JP7529094B2 - Coloring composition, color filter, solid-state imaging device and liquid crystal display device - Google Patents

Description

The present invention relates to a coloring composition used in the manufacture of color filters for use in solid-state imaging devices, liquid crystal display devices, etc.

Color filters used in solid-state imaging devices, liquid crystal display devices, etc. are formed by forming fine patterns from photosensitive coloring compositions using a photolithography method. There is a demand for further improvements in the quality and definition of solid-state imaging devices and liquid crystal display devices, and there is also a demand for further finer color filters.

Patent Document 1 discloses a coloring composition containing a dispersant with a block structure.

JP 2002-31713 A

However, conventional coloring compositions have problems such as a high viscosity and poor storage stability, resulting in a short self-life and the tendency for foreign matter to form in the coating. Furthermore, photosensitive coloring compositions containing the above-mentioned coloring composition have problems such as a tendency for residues to form after development in a photolithography method, and a problem of high surface roughness on the coating surface.

The present invention aims to provide a photosensitive coloring composition that has a suitable viscosity and good viscosity stability (dispersion stability), produces little foreign matter, leaves little residue, and can form a coating with reduced surface roughness.

The photosensitive coloring composition of the present invention is a photosensitive coloring composition comprising 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),
The organic pigment (A) includes at least one pigment selected from the group consisting of a zinc phthalocyanine pigment (A1) and an aluminum phthalocyanine pigment (A2);
The content of the organic pigment (A) is 40 to 90 mass% based on 100 mass% of the nonvolatile content of the photosensitive coloring composition,
The resin-type dispersant (B) includes a resin-type dispersant (B1) having a vinyl polymer moiety having an aromatic carboxylic acid structure and a (meth)acryloyl group, and a resin-type dispersant (B3) having a basic group,
The resin type dispersant (B) contains 34 to 100 parts by mass of the resin type dispersant (B1) in 100 parts by mass of the resin type dispersant (B), and the binder resin (C) is contained in an amount of 0.5 to 50 parts by mass relative to 100 parts by mass of the resin type dispersant (B).

According to the present invention, it is possible to provide a coloring composition, a color filter, and a solid-state imaging device that can produce a photosensitive coloring composition that has a suitable viscosity and good viscosity stability (dispersion stability), produces little foreign matter, leaves little residue, and can form a coating with reduced surface roughness.

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

The terms used in this specification are defined as follows: "(meth)acryloyl", "(meth)acrylic",
Unless otherwise specified, when "(meth)acrylic acid", "(meth)acrylate", or "(meth)acrylamide" is written, it means "acryloyl and/or methacryloyl", "acrylic and/or methacrylic", "acrylic acid and/or methacrylic acid", "acrylate and/or methacrylate", or "acrylamide and/or methacrylamide", respectively. "C.I." mentioned in this specification means Color Index (C.I.). Colorants include pigments and dyes. Monomers are ethylenically unsaturated group-containing monomers.

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) includes at least one pigment selected from the group consisting of a zinc phthalocyanine pigment (A1) and an aluminum phthalocyanine pigment (A2);
The content of the organic pigment (A) is 40 to 90 mass% based on 100 mass% of the nonvolatile content of the coloring composition,
The resin-type dispersant (B) contains a resin-type dispersant (B1) having an aromatic carboxylic acid structure and a vinyl polymer moiety having a (meth)acryloyl group.

<Organic pigment (A)>
The organic pigment (A) includes at least one pigment selected from the group consisting of a zinc phthalocyanine pigment (A1) and an aluminum phthalocyanine pigment (A2).
The zinc phthalocyanine pigment (A1) and the aluminum phthalocyanine pigment (A2) preferably contain a halogen atom such as chlorine or bromine as a substituent. For 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) in order to adjust the color tone of the coating.

(Yellow Pigment (a))
Yellow pigments are organic pigments, for example, C.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, 1 20, 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, etc. Among these, C.I. Pigment Yellow 138, 139, 150, 185, 231, 233 are preferred.

