composition is preferably dispersed in beads using zirconium oxide, inorganic glass, or the like in the manufacturing process. Bead dispersion can use beads of different diameters. In addition, after dispersing the beads, by centrifugation at a gravitational acceleration of 3000 to 25000 G, sintered filter, membrane filter, etc., coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more, and mixed It is preferable to remove the dust that has accumulated.

The photosensitive coloring composition is preferably prepared as a solvent-developable or alkali-developable photosensitive coloring composition. These photosensitive coloring compositions are mixed with a coloring composition, a photopolymerizable monomer and/or a photopolymerization initiator, if necessary, a solvent, other dispersing aids, and additives. can be adjusted. The photopolymerization initiator may be added at the stage of preparing the colored composition, or may be added later to the prepared colored composition.

<Color filter>
The color filter of the specification preferably comprises a filter segment formed from a photosensitive coloring composition, and more preferably comprises a substrate (also referred to as a transparent substrate).
The color filter segment (hereinafter also referred to as filter segment) preferably has a red filter segment, a green filter segment, and a blue filter segment by appropriately selecting the type of coloring agent used. Moreover, the color filter can have a magenta color filter segment, a cyan color filter segment, and a yellow color filter segment separately as color filter segments. A reflective substrate can be used instead of the transparent substrate. Examples of the transparent substrate include a glass substrate. Examples of the reflective substrate include a substrate using an aluminum electrode or a metal thin film as a reflective surface. The color filter of this specification preferably contains a green filter segment formed from a photosensitive coloring composition containing an organic pigment (A).

<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.

Filter segments can be formed by, for example, a printing method, an electrodeposition method, a transfer method, an inkjet method, a photolithography method, or the like.
In the printing method, a pattern can be formed only by repeating printing and drying of a photosensitive coloring composition prepared as a printing ink, and therefore, as a method for producing a color filter, it is low cost and excellent in mass productivity. Furthermore, the development of printing technology has made it possible to print fine patterns with high dimensional accuracy and smoothness. For printing, it is preferable to have a composition that does not allow the ink to dry or solidify on the printing plate or blanket. In addition, it is also important to control the fluidity of the ink on the printing press, and it is also possible to adjust the viscosity of the ink using a dispersant or an extender.

In the electrodeposition method, a transparent conductive film formed on a transparent substrate is used to fabricate a color filter by electrodepositing filter segments of each color on the transparent conductive film by electrophoresis of colloidal particles. In the transfer method, filter segments are formed on the release-treated surface of the release sheet. Next, this filter segment is transferred to a transparent substrate to produce.

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. The photolithography method is preferable because a color filter with higher precision can be produced than the printing method.

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 attached to 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 added. A color liquid crystal display device is manufactured by laminating it to the outside of the substrate. 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.

<Solid-state image sensor>
The solid-state imaging device of this specification includes at least color filters.
The solid-state imaging device has, for example, a plurality of photodiodes forming a light receiving area of the solid-state imaging device (CCD sensor, CMOS sensor, organic CMOS sensor, etc.) and transfer electrodes made of polysilicon or the like on a substrate. A device comprising a light shielding film made of tungsten or the like with only the light receiving portion of the photodiode being opened on the diode and the transfer electrode, and made of silicon nitride or the like formed on the light shielding film so as to cover the entire surface of the light shielding film and the light receiving portion of the photodiode. It has a protective film, and has the color filter for a solid-state imaging device of the present invention on the device protective film.
Furthermore, a configuration having a condensing means (for example, a microlens or the like; the same shall apply hereinafter) above the device protective layer and below the color filter (on the side close to the substrate), or a configuration having a condensing means above the color filter, etc. may be
The organic CMOS sensor includes a thin panchromatic photosensitive organic photoelectric conversion film as a photoelectric conversion layer and a CMOS signal readout substrate. It is a two-layered hybrid structure in which an inorganic material plays a role of extracting a signal to the outside, and in principle, an aperture ratio can be made 100% for incident light. Since the organic photoelectric conversion film is a structure-free continuous film and can be laid on a CMOS signal readout substrate, it does not require an expensive microfabrication process and is suitable for miniaturization of filter segments.
Arrangement of the color filter segments is not particularly limited, and a known method can be used.

<Liquid crystal display device>
The liquid crystal display device of this specification includes a color filter.
A liquid crystal display device comprises the color filter of the present invention and a light source. Examples of the light source include a cold cathode fluorescent lamp (CCFL) and a white LED. In the present invention, 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. FIG. 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). On the inner surface of the first transparent substrate 11,
A TFT (thin film transistor) array 12 is formed, and a transparent electrode layer 13 made of, for example, ITO is formed thereon. An alignment layer 14 is provided on the transparent electrode layer 13 . 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 .

The white LED light source includes, for example, a blue LED with a fluorescent filter formed on its surface, and a blue LED resin package containing a phosphor. (λ3), a wavelength (λ4) at which the emission intensity is maximum within the range of 530 nm to 580 nm, and a wavelength (λ5) at which the emission intensity is maximum within the range of 600 nm to 650 nm, and The ratio (I4/I3) of the emission intensity I3 at the wavelength λ3 to the emission intensity I4 at the wavelength λ4 is 0.2 or more and 0.4 or less, and the ratio (I5/ A white LED light source (LED1) having a spectral characteristic in which I3) is 0.1 or more and 1.3 or less, or a wavelength (λ1) at which the emission intensity is maximized in the range of 430 nm to 485 nm, and 530 nm to 580 nm. A spectrum having a second emission intensity peak wavelength (λ2) within the range, and having a ratio (I2/I1) between the emission intensity I1 at the wavelength λ1 and the emission intensity I2 at the wavelength λ2 of 0.2 or more and 0.7 or less A white LED light source (LED2) with properties is preferred.

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

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

The following examples illustrate the invention. "Parts" and "%" in the examples represent "mass parts" and "mass%", respectively. It goes without saying that the present invention is not limited to the examples.

First, each measuring method will be described.

(Average molecular weight of resin)
The number average molecular weight (Mn) and weight average molecular weight (Mw) were measured by gel permeation chromatography (GPC) equipped with an RI detector. HLC-8220GPC (manufactured by Tosoh Corporation) was used as the apparatus, two separation columns were connected in series, and "TSK-GEL SUPER HZM-N" was used as both packing materials, and the oven temperature was 40 ° C. , 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 (mgKOH/g))
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.