The coloring composition may contain inorganic pigments and dyes.
Examples of inorganic pigments include titanium oxide, barium sulfate, zinc oxide, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron (III) oxide), cadmium red, ultramarine, Prussian blue, chromium oxide green, cobalt green, umber, and synthetic iron black.

<Dye>
Examples of the dye include acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, sulfur dyes, etc. In addition, examples of the dye include dye derivatives and lake pigments obtained by converting dyes into lakes.

The dye may be an acid dye having an acidic group such as sulfonic acid or carboxylic acid, or in the case of a direct dye, an inorganic salt of an acid dye; a salt-forming compound of an acid dye with a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, or a primary amine compound; or a salt-forming compound of a resin component having an amino group and an acid dye. A salt-forming compound of an acid dye with a compound having an onium base is also preferred because of its excellent fastness. The compound having an onium base is preferably a resin having a cationic group in the side chain.

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

The chemical structure of dyes includes, for example, azo dyes, disazo dyes, azomethine dyes (indoaniline dyes, indophenol dyes, etc.), dipyrromethene dyes, quinone dyes (benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, anthrapyridone dyes, etc.), carbonium dyes (diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, etc.), quinoneimine dyes (oxazine dyes, etc.), 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, indigo dyes, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, rhodamine dyes, etc. Among these, from the viewpoint of color characteristics such as hue, color separation, and color unevenness, azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, squarylium dyes, quinophthalone dyes, phthalocyanine dyes, and subphthalocyanine dyes are preferred, and xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, and phthalocyanine dyes are more preferred. Specific structures of dyes are described in "New Edition Dye Handbook" (edited by the Society of Organic Synthesis Chemistry; Maruzen, 1970), "Color Index" (The Society of Dyers and Colourists), "Dye Handbook" (edited by Okawara et al.; Kodansha, 1986), etc.

<Micronization of organic pigment (A)>
The organic pigment (A) is preferably mixed with other raw materials after being subjected to a micronization treatment. Examples of the method of the micronization treatment include wet grinding, dry grinding, and dissolution precipitation. Among these, salt milling treatment using a kneader method, which is a type of wet grinding, is preferable. The average primary particle size of the organic pigment after the micronization treatment is preferably 10 to 80 nm, more preferably 15 to 70 nm. A moderate particle size further improves dispersibility and the contrast ratio of the coating. 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.

Salt milling is a process in which a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent is mechanically kneaded while being heated using a batch or continuous mixer such as a kneader, a two-roll mill, a three-roll mill, a ball mill, an attritor, a sand mill, or a planetary mixer, and then the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt acts as a crushing aid, and the high hardness of the inorganic salt is used to crush the pigment during salt milling. By optimizing the conditions for salt milling the pigment, it is possible to obtain a pigment with a very fine primary particle size, a narrow distribution range, and a sharp particle size distribution.

Examples of water-soluble inorganic salts include sodium chloride, barium chloride, potassium chloride, and sodium sulfate. Of these, sodium chloride (table salt) is preferred from the standpoint of cost. From the standpoint of both processing efficiency and production efficiency, the amount of water-soluble inorganic salt used is preferably 50 to 2,000 parts by weight, and more preferably 300 to 1,000 parts by weight, per 100 parts by weight of pigment.

The water-soluble organic solvent moistens the pigment and the water-soluble inorganic salt. The water-soluble organic solvent is a compound that dissolves (is mixed) in water and does not substantially dissolve the water-soluble inorganic salt. The water-soluble organic solvent is preferably a high-boiling solvent having a boiling point of 120°C or more, in that it is less likely to volatilize due to the temperature rise during salt milling. Examples of the water-soluble organic solvent include 2-methoxyethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol, etc. 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, per 100 parts by mass of the pigment.

When the pigment is subjected to salt milling, a resin may be added as necessary. There are no particular limitations on the type of resin used, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, etc. can be used. The resin used is preferably solid at room temperature and insoluble in water, and more preferably partially soluble in the above organic solvents. The amount of resin used is preferably in the range of 5 to 200 parts by mass per 100 parts by mass of the pigment.