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

<Production of micronized phthalocyanine pigment>
(Micronized phthalocyanine pigments A-1 to 5)
Micronized phthalocyanine pigments (A-1) to (A-5) represented by the following chemical formulas (51) to (55) were produced according to the examples of JP-A-2017-111398.

(Micronized phthalocyanine pigment (A-6))
phthalocyanine pigment C.I. I. Pigment Green 58 ("FASTGEN" manufactured by DIC)
GREEN A110"), 1200 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 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. 97 parts of zinc oxide phthalocyanine pigment (A-6) were obtained.

(Micronized phthalocyanine pigment (A-7))
The finely divided phthalocyanine pigment (A-1) and the finely divided phthalocyanine pigment (A-6) were mixed in equal amounts to prepare a finely divided phthalocyanine pigment (A-7).

(Micronized phthalocyanine pigment (A-8))
phthalocyanine pigment C.I. I. Pigment Green 36 200 parts, sodium chloride 1
400 parts and 360 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80° C. for 6 hours. Next, this kneaded product is put into 8 liters of hot water, stirred for 2 hours while heating to 80° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85° C. for a day and night. , 190 parts of finely divided copper phthalocyanine pigment (A-8) were obtained.

(Micronized phthalocyanine 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 74 parts of bromine. After raising the temperature to 130° C. over 40 hours, taking out into water and filtering, a crude green pigment was obtained. 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 pulverized to obtain a finely divided phthalocyanine pigment (A-9). The finely divided phthalocyanine pigment (A-9) thus obtained had an average number of halogen atoms per molecule of 13.97, of which an average number of bromine atoms was 11.46, according to a fluorescent X-ray analysis using ZSX100E manufactured by Rigaku Corporation. It was a halogenated zinc phthalocyanine pigment having an average number of chlorine atoms of 2.51.

(Micronized phthalocyanine pigment (A-10))
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 filtered to obtain a crude green pigment. 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 pulverized to obtain a finely divided phthalocyanine pigment (A-10). The finely divided phthalocyanine pigment (A-10) thus obtained had an average number of halogen atoms per molecule of 12.71, of which an average number of bromine atoms of 10.22 and a number of chlorine atoms per molecule was determined by X-ray fluorescence analysis. was 2.49 on average.

(Micronized phthalocyanine pigment (A-11))
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. After raising the temperature to 130° C. over 40 hours, taking out into water and filtering, a crude green pigment was obtained. 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 pulverized to obtain a finely divided phthalocyanine pigment (A-11). The finely divided phthalocyanine pigment (A-11) 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 9.00, according to fluorescent X-ray analysis. was 2.98 on average.

(Micronized phthalocyanine pigment (A-12))
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 filtered to obtain a crude green pigment. 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 pulverized to obtain a finely divided phthalocyanine pigment (A-12). The finely divided phthalocyanine pigment (A-12) thus obtained had an average number of halogen atoms per molecule of 12.69, of which an average number of 8.54 bromine atoms and an average number of chlorine atoms per molecule was determined by X-ray fluorescence analysis. was a halogenated zinc phthalocyanine pigment with an average of 4.16.

(Micronized phthalocyanine pigment (A-13))
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. After raising the temperature to 130° C. over 40 hours, taking out into water and filtering, a crude green pigment was obtained. 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 pulverized to obtain a finely divided phthalocyanine pigment (A-13). The finely divided phthalocyanine pigment (A-13) thus obtained had an average number of halogen atoms per molecule of 8.88, of which an average number of bromine atoms of 6.90 and a number of chlorine atoms per molecule was determined by fluorescent X-ray analysis. was a halogenated zinc phthalocyanine pigment with an average of 1.98.

<Production of fine yellow pigment>
(Finely divided yellow pigments (a-1) to (a to 3))
Finely divided phthalocyanine pigments (a-1) to (a-3) of quinophthalone pigments represented by the following chemical formulas (56) to (58) were prepared according to the examples of JP-A-2012-226110. Its structure is shown below.

(Micronized yellow pigment (a-4))
C. I. Pigment Yellow 138 (PY138) (BASF "Pariotol Yellow K0960-HD") 100 parts, sodium chloride 700 parts, and diethylene glycol 180 parts are charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and heated at 80 ° C. for 6 hours. Kneaded. This mixture was poured into 2000 parts of hot water and stirred for 1 hour while heating to 80°C to form a slurry, which was repeatedly filtered and washed with water to remove salt and solvent. A yellow pigment (a-4) was obtained.

(Micronized yellow pigment (a-5))
isoindoline yellow pigment C.I. I. 100 parts of pigment yellow 139 (“Irgafor Yellow 2R-CF” manufactured by Ciba 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 yellow pigment (a-5).

(Micronized yellow pigment (a-6))
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 was put into 3 liters of hot water, and stirred with a high-speed mixer for about 1 hour while heating to about 80° C. to form a slurry.
Filtration and washing with water were repeated to remove sodium chloride and the solvent, followed by drying at 80° C. for one day to obtain a finely divided yellow pigment (a-6).

(Micronized yellow pigment (a-7))
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 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, and then dried at 80°C for a day and night. , to obtain a finely divided yellow pigment (a-7).

(Micronized yellow pigment (a-8))
C. I. Pigment Yellow 185 (BASF "Pariogen Yellow D1155") 95 parts, dye derivative b-2, 5 parts, rosin maleic acid resin (manufactured by Arakawa Chemical Industries, Ltd. "Marquedo 32") 10 parts, sodium chloride 1200 parts, and 120 parts of diethylene glycol was charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60° C. for 8 hours. Next, this kneaded product is put into 8000 parts of warm water and stirred for 1 hour while heating to about 70°C to form a slurry, which is 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 105 parts of yellow fine pigment (a-8).

<Dye derivative (b)>
The following dye derivatives were used.