<Resin-type dispersant (B)>
The resin-type dispersant (B) contains a resin-type dispersant (B1) having an aromatic carboxylic acid structure and a vinyl polymer moiety having a (meth)acryloyl group.
The aromatic carboxylic acid structure is adsorbed to the zinc phthalocyanine pigment (A1) or aluminum phthalocyanine pigment (A2) and adheres to it 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. Usually, when preparing a photosensitive coloring composition, when the organic pigment (A) is blended at a high concentration, the blending amount of the binder resin is relatively reduced, and the film-forming property may be reduced, but the resin-type dispersant (B) of this specification has photocuring properties, contributes to film formation, and is less likely to reduce developability. In addition, when a color filter containing the zinc phthalocyanine pigment (A1) or aluminum phthalocyanine pigment (A2) is heated in a post-bake process or a subsequent heat treatment process, the pigment may aggregate to generate crystalline foreign matter, but the use of the resin-type dispersant (B1) can suppress aggregation due to thermal movement of pigment particles, improving heat resistance and preventing precipitation of crystalline foreign matter.

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

Examples of tetracarboxylic dianhydrides include 1,2,3,4-butane tetracarboxylic dianhydride, 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic dianhydride, 3,5,6-tricarboxynorbornane-2-acetic dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 5-(2,5-dioxotetrahydrofural)-3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, and bicyclo[2,2,2]-oct-7-ene. Aliphatic tetracarboxylic dianhydrides such as 2,3,5,6-tetracarboxylic dianhydride, pyromellitic dianhydride, ethylene glycol ditrimellitic anhydride, propylene glycol ditrimellitic anhydride, butylene glycol ditrimellitic anhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenylsulfone tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 3,3',4,4'-biphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-dimethyldiphenylsilane Tetracarboxylic acid dianhydride, 3,3',4,4'-tetraphenylsilane tetracarboxylic acid dianhydride, 1,2,3,4-furan tetracarboxylic acid dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfone dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropylidenediphthalic dianhydride, 3,3',4,4'-biphenyl tetracarboxylic acid dianhydride, bis(phthalic acid)phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylfuran Examples of the aromatic tetracarboxylic acid dianhydride include aromatic tetracarboxylic acid dianhydrides such as m-phenylene-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4'-diphenyl ether dianhydride, bis(triphenylphthalic acid)-4,4'-diphenyl methane 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-naphthalene succinic acid dianhydride, and 3,4-dicarboxy-1,2,3,4-tetrahydro-6-methyl-1-naphthalene succinic acid dianhydride. Among these, aromatic tetracarboxylic acid dianhydrides are preferred in terms of excellent adsorption to colorants, and tetracarboxylic acid dianhydrides having two or more aromatic rings are more preferred.

Examples of tricarboxylic anhydrides include benzenetricarboxylic anhydride (1,2,3-benzenetricarboxylic anhydride, trimellitic anhydride [1,2,4-benzenetricarboxylic anhydride], etc.), naphthalenetricarboxylic anhydride (1,2,4-naphthalenetricarboxylic anhydride, 1,4,5-naphthalenetricarboxylic anhydride, 2,3,6-naphthalenetricarboxylic anhydride, 1,2,8-naphthalenetricarboxylic anhydride, 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, etc. Among these, trimellitic anhydride is more preferable.

(Vinyl polymer moiety having (meth)acryloyl group)
The vinyl polymer moiety having a (meth)acryloyl group can be synthesized by reacting a hydroxyl group of the vinyl polymer portion with an isocyanate group in an isocyanate group-containing monomer, thereby imparting photocurability to the vinyl polymer moiety, which is the relaxation moiety.

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

The hydroxyl group-containing thiol is preferably a compound having two hydroxyl groups and one thiol group. Examples of the hydroxyl group-containing thiol include 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, and 2-mercaptoethyl-2-ethyl-1,3-propanediol.

Monomers used in the synthesis of the vinyl polymer portion include, for example, at least one thermally crosslinkable functional group selected from the group consisting of a hydroxyl group, an oxetane group, a t-butyl group, and a blocked isocyanate group, a carboxyl group-containing monomer, and other monomers.