<Resin dispersant (B1) having an aromatic carboxylic acid structure and a (meth)acryloyl group>
(Production of resin type dispersant (B1-1) solution)
3-Mercapto-
108 parts of 1,2-propanediol, 174 parts of pyromellitic dianhydride, 650 parts of propylene glycol monomethyl ether acetate, and 0.1 part of monobutyl tin oxide as a catalyst.
After preparing 2 parts and replacing with nitrogen gas, it was made to react at 120 degreeC for 5 hours (1st process). It was confirmed by acid value measurement that 95% or more of the acid anhydride groups were half-esterified. Next, 160 parts of the compound obtained in the first step in terms of non-volatile content, 200 parts of 2-hydroxypropyl methacrylate, 200 parts of ethyl acrylate, 150 parts of t-butyl acrylate, 200 parts of 2-methoxyethyl acrylate, 200 parts of methyl methacrylate 50 parts of methacrylic acid and 663 parts of propylene glycol monomethyl ether acetate were charged, the inside of the reaction vessel was heated to 80° C., and 1.2 parts of 2,2′-azobis(2,4-dimethylvaleronitrile) was added. , reacted for 12 hours (second step). It was confirmed by measuring the non-volatile content that 95% had reacted. Finally, 500 parts of a 50% propylene glycol monomethyl ether acetate solution of the compound obtained in the second step, 27.0 parts of 2-methacryloyloxyethyl isocyanate (MOI), and 0.1 part of hydroquinone were charged, and the isocyanate was measured by IR. The reaction was carried out until the disappearance of the peak at 2270 cm −1 based on the group was confirmed (third step). After confirming the disappearance of the peak, the reaction solution was cooled and the non-volatile content was adjusted with propylene glycol monomethyl ether acetate to obtain a resin-type dispersant (B1-1) solution having a non-volatile content of 30%. The resulting dispersant had an acid value of 68, an unsaturated double bond equivalent of 1,593, and a weight average molecular weight of 13,000.

(Production of resin type dispersant (B1-2) to (B1-10) solution)
Synthesis was carried out in the same manner as the production of the resin type dispersant (B1-1) except that the raw materials and charging amounts shown in Table 1 were used, and the resin type dispersants (B1-2) to (B1) having a nonvolatile content of 30% -10) was obtained.

Abbreviations in the table are as follows.
1,6-HD: 1,6-hexanediol PMA: pyromellitic dianhydride BTA: 1,2,3,4-butanetetracarboxylic dianhydride BPDA: 3,3',4,4'-biphenyl Tricarboxylic anhydride TMEG: ethylene glycol dianhydride trimellitate (manufactured by Shin Nippon Rika Co., Ltd.: Rikashid TMEG-100)
BTDA: 3,3',4,4'-benzophenonetetracarboxylic dianhydride DSDA: 3,3',4,4'-biphenylsulfonetetracarboxylic dianhydride BPAF: 9,9-bis(3,4 -Dicarboxyphenyl)fluorene dianhydride T
MA: trimellitic anhydride HEMA: 2-hydroxyethyl methacrylate 2HPMA: 2-hydroxypropyl methacrylate 4HBA: 2-hydroxybutyl acrylate FM-3: terminal hydroxyl group polycaprolactone-modified methacrylate (manufactured by Daicel Chemical Industries: Plaxel FM-3)
EA: ethyl acrylate t-BA: t-butyl acrylate 2MTA: 2-methoxyethyl acrylate MMA: methyl methacrylate BMA: n-butyl methacrylate BzMA: benzyl methacrylate St: styrene MAA: methacrylic acid MOI: 2-methacryloyloxyethyl isocyanate (Showa Denkosha: Karenz MOI)
AOI: 2-acryloyloxyethyl isocyanate (manufactured by Showa Denko: Karenz AOI)
BEI: 1,1-bis(acryloyloxymethyl)ethyl isocyanate (manufactured by Showa Denko: Karenz BEI)
MOI-EG: 2-methacryloyloxyethoxyethyl isocyanate (manufactured by Showa Denko: Karenz MOI-EG)

<Production of resin-type dispersant (B2) solution having aromatic carboxylic acid structure and vinyl polymer moiety having no (meth)acryloyl group>
(Production of resin type dispersant (B2-1) solution)
10 parts of methacrylic acid, 20 parts of methyl methacrylate, 90 parts of 2-methoxyethyl methacrylate, 40 parts of t-butyl methacrylate, 20 parts of n-butyl acrylate, tert- 20 parts of butyl acrylate and 50 parts of propylene glycol monomethyl ether acetate were charged, and the atmosphere was purged with nitrogen gas. 12 parts of 3-mercapto-1,2-propanediol was added while heating the inside of the reaction vessel to 50° C. and stirring. The temperature was raised to 90° C., and the mixture was reacted for 7 hours while adding a solution obtained by adding 0.1 part of 2,2′-azobisisobutyronitrile to 90 parts of propylene glycol monomethyl ether acetate. It was confirmed by measuring the non-volatile content that 95% of the monomer reacted.
Then 35 parts of trimellitic anhydride, 50 parts of propylene glycol monomethyl ether acetate, 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. let me Confirm that 98% or more of the acid anhydride groups are half-esterified by measuring the acid value, terminate the reaction, add propylene glycol monomethyl ether acetate so that the nonvolatile content is 30% by measuring the nonvolatile content, and increase the acid value. A solution of a resin-type dispersant (B2-1) having a weight-average molecular weight of 8,500 at a vinyl polymer moiety of 62 mg KOH/g was obtained.

(Production of resin type dispersant (B2-2) ~ (B2-6) solution)
Synthesis was carried out in the same manner as the resin-type dispersant (B2-1) solution except that the raw materials and charging amounts shown in Table 2 were used, and resin-type dispersants (B2-2) to (B2-6) were prepared. Got each.

(Production of resin type dispersant (B2-7) 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 groups are 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 / A resin-type dispersant (B2-7) solution having a weight average molecular weight of 8,500 was obtained.

(Production of resin type dispersant (B2-8) solution)
80 parts of n-butyl acrylate, 60 parts of methyl methacrylate, 20 parts of methacrylic acid, 20 parts of Karenz MOI-BM (manufactured by Showa Denko), ETERNA COLLO XMA (Ube Kosan Co., Ltd.) and 100 parts of propylene glycol monomethyl ether acetate were charged and purged with nitrogen gas. The inside of the reaction vessel is heated to 80° C., and a solution of 0.1 part of 2,2′-azobisisobutyronitrile dissolved in 14 parts of 2-mercapto-2-methyl-1,3-propanediol is added. and reacted for 10 hours. It was confirmed by measuring the non-volatile content that 95% had reacted. Next, BPAF: 39 parts of 9,9-bis(3,4-dicarboxyphenyl)fluorene diacid anhydride (manufactured by JFE Chemical Co., Ltd.), C-1015N (bifunctional polycarbonate polyol, trade name Kuraray Polyol C-1015N ( Hydroxyl value 112 mgKOH/g, manufactured by Kuraray Co., Ltd.)) 106 parts, trimellitic anhydride 33 parts, cyclohexanone 392 parts, 1,8-diazabicyclo-[5.4.0]-7-undecene 0.40 parts as a catalyst was added and reacted at 100° C. for 7 hours. It was confirmed by acid value measurement that 98% or more of the acid anhydride groups were half-esterified, and the reaction was terminated. The nonvolatile content was adjusted to 30% with propylene glycol monomethyl ether acetate to obtain a resin type dispersant (B2-8) liquid having an acid value of 94 mgKOH/g and a weight average molecular weight of 25,000.

(Production of resin type dispersant (B2-9) solution)
3 parts of trimellitic anhydride, 1 part of 3-mercapto-1,2-propanediol, 50 parts of PGMAc, and 0.1 part of dimethylbenzylamine were placed in a reactor equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer. I prepared. After purging with nitrogen gas, the inside of the reaction vessel was heated to 120° C. and reacted for 4 hours, and then reacted at 80° C. for 2 hours. Further, 30 parts of tertiary butyl acrylate, 20 parts of ETERNACOLL OXMA ((3-ethyloxetane-3-yl)methyl methacrylate, manufactured by Ube Industries), 5 parts of methacrylic acid, 40 parts of ethyl acrylate, and 10 parts of PGMAc were charged, and the reaction vessel was While maintaining the inside at 80° C., 0.2 part of 2,2′-azobisisobutyronitrile was added in 15 portions every 30 minutes. A non-volatiles measurement was taken one hour after the final addition and confirmed that 95% of the monomer had reacted. PGMAc was added to dilute the nonvolatile content to 30% by nonvolatile measurement to obtain a resin type dispersant (B2-9) solution having an acid value per nonvolatile content of 51 mgKOH/g and a weight average molecular weight (Mw) of 24,000. rice field.

<Production of basic resin-type dispersant (B3) solution>
(Basic resin type dispersant (B3-1) solution)
40 parts of methyl methacrylate, 10 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine as a catalyst were charged into a reaction apparatus equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer. After stirring for 1 hour, the inside of the system was replaced with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate as an initiator, 5.6 parts of cuprous chloride as a catalyst, and 133 parts of PGMAc are charged, and the temperature is raised to 110° C. under a nitrogen stream to form the first block (B block). Polymerization started. After polymerization for 4 hours, the polymerization solution was sampled and the non-volatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more in terms of the non-volatile content. Next, 61 parts of PGMAc, 40 parts of dimethylaminoethyl methacrylate as a second block (A block) monomer, and 10 parts of methacryloyloxyethylbenzyldimethylammonium chloride were added to this reactor, and the temperature was maintained at 110° C. under a nitrogen atmosphere. Stir and continue the reaction. Two hours after the addition, the polymerization solution was sampled and the nonvolatile content was measured to confirm that the polymerization conversion rate of the second block (A block) was 98% or more in terms of the nonvolatile content, and the reaction solution was cooled to room temperature. Polymerization was stopped by cooling. As a result of GPC measurement, the polymer had a mass average molecular weight of 20,000, a molecular weight distribution Mw/Mn of 1.4, and a reaction conversion rate of 98.5%. Thus, a basic resin-type dispersant (B3-1) having an amine value per non-volatile content of 169.8 mgKOH/g was obtained. After cooling to room temperature, about 2 g of the resin-type dispersant solution was sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content. Propylene glycol monomethyl ether acetate (PGMAc) was added so that the content was 30% by mass to prepare a basic resin-type dispersant (B3-1) solution of ABA block polymer.

(Basic resin type dispersant (B3-2) solution)
133 parts of PGMAc was charged into a reactor equipped with a gas inlet pipe, a condenser, a stirring blade, and a thermometer, and the temperature was raised to 110° C. while replacing with nitrogen. 177 parts of diethylaminoethyl methacrylate, 3 parts of methyl acrylate, 20 parts of 2-hydroxyethyl methacrylate, 61 parts of PGMAc, and 6 parts of 2,2′-azobis(2,4-dimethylvaleronitrile) were charged into a dropping vessel until uniform. After stirring, the mixture was added dropwise to the reactor over 2 hours, and the reaction was continued at the same temperature for 3 hours. Thus, a basic resin dispersant (B3-2) having an amine value per non-volatile content of 345 mgKOH/g and a number average molecular weight (Mn) of 3,000 was obtained. A basic resin-type dispersant (B3-2) solution of random polymer was prepared by diluting in the same manner as the resin-type dispersant (B3-1) solution.

(Basic resin type dispersant (B3-3) solution)
133 parts of PGMAc was charged into a reactor equipped with a gas inlet pipe, a condenser, a stirring blade, and a thermometer, and the temperature was raised to 110° C. while replacing with nitrogen. 177 parts of 1,2,2,6,6-pentamethylpiperidyl methacrylate, 3 parts of methyl acrylate, 20 parts of 2-hydroxyethyl methacrylate, 61 parts of PGMAc, and 2,2′-azobis(2,4-dimethylvalero Nitrile) was charged in 6 parts, stirred until uniform, added dropwise to the reactor over 2 hours, and then the reaction was continued at the same temperature for 3 hours. Thus, a basic resin type dispersant (B3-3) having an amine value per non-volatile content of 201 mgKOH/g and a number average molecular weight of 3,800 (Mn) was obtained. A basic resin-type dispersant (B3-3) solution of random polymer was prepared by diluting in the same manner as the basic resin-type dispersant (B3-1) solution.