Examples of the hydroxyl group-containing monomer include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2 (or 3)-hydroxypropyl (meth)acrylate, 2 (or 3 or 4)-hydroxybutyl (meth)acrylate, and cyclohexanedimethanol mono(meth)acrylate, and alkyl-α-hydroxyalkyl acrylates such as ethyl-α-hydroxymethyl acrylate;
Examples of (meth)acrylamide monomers having a hydroxyl group include N-(hydroxyalkyl)(meth)acrylamides such as N-(2-hydroxyethyl)(meth)acrylamide, N-(2-hydroxypropyl)(meth)acrylamide, and N-(2-hydroxybutyl)(meth)acrylamide;
Examples of vinyl ether monomers having a hydroxyl group include hydroxyalkyl vinyl ethers such as 2-hydroxyethyl vinyl ether, 2-(or 3-)hydroxypropyl vinyl ether, and 2-(or 3- or 4-)hydroxybutyl vinyl ether;
Examples of the allyl ether monomer having a hydroxyl group include hydroxyalkyl allyl ethers such as 2-hydroxyethyl allyl ether, 2-(or 3-)hydroxypropyl allyl ether, and 2-(or 3- or 4-)hydroxybutyl allyl ether.

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

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

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

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, of the total monomers. Using an appropriate amount will further improve the solvent resistance of the coating.

Examples of carboxyl group-containing monomers include (meth)acrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid. Of these, (meth)acrylic acid is preferred.

Other monomers include (meth)acrylic acid esters, nitrogen-containing group monomers, and vinyl monomers. (Meth)acrylic acid esters include, for example, (meth)acrylic acid alkyl esters such as 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, and lauryl (meth)acrylate; cyclohexyl (meth)acrylate, tertiary butyl cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and dicyclopentenyl (meth)acrylate. aliphatic ring (meth)acrylates such as phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, and phenoxydiethylene glycol (meth)acrylate; heterocyclic (meth)acrylates such as tetrahydrofurfuryl (meth)acrylate and 3-methyl-3-oxetanyl (meth)acrylate; alkoxy polyalkylene glycol (meth)acrylates such as methoxy polypropylene glycol (meth)acrylate and ethoxy polyethylene glycol (meth)acrylate;

Examples of nitrogen-containing group monomers include N-substituted (meth)acrylamides such as (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, and acryloylmorpholine; amino group-containing (meth)acrylates such as N,N-dimethylaminoethyl(meth)acrylate and N,N-diethylaminoethyl(meth)acrylate; and nitriles such as meth)acrylonitrile.

Examples of vinyl monomers include styrenes such as styrene and α-methylstyrene, vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether, and vinyl fatty acids such as vinyl acetate and vinyl propionate.

(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) is 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. 4396777 and Japanese Patent No. 5181664. By using the resin type dispersant (B1) and the resin type dispersant (B2) in combination, the photocurability of the coating can be appropriately adjusted.

(Resin-type dispersant (B3))
The resin-type dispersant (B) may be used in combination with a resin-type dispersant (B3) having a basic group. Examples of the basic group include a tertiary amino group, a quaternary ammonium base, and a nitrogen-containing heterocycle. Examples of the resin skeleton include an acrylic resin and a urethane resin.

(Other dispersants)
The resin-type dispersant (B) may be used in combination with other dispersants other than those mentioned above.
Other dispersants include, for example, urethane-based dispersants such as polyurethane, polycarboxylate esters such as polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylate (partial) amine salts, polycarboxylate ammonium salts, polycarboxylate alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl-containing polycarboxylate esters, and modified products thereof, poly(lower alkylene imines) and free carboxyl groups formed by reaction with polyesters, and oil-based dispersants such as amides and salts thereof, (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, water-soluble resins and water-soluble polymer compounds such as polyvinylpyrrolidone, polyesters, modified polyacrylates, ethylene oxide/propylene oxide adducts, and phosphate esters.

Resin-type dispersants (B) can be used alone or in combination of two or more types.

The amount of resin-type dispersant (B) used is preferably 3 to 200% by mass, and more preferably 5 to 100% by mass, per 100 parts by mass of organic pigment (A). Using an appropriate amount further improves film-forming properties.