(Basic resin type dispersant (B3-4) solution)
A flask equipped with a condenser and a stirrer was charged with 1.0 parts by mass of AIBN and 186 parts by mass of propylene glycol monomethyl ether acetate, followed by 27 parts by mass of methyl methacrylate, 27 parts by mass of butyl methacrylate, 19 parts by mass of 2-ethylhexyl methacrylate, and benzyl methacrylate. 16 parts by mass, 16 parts by mass of triethylene glycol ethyl ether methacrylate, and 3.6 parts by mass of cumyldithiobenzoate were charged, and purged with nitrogen for 30 minutes. Thereafter, the temperature of the reaction solution was raised to 60° C. by gentle stirring, and this temperature was maintained for 24 hours to carry out living radical polymerization.
Next, to this reaction solution, a solution obtained by dissolving 1.0 parts by mass of AIBN and 54 parts by mass of dimethylaminoethyl methacrylate in 108 parts by mass of propylene glycol monomethyl ether acetate and performing nitrogen substitution for 30 minutes was added, and living at 60 ° C. for 24 hours. Radical polymerization was performed and then diluted in the same manner as the basic resin dispersant (B3-1) solution to prepare a random polymer basic resin dispersant (B3-4) solution.

(Basic resin type dispersant (B3-5) solution)
500 parts of methyl methacrylate, 22 parts of thioglycerol, and 511 parts of propylene glycol monomethyl ether acetate were introduced into a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser and a stirrer, and the contents were purged with nitrogen gas. The inside of the reaction vessel was heated to 90° C., and after adding 0.50 parts of AIBN, the reaction was carried out for 7 hours. After confirming that 95% of the nonvolatile matter had reacted, the solution was cooled to room temperature to obtain a 50% nonvolatile matter solution of a vinyl polymer having a weight average molecular weight of 5,200 and two free hydroxyl groups at one terminal region. Then, 90.4 parts of isophorone diisocyanate, 45.1 parts of propylene glycol monomethyl ether acetate, and 0.11 part of dibutyltin dilaurate as a catalyst were charged, and the atmosphere was purged with nitrogen gas. The inside of the reaction vessel was heated to 100° C., reacted for 3 hours, and then cooled to 40° C. to obtain a prepolymer solution having isocyanate groups. 22.2 parts of methyliminobispropylamine, 13.2 parts of dibutylamine, and 304.6 parts of propylene glycol monomethyl ether acetate were charged into a reaction vessel 2 equipped with a gas inlet tube, a thermometer, a condenser and a stirrer, and heated to 100°C. . The prepolymer solution was added dropwise thereto over a period of 30 minutes, and the reaction was continued for 1 hour, followed by cooling to room temperature to terminate the reaction. If necessary, part of the solvent is removed by distillation under reduced pressure, and then diluted in the same manner as the basic resin dispersant (B3-1) solution to obtain the basic resin dispersant (B3-5) solution. prepared.

(Basic resin type dispersant (B3-6) solution)
30 parts of methyl methacrylate, 30 parts of n-butyl methacrylate, 20 parts of hydroxyethyl methacrylate, and 13.2 parts of tetramethylethylenediamine were charged into a reaction apparatus equipped with a gas inlet tube, condenser, stirring blade, and thermometer, and nitrogen was flowed. While stirring at 50° C. for 1 hour, the inside of the system was replaced with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate, 5.6 parts of cuprous chloride, and 133 parts of PGMAc were charged, and the temperature was raised to 110° C. under a nitrogen stream to initiate polymerization of the first block (B block). After polymerization for 4 hours, the polymerization solution was sampled and the non-volatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more in terms of the non-volatile content.
Next, 61 parts of PGMAc and 20 parts of 1,2,2,6,6-pentamethylpiperidyl methacrylate (manufactured by Hitachi Chemical Co., Ltd., Fancryl FA-711MM) as a second block (A block) monomer were added to the reactor. The reaction was continued by stirring while maintaining the temperature at 110° C. under a nitrogen atmosphere. Two hours after the addition of 1,2,2,6,6-pentamethylpiperidyl methacrylate, the polymerization solution was sampled and the nonvolatile content was measured. % or more, the reaction solution was cooled to room temperature to terminate the polymerization.
Thus, a basic group resin-type dispersant (B3-6) having a piperidyl skeleton having an amine value per non-volatile content of 57 mgKOH/g and a number average molecular weight of 4,500 (Mn) was obtained.
Dilute in the same manner as the resin type dispersant (B3-1) solution to prepare a basic group resin type dispersant (B3-6) solution of ABA block polymer.

(Basic resin type dispersant (B3-7) solution)
[(3-(N,N-dimethylamino)propylacrylamide/methoxypolyethyleneglycol methacrylate copolymer (23/77 weight %) quaternized product; quaternization rate 27 mol%)], diluted in the same manner as the resin type dispersant (B3-1) solution, and a basic group resin type dispersant (B3-7) solution was prepared.

<Production example of binder resin (C)>
(Preparation of binder resin (C-1) liquid)
196 parts of cyclohexanone was charged into a reaction vessel equipped with a separable 4-necked flask, a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube and a stirring device, heated to 80°C, and after replacing the inside of the reaction vessel with nitrogen, dropwise. From the tube, 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, 20.7 parts of paracumylphenol ethylene oxide-modified acrylate ("Aronix M110" manufactured by Toagosei Co., Ltd.) , 2,2'-azobisisobutyronitrile 1.1 parts 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 non-volatile content. to prepare a binder resin (C-1) liquid. The weight average molecular weight (Mw) was 26,000.

(Preparation of binder resin (C-2) liquid)
207 parts of cyclohexanone was charged into a reaction vessel equipped with a separable 4-necked flask, a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube and a stirring device, heated to 80 ° C., the inside of the reaction vessel was replaced with nitrogen, and then dropped. From the tube, 20 parts of methacrylic acid, 20 parts of paracumylphenol ethylene oxide-modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 2,2'-azobis A mixture of 1.33 parts of isobutyronitrile was added dropwise over 2 hours. After completion of dropping, the reaction was continued for 3 hours to obtain a copolymer resin solution. Next, the nitrogen gas was stopped and the total amount of the copolymer solution obtained was stirred while injecting dry air for 1 hour, and then cooled to room temperature. A mixture of 6.5 parts of MOI, 0.08 parts of dibutyl tin laurate and 26 parts of cyclohexanone was added dropwise at 70° C. over 3 hours. After the dropwise addition was completed, the reaction was continued for an additional hour to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled and dried by heating at 180° C. for 20 minutes to measure the non-volatile content. to prepare a binder resin (C-2). The weight average molecular weight (Mw) was 18,000.