<Dye derivative (b)>
The coloring composition may 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 the organic dye residue. For example, the dye derivative has an acidic substituent such as a sulfo group, a carboxy group, or a phosphate group. Examples of the resin to be used in combination include compounds and their amine salts, compounds having a basic substituent such as a sulfonamide group or a tertiary amino group at the terminal, and compounds having a neutral substituent such as a phenyl group or a phthalimidoalkyl group. Since the dispersant has an acidic group, a dye derivative having a basic group is preferred.
Examples of organic pigments include diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiazineindigo pigments, triazine pigments, benzimidazolone pigments, and benzoiso Examples of pigments include 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, etc. .

<Binder Resin (C)>
The coloring composition may contain a binder resin (C), which makes it easier to form a coating film.
The amount of the binder resin (C) used is preferably 0.5 to 50 parts by weight, more preferably 1 to 40% by weight, based on 100 parts by weight of the resin-type dispersant (B).
The binder resin (C) is preferably a resin having a transmittance of 80% or more, more preferably 95% or more, in the entire wavelength region of 400 to 700 nm, so that the color tone of the colorant used is not deteriorated.
The binder resin (C) can be classified according to its main curing method into thermoplastic resin, thermosetting resin, and active energy ray curable resin. The active energy ray curable resin is a resin obtained by imparting active energy ray curability to a thermoplastic resin or a thermosetting resin. In addition, the binder resin (C) is preferably an alkali-soluble resin having developability. The alkali solubility is for imparting development solubility in the alkali development step during the production of 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 resins can be used alone or in combination of two or more types.

The content of the binder resin is preferably 20 to 400 parts by weight, more preferably 50 to 250 parts by weight, per 100 parts by weight of the colorant. If an appropriate amount is included, the coating can be easily formed and good color characteristics can be easily obtained.

<Thermoplastic resin>
Examples of thermoplastic resins include acrylic resins, butyral resins, styrene-maleic acid copolymers, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, polyvinyl acetate, polyurethane resins, 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 the acidic group include a carboxyl group and a sulfone group. Examples of the alkali-soluble resin include an acrylic resin having an acidic group, an α-olefin/maleic acid (anhydride) copolymer, a styrene/styrene sulfonic acid copolymer, an ethylene/(meth)acrylic acid copolymer, or an isobutylene/maleic acid (anhydride) copolymer. Among these, an acrylic resin having an acidic group and a styrene/styrene sulfonic acid copolymer are preferred in terms of developability, heat resistance, and transparency, and an acrylic resin having an acidic group is more preferred.

<Alkali-soluble resin>
When a color filter is produced by photolithography, the alkali-soluble resin imparts development solubility to a coating film formed from a photosensitive coloring composition.

The weight average molecular weight (Mw) of the alkali-soluble resin is preferably from 2,000 to 40,000, more preferably from 3,000 to 30,000, and even more preferably from 4,000 to 20,000. The value of Mw/Mn is preferably not more than 10. A suitable Mw further improves the solubility in alkali development.
The acid value of the alkali-soluble resin is preferably from 50 to 200 mgKOH/g, more preferably from 70 to 180, and even more preferably from 90 to 170. When the alkali-soluble resin has a suitable 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. The ethylenically unsaturated group can be introduced, for example, by the following methods (i) and (ii). When an active energy ray-curable alkali-soluble resin is used, the coating is three-dimensionally crosslinked, increasing the crosslink density and improving chemical resistance.

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

Examples of epoxy group-containing monomers include glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4-epoxycyclohexyl (meth)acrylate. Among these, glycidyl (meth)acrylate is preferred from the viewpoint of reactivity.

Examples of carboxyl group-containing monomers include monocarboxylic acids such as (meth)acrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid, and (meth)acrylic acid substituted with haloalkyl, alkoxyl, halogen, nitro, or cyano at the α-position.

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

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

In addition, a method similar to method (i) can be used in which, for example, a carboxyl group-containing monomer and other monomers are synthesized to produce a polymer. Then, an epoxy group-containing monomer is added to some of the carboxyl groups of the polymer to obtain an alkali-soluble resin.

[Method (ii)]
Method (ii) is, for example, a method of polymerizing a hydroxyl group-containing monomer, a carboxyl group-containing monomer, and other monomers to prepare a polymer. Then, the hydroxyl group of the polymer is reacted with an isocyanate group of an isocyanate group-containing monomer. Examples of the other monomers include the 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.

Examples of maleimides include cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimideethane 1,6-bismaleimidehexane, 3-maleimidopropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimidocoumarin, 4,4'-bismaleimidediphenylmethane, 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-trimethylphenyl)maleimide, Examples of N-substituted maleimides include N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-3-maleimide propionate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl-6-maleimide hexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, and 9-maleimide acridine.

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

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

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

<Thermosetting Compound>
When the coloring composition uses a thermoplastic resin as a binder resin, it is preferable to use a thermosetting compound in combination. This improves the crosslinking density in the heating step after forming a pattern on the coating by photolithography when producing a color filter, thereby improving heat resistance. In addition, the coloring agent (A) is less likely to aggregate in the heating step, so the contrast ratio is further improved.

The thermosetting compound is a low molecular weight compound or a polymer (thermosetting resin) and is not limited by its molecular weight.
Examples of the thermosetting compound include epoxy compounds, oxetane compounds, benzoguanamine compounds, rosin-modified maleic acid compounds, rosin-modified fumaric acid compounds, melamine compounds, urea compounds, and phenol compounds. Among these, epoxy compounds and oxetane compounds are preferred.

(Epoxy Compound)
Examples of the epoxy compound include polycondensates of bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkyl aldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.), polycondensates of phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene ... Examples of such epoxy resins include polymers of phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.), polycondensates of phenols and aromatic dimethanols (benzene dimethanol, α,α,α',α'-benzene dimethanol, biphenyl dimethanol, α,α,α',α'-biphenyl dimethanol, etc.), polycondensates of phenols and aromatic dichloromethyls (α,α'-dichloroxylene, bischloromethylbiphenyl, etc.), polycondensates of bisphenols and various aldehydes, glycidyl ether epoxy resins obtained by glycidylating alcohols, alicyclic epoxy resins, heterocyclic epoxy resins, aliphatic epoxy resins, glycidyl amine epoxy resins, and glycidyl ester epoxy resins.

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

(Oxetane Compounds)
The 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 functional oxetane compounds.

Examples of the monofunctional oxetane compound include (3-ethyloxetan-3-yl)methyl acrylate, (3-ethyloxetan-3-yl)methyl methacrylate, and 3-ethyl-3-
Examples of the oxetane include hydroxymethyloxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(phenoxymethyl)oxetane, 3-ethyl-3-(2-methacryloxymethyl)oxetane, and 3-ethyl-3-{[3-(triethoxysilyl)propoxy]methyl}oxetane.

Examples of the bifunctional oxetane compound include 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-oxetanylmethyl)ether, bisphenol A bis(3-ethyl-3-oxetanylmethyl)ether, ethylene oxide (EO)-modified bisphenol A bis(3-ethyl-3-oxetanylmethyl)ether, propylene oxide (PO)-modified bisphenol A bis(3-ethyl-3-oxetanylmethyl)ether, EO-modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl)ether, PO-modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl)ether, EO-modified bisphenol F (3-ethyl-3-oxetanylmethyl)ether, and the like.

Examples of trifunctional or higher oxetane compounds include 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, and caprolactone-modified dipentaerythritol. Examples include erythritol 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 (such as the oxetane-modified phenol novolac resin described in Japanese Patent No. 3783462), and polymers obtained by radical polymerization of (meth)acrylic monomers such as the aforementioned OXE-30.

The content of the oxetane compound is preferably 0.5 to 50 parts by mass, more preferably 1 to 40 parts by mass. When an appropriate amount is contained, the solvent resistance of the coating is further improved.