(Preparation of binder resin (C-3) liquid)
A separable 4-necked flask equipped with a thermometer, a condenser tube, 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, parachlorate was added from the dropping tube. Milphenol ethylene oxide-modified acrylate (Toagosei Aronix M110) 18 parts, benzyl methacrylate 10 parts, glycidyl methacrylate 18.2 parts, methyl methacrylate 25 parts, and 2,2'-azobisisobutyronitrile 2.0 The mixture of parts 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 9.3 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, 19.5 parts of tetrahydrophthalic anhydride (100 mol % of the generated hydroxyl groups) 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 non-volatile content. to prepare a binder resin (C-3) liquid. The weight average molecular weight (Mw) was 19,000.

(Preparation of binder resin (C-4) liquid)
A separable flask equipped with a cooling pipe was prepared as a reaction tank, and on the other hand, as a monomer dropping tank, dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate 40 parts, methacrylic acid 40 parts, methacrylic acid 120 parts of methyl, 4 parts of t-butylperoxy-2-ethylhexanoate (NOF "Perbutyl O"), and 40 parts of PGMAc are prepared by stirring well, and n-dodecane is used as a chain transfer agent dropping tank. A well-stirred mixture of 8 parts of thiol and 32 parts of PGMAc was prepared.
After charging 395 parts of PGMAc into a reaction vessel and purging with nitrogen, the temperature of the reaction vessel was raised to 90° C. by heating with an oil bath while stirring. After the temperature of the reactor was stabilized at 90°C, dropping was started from the monomer dropping tank and the chain transfer agent dropping tank. Each dropping was performed over 135 minutes while maintaining the temperature at 90°C. After 60 minutes from the end of dropping, the temperature of the reactor was raised to 110°C. After maintaining the temperature at 110° C. for 3 hours, a gas introduction tube was attached to the separable flask, and bubbling of a mixed gas of oxygen/nitrogen=5/95 (volume ratio) was started. Then, 70 parts of glycidyl methacrylate, 0.4 parts of 2,2′-methylenebis(4-methyl-6-t-butylphenol), and 0.8 parts of triethylamine were charged into the reactor, and reacted at 110° C. for 12 hours. . Then, add 150 parts of PGMAc and cool to room temperature, sample about 2 g of the resin solution, heat and dry at 180 ° C. for 20 minutes to measure the non-volatile content, and the non-volatile content of the previously synthesized resin solution becomes 20% by mass. A binder resin (C-4) liquid was obtained by adding PGMAc in the manner described above. The resin had a weight average molecular weight of 18,000 and an acid value of 2 mgKOH/g per nonvolatile matter.

<Method for producing colored composition (single color)>
[Example 1]
(Preparation of colored composition (R-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. Filtration through a 0 μm filter produced a coloring composition (R-1) having a pigment content of 80% and a nonvolatile content of 24.3% by mass.
Pigment (A-2): 20.0 parts Resin-type dispersant solution ((B1-1): non-volatile content 30%): 16.7 parts Solvent (P): 63.3 parts

[Examples 2 to 42, Comparative Examples 1 to 2, Production Examples 1 to 10]
(Preparation of colored composition (R-2 to 54))
A coloring composition (R-2 to 54) having a pigment content of 80% in the nonvolatile matter was prepared in the same manner as in Example 1, except that the material species and mass were changed as described in Table 3.

<Method for producing colored composition (colorant mixture)>
[Example 101]
(Preparation of colored composition (X-1))
The following raw materials were mixed, stirred, and filtered through a filter with a pore size of 1.0 μm to obtain a colored composition (X-1).
Coloring composition (R-1: non-volatile content 25.0% liquid): 50.0 parts Coloring composition (R-45: non-volatile content 25.0% liquid): 25.0 parts binder resin (C-1: non-volatile 20% liquid): 5.0 parts Organic solvent (P): 20.0 parts

[Examples 102 to 154, Comparative Example 101]
(Preparation of colored composition (X-2 to 55))
A coloring composition (X-2 to 55) was prepared in the same manner as in Example 101, except that the material species and mass were changed as described in Table 4.

<Evaluation of coloring composition>
The obtained colored compositions (R-1 to 44, X-1 to 55) were tested for viscosity and storage stability by the following methods. Table 5 shows the results of the test.
The evaluation is as follows.
◎: Very good, 〇: Good, △: Practical, ×: Not suitable for practical use

(Measurement of viscosity characteristics)
An E-type viscometer ("ELD type viscometer" manufactured by Toki Sangyo Co., Ltd.) was used to measure the viscosity at a rotation speed of 20 rpm. The rank of evaluation is as follows.
○: Viscosity 4.0 or more and less than 20.0 ×: Viscosity 20 or more

(Storage stability)
The storage stability of the colored compositions obtained in Examples and Comparative Examples was evaluated by the following method.
The initial viscosity the day after the colored composition was prepared and the viscosity over time accelerated at 40 ° C. for 1 week were measured at 25 ° C. using an E-type viscometer (“ELD type viscometer” manufactured by Toki Sangyo Co., Ltd.). Measurement was performed under the condition of a rotation speed of 50 rpm. From the values of the initial viscosity and the viscosity over time, the rate of change in viscosity over time was calculated according to the following formula, and the storage stability was evaluated in two stages.
[Rate of viscosity change over time] = | ([initial viscosity] - [viscosity over time]) / [initial viscosity] | × 100
◎: Change rate of less than 5% ○: Change rate of 5% or more and less than 10% △: Change rate of 10% or more and less than 15% ×: Change rate of 15% or more

(Contaminant evaluation)
Foreign matter evaluation is carried out by applying the coloring composition to a transparent substrate so that the dry film has a thickness of about 2.0 μm, and heat-treating it in an oven at 230° C. for 1 hour. bottom. For the evaluation, surface observation was performed using a metallurgical microscope "BX60" (manufactured by Olympus System Co., Ltd.). Magnification was set to 500 times, and the number of foreign particles observable in arbitrary five fields of view was counted. The evaluation criteria are as follows.
◎: The number of foreign substances is less than 5 ○: The number of foreign substances is 5 or more and less than 20 △: The number of foreign substances is 21 or more and less than 100 ×: The number of foreign substances is 100 or more

<Method for producing a photosensitive coloring composition>
[Example 201]
(Photosensitive coloring composition (Y-1))
The following raw materials are mixed, stirred, and filtered through a filter with a pore size of 1.0 μm to obtain a photosensitive coloring composition (Y
-1) was obtained.
Coloring composition (R-1: non-volatile content 25%): 80.0 parts thermosetting compound (CE-1): 0.5 parts thermosetting compound (CE-2): 0.5 parts photopolymerizable unit Polymer (D): 2.0 parts Photoinitiator (E): 1.8 parts Sensitizer (H): 0.2 parts Thiol chain transfer agent (I): 0.4 parts Polymerization inhibitor ( J): 0.1 part UV absorber (K): 0.1 part Antioxidant (L): 0.1 part Leveling agent (M: 3% nonvolatile): 1.0 part Storage stabilizer (N) : 0.1 parts Silane coupling agent (O): 0.2 parts Solvent (P): 13.0 parts

[Examples 202-302, Comparative Examples 201-203]
(Preparation of photosensitive coloring composition (Y-2 to 105))
Photosensitive coloring compositions (Y-2 to 105) were prepared in the same manner as in Example 201 except that the types of the coloring composition and binder resin solution of Example 201 were changed as shown in Table 6. In addition, about each raw material, it is as follows.

<Thermosetting compound>
・ Epoxy compound (CE-1)
(CE-1-1) 1,2- of 2,2′-bis(hydroxymethyl)-1-butanol
Epoxy-4-(2-oxiranyl)cyclohexane adduct
[EHPE-3150 (manufactured by Daicel Corporation)],
(CE-1-2) Glycidyl etherified epoxy compound of sorbitol
[Denacol EX611 (manufactured by Nagase ChemteX Corporation)],
(CE-1-3) Equal amounts of triglycidyl isocyanurate (CE-1-1) to (CE-1-3) were mixed to obtain an epoxy compound (CE-1).
- Oxetane compound (CE-2):
3-ethyl-3-[(3-ethyloxetan-3-yl)methoxymethyl]oxetane
[Aron oxetane OXT-221 (manufactured by Toagosei Co., Ltd.)]

<Polymerizable compound (D)>
(D-1) trimethylolpropane triacrylate
[Aronix M309 (manufactured by Toagosei Co., Ltd.)]
(D-2) Dipentaerythritol penta and hexaacrylate (E-2)
[Aronix M402 (manufactured by Toagosei Co., Ltd.)]
(D-3) Polybasic acidic acrylic oligomer
[Aronix M520 (manufactured by Toagosei Co., Ltd.)]
(D-4) Caprolactone-modified dipentaerythritol hexaacrylate
[KAYARAD DPCA-30 (manufactured by Nippon Kayaku Co., Ltd.)]

(D-5) Polyfunctional urethane acrylate according to the following Pentaerythritol triacrylate (432 g, hexamethylene diisocyanate 84 g) was charged into a 1-liter 5-neck reaction vessel, reacted at 60 ° C. for 8 hours, and (meth) acryloyl group In the product, the proportion of polyfunctional urethane acrylate (D-5) is 70% by mass, and the remainder is other photopolymerizable It was confirmed by IR analysis that no isocyanate group was present in the reaction product.

(D-6) Bifunctional bisphenol A type (meth)acrylate
[ABE-300 (manufactured by Shin-Nakamura Chemical Co., Ltd.)]
(D-7) Ethoxylated isocyanuric acid triacrylate
[A-9300 (manufactured by Shin-Nakamura Chemical Co., Ltd.)]
The above (D-1) to (D-7) were mixed in equal amounts to obtain a photopolymerizable monomer (D).

<Photoinitiator (E)>
(E-1) 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one [Irgacure 907 (manufactured by BASF Japan)]
(E-2) 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone [Irgacure 379 (manufactured by BASF Japan)]
(E-3) 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide [Lucirin TPO (manufactured by Ciba Japan)]
(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) Ethan-1-one, 1-[9-ethyl-6-(2-methylbenzoyl)-9H
-carbazol-3-yl], 1-(O-acetyloxime) [Irgacure OXE02
(manufactured by BASF Japan)]
(E-7) 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-
Methyl-1-propan-1-one [Irgacure 2959 (manufactured by BASF Japan)]
(E-8) bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide
[Irgacure 819 (manufactured by BASF Japan)]
The above (E-1) to (E-8) were mixed in equal amounts to obtain a photopolymerization initiator (E).

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

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

<Polymerization inhibitor (J)>
(J-1) 3-methylcatechol (J-2) methylhydroquinone (J-3) t-butylhydroquinone or more, (J-1) to (J-3) are mixed in equal amounts, and a polymerization inhibitor is added. (J).

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

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

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

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

<Adhesion improver (O)>
(O-1) 3-glycidoxypropyltriethoxysilane
[Shin-Etsu Silicone Silane Coupling Agent KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.)]
(O-2) 3-methacryloxypropyltriethoxysilane
[Shin-Etsu Silicone Silane Coupling Agent KBE-503 (manufactured by Shin-Etsu Chemical Co., Ltd.)]
(O-3) N-2-(aminoethyl)-3-aminopropyltrimethoxysilane
[Shin-Etsu Silicone Silane Coupling Agent KBM-603 (manufactured by Shin-Etsu Chemical Co., Ltd.)]
(O-4) 3-mercaptopropyltrimethoxysilane
[Shin-Etsu Silicone Silane Coupling Agent KBM-803 (manufactured by Shin-Etsu Chemical Co., Ltd.)]
The above (O-1) to (O-4) were mixed in equal amounts to obtain a silane coupling agent (O).

<Solvent (P)>
(P-1) 30 parts of PGMAc (P-2) 30 parts of cyclohexanone (P-3) 10 parts of ethyl 3-ethoxypropionate (P-4) 10 parts of propylene glycol monomethyl ether (P-5) 10 parts of cyclohexanol acetate (P-6) Dipropylene glycol methyl ether acetate 10 parts The above and (P-1) to (P-6) were mixed in the above parts by mass to obtain a solvent (P).