(Melamine compounds)
The melamine compound is a compound having a melamine ring structure. The melamine compound includes low molecular weight compounds and high molecular weight compounds. In the present specification, the melamine compound is preferably a compound having a methylol group or an ether group bonded to a melamine ring. The number of methylol groups and/or ether groups bonded to one melamine ring is preferably 5.0 or more on average. If there is an appropriate number of bonds, the solvent resistance of the coating is further improved and the contrast ratio is less likely to decrease.

(Hardening agent)
In the present specification, a curing agent may be included to assist in the curing of the thermosetting compound. Examples of the curing agent include amine compounds, acid anhydrides, active esters, carboxylic acid compounds, and sulfonic acid compounds.
Examples of the amine compounds include dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine, etc., quaternary ammonium salt compounds (e.g., triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (e.g., dimethylamine, etc.), imidazole derivatives, bicyclic amidine compounds and their salts (e.g., imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methyl ... nylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, etc.), phosphorus compounds (for example, triphenylphosphine, etc.), S-triazine derivatives (for example, 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 per 100 parts by mass of the thermosetting compound.

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

<Polymerizable compound (D)>
The polymerizable compound (D) includes a monomer or oligomer that is cured by exposure to ultraviolet light, heat, or the like to form a transparent resin.

Examples of the polymerizable compound (D) include 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, phenoxyhexaethylene glycol (meth)acrylate, trimethylolpropane PO-modified tri(meth)acrylate, trimethylolpropane EO-modified tri(meth)acrylate, isocyanuric acid EO-modified di(meth)acrylate, isocyanuric acid EO-modified tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, Examples of the acrylic acid esters and methacrylic acid esters include 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, (meth)acrylic acid esters of methylolated melamine, epoxy (meth)acrylate, and urethane acrylate, as well as (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-vinyl formamide, and acrylonitrile.

These commercially available products include KAYARAD R-128H, R526, PEG400DA, MAND, NPGDA, R-167, HX-220, R-551, R712, R-604, R-684, GPO-303, TMPTA, DPHA, DPEA-12, DPHA-2C, D-310, D-330, DPCA-20, DPCA-30, DPCA-60, and DPCA-120 manufactured by Nippon Kayaku Co., Ltd., and Aronix M-303, M-305, M-306, M-309, M-310, manufactured by Toagosei Co., Ltd. Examples include 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, and M-101A, Viscoat #310HP, #335HP, #700, #295, #330, #360, #GPT, #400, and #405 manufactured by Osaka Organic Chemicals, and NK Ester A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd.

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

Examples of polymerizable compounds having an acid group include esters of free hydroxyl group-containing poly(meth)acrylates of polyhydric alcohols and (meth)acrylic acid with dicarboxylic acids; esters of polycarboxylic acids with monohydroxyalkyl (meth)acrylates, etc. Specific examples include free carboxyl group-containing monoesters of monohydroxy oligoacrylates or monohydroxy oligomethacrylates such as trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate with dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, and phthalic acid; and free carboxyl group-containing oligoesters of tricarboxylic acids such as propane-1,2,3-tricarboxylic acid (tricarballylic acid), butane-1,2,4-tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, and benzene-1,3,5-tricarboxylic acid with monohydroxy monoacrylates or monohydroxy monomethacrylates such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl methacrylate.

Examples of these commercially available products include Viscoat #2500P manufactured by Osaka Organics Co., Ltd., and Aronix M-5300, M-5400, M-5700, M-510, and M-520 manufactured by Toagosei Co., Ltd.

(Polymerizable compound having a urethane bond)
The polymerizable compound (D) can contain a polymerizable compound having an ethylenically unsaturated group and a urethane bond. Examples of the polymerizable compound include a polyfunctional urethane acrylate obtained by reacting a (meth)acrylate having a hydroxyl group with a polyfunctional isocyanate, and a polyfunctional urethane acrylate obtained by reacting an alcohol with a polyfunctional isocyanate and further reacting the alcohol with a (meth)acrylate having a hydroxyl group.

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

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

The polymerizable compounds can be used alone or in combination of two or more types.