<Evaluation of photosensitive coloring composition>
Each test was performed by the following method. The results of the tests are shown in Tables 7-1 and 7-2.
The meaning of the evaluation rank is as follows.
◎: Excellent 〇: Good △: Practical ×: Not suitable for practical use

(Measurement of viscosity characteristics)
An E-type viscometer ("ELD type viscometer" manufactured by Toki Sangyo Co., Ltd.) was used to measure the viscosity at a rotation speed of 20 rpm. The rank of evaluation is as follows.
○: Viscosity 2.0 or more and less than 10.0 ×: Viscosity 10.0 or more (storage stability)
The storage stability of the photosensitive coloring compositions obtained in Examples and Comparative Examples was evaluated by the following method.
The initial viscosity on the next day after preparing the photosensitive coloring composition and the viscosity over time accelerated at 40 ° C. for 1 week were measured using an E-type viscometer (“ELD type viscometer” manufactured by Toki Sangyo Co., Ltd.). It was measured under the condition of 50 rpm at ℃. From the values of the initial viscosity and the viscosity over time, the rate of change in viscosity over time was calculated according to the following formula, and the storage stability was evaluated in two stages.
[Rate of viscosity change over time] = | ([initial viscosity] - [viscosity over time]) / [initial viscosity] | × 100
◎: Change rate of less than 5% ○: Change rate of 5% or more and less than 10% △: Change rate of 10% or more and less than 15% ×: Change rate of 15% or more

(Development speed evaluation)
The photosensitive coloring composition was spin-coated on a glass substrate of 0.7 mm thickness and 10 mm×10 mm using a spin coater so that the dry film thickness would be 1.0 μm, and dried at 70° C. for 20 minutes. 2 ml of a 2% by mass potassium hydroxide aqueous solution was added dropwise to the film, and the time until the film was completely dissolved was measured to evaluate the development speed of the photosensitive coloring composition. The rank of evaluation is as follows.
○: Less than 10 seconds △: 10 seconds or more, less than 15 seconds ×: 15 seconds or more

[Residue evaluation]
A black matrix is patterned on a glass substrate of 100 mm × 100 mm and a thickness of 0.7 mm, the obtained photosensitive coloring composition is applied on the substrate with a spin coater, and the solvent is removed by drying at 90 ° C. for 90 seconds. A coating with a thickness of 1.0 μm was obtained. Through a photomask having a predetermined pattern, the film was irradiated with ultraviolet rays of 100 mJ/cm ² using an ultra-high pressure mercury lamp, and spray-developed with an alkaline developer consisting of a 0.2% by mass sodium carbonate aqueous solution. The uncured portion was removed to form the desired pattern. The resulting film was heat-treated in an oven at 230° C. for 20 minutes to form a filter segment. Dektak 3030 (manufactured by Japan Vacuum Engineering Co., Ltd.) was used to determine the thickness of the coating. Using the evaluation substrate thus produced, the portion removed with the developer was observed with an electron microscope, and the presence or absence of residue was evaluated according to the following criteria.
◯: No adhesion of residue Δ: Slight adhesion of residue.
×: with residue

(Contaminant evaluation)
Foreign matter evaluation is carried out by coating a photosensitive coloring composition on a transparent substrate so that the dried film has a thickness of about 2.0 μm, and performing heat treatment in an oven at 230° C. for 1 hour. was measured. For the evaluation, surface observation was performed using a metallurgical microscope "BX60" (manufactured by Olympus System Co., Ltd.). Magnification was set to 500 times, and the number of foreign particles observable in arbitrary five fields of view was counted. The evaluation criteria are as follows.
◎: The number of foreign substances is less than 5 ○: The number of foreign substances is 5 or more and less than 20 △: The number of foreign substances is 21 or more and less than 100 ×: The number of foreign substances is 100 or more

[Surface roughness evaluation]
Using the sample used in the foreign matter evaluation, the surface roughness of the film was measured using a Nano Scope IIIa (AFM) device manufactured by Digital Instruments Co., Ltd. in a 10 μm square area, and the surface roughness (Ra) was measured according to the following criteria. evaluated.
○: less than 5 nm △: 5 nm or more to less than 10 nm ×: 10 nm or more

[Crystal foreign matter evaluation]
The pattern obtained by residue evaluation was heated on a hot plate at 230° C. for 300 seconds, and the presence or absence of crystal precipitates was confirmed by observing 10 locations of the pixel pattern with a microscope.
○: No precipitates △: 1 or more and less than 5 precipitates ×: 5 or more precipitates

Claims (6)

An organic pigment (A), a resin-type dispersant (B), a binder resin (C) (excluding resins having a maleimide structure), a polymerizable compound (D), and a photopolymerization initiator (E ) A photosensitive coloring composition comprising
The organic pigment (A) contains one or more selected from zinc phthalocyanine pigment (A1) and aluminum phthalocyanine pigment (A2),
The content of the organic pigment (A) is 40 to 90% by mass in the non-volatile content of 100% by mass of the photosensitive coloring composition,
The resin-type dispersant (B) includes a resin-type dispersant (B1) having an aromatic carboxylic acid structure and a vinyl polymer moiety having a (meth)acryloyl group, and a resin-type dispersant (B3) having a basic group. including
In 100 parts by mass of the resin type dispersant (B), 34 to 100 parts by mass of the resin type dispersant (B1),
A photosensitive coloring composition containing 0.5 to 50 parts by mass of a binder resin (C) with respect to 100 parts by mass of a resin type dispersant (B). 2. The resin type dispersant (B) according to claim 1, further comprising a resin type dispersant (B2) having a vinyl polymer moiety having an aromatic carboxylic acid structure and no (meth)acryloyl group. A photosensitive coloring composition. The photosensitive coloring composition according to claim 1 or 2, wherein the organic pigment (A) comprises a yellow pigment (a). A color filter formed from the photosensitive coloring composition according to any one of claims 1 to 3. A solid-state imaging device comprising the color filter according to claim 4 . A liquid crystal display device comprising the color filter according to claim 4 .

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