The blending amount of the polymerizable compound (D) is 1 to 100% by mass of the nonvolatile content of the photosensitive coloring composition.
The content is preferably 50% by mass, and more preferably 2 to 40 parts by mass. When an appropriate amount is added, the curing property and the developability are further improved.

<Photopolymerization initiator (E)>
Examples of the photopolymerization initiator (E) include acetophenone-based compounds such as 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-1-[4-(4-morpholino)phenyl]-2-(phenylmethyl)-1-butanone, and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone; benzoin, benzoin methyl ether, benzo benzoin compounds such as benzoin ethyl ether, benzoin isopropyl ether, or benzil dimethyl ketal; benzophenone compounds such as benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone; thioxanthone compounds such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazine , 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy-naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, or 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine. Examples of the compounds include triazine-based compounds such as azine, oxime ester-based compounds such as 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)], or ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, or 1-(O-acetyloxime), phosphine-based compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide or diphenyl-2,4,6-trimethylbenzoylphosphine oxide, quinone-based compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone, borate-based compounds, carbazole-based compounds, imidazole-based compounds, and titanocene-based compounds. Among these, oxime ester-based compounds are preferred.

Photopolymerization initiators can be used alone or in combination of two or more types.

(Oxime ester compounds)
In the oxime ester compound, the N-O bond of the oxime is cleaved by absorbing ultraviolet light, generating an iminyl radical and an alkyloxy radical. These radicals further decompose to generate highly active radicals, making it possible to form a pattern with a small amount of exposure. When the colorant concentration of the photosensitive coloring composition is high, the ultraviolet transmittance of the coating film decreases, which may result in a low degree of curing of the coating film, but the oxime ester compound has a high quantum efficiency and therefore promotes curing.

Examples of oxime ester compounds include the oxime ester photopolymerization initiators described in JP-A-2007-210991, JP-A-2009-179619, JP-A-2010-037223, JP-A-2010-215575, and JP-A-2011-020998.

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

<Sensitizer (H)>
The photosensitive coloring composition may further contain a sensitizer.
Examples of the sensitizer include polymethine dyes such as chalcone derivatives, unsaturated ketones typified by dibenzalacetone, 1,2-diketone derivatives typified by benzil and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, and 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, and tetrapyrazinoporphyrazine. derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalylporphyrazine 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's ketone derivatives, α-acyloxy esters, acyl oxides, methylphenyl glyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl anthraquinone, 4,4'-diethylisophthalophenone, 3,3' or 4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 4,4'-bis(diethylamino)benzophenone, and the like.

Among these, thioxanthone derivatives, Michler's ketone derivatives, and carbazole derivatives are preferred. 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.

Sensitizers can be used alone or in combination of two or more types.

The content of the sensitizer is preferably 3 to 60 parts by weight, more preferably 5 to 50 parts by weight, per 100 parts by weight of the photopolymerization initiator. When an appropriate amount is included, the curing property and developability are further improved.

<Thiol-based chain transfer agent>
The photosensitive coloring composition can contain a chain transfer agent. The chain transfer agent is preferably a thiol-based chain transfer agent. When the thiol-based chain transfer agent is used in combination with a photopolymerization initiator, a thiyl radical that is not easily inhibited by oxygen during radical polymerization after irradiation with light is generated, and the sensitivity of the photosensitive coloring composition is improved.

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

Polyfunctional thiols include, for example, hexanedithiol and 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, trimercaptopropionic acid tris(2-hydroxyethyl)isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine, etc. are included, and preferably, ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthiopropionate, etc. are included.

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

The content of the thiol chain transfer agent is preferably 1 to 10% by mass, and more preferably 2 to 8% by mass, based on 100% by mass of the nonvolatile content of the photosensitive coloring composition. When an appropriate amount is included, the photosensitivity and the tapered shape of the coating cross section after development are improved, and wrinkles are less likely to occur on the coating surface.

<Polymerization inhibitor>
The photosensitive coloring composition may contain a polymerization inhibitor, which suppresses photosensitivity due to diffracted light from a mask during exposure in a photolithography method, making it easier to obtain a good pattern shape.

Polymerization inhibitors include, for example, alkyl catechol compounds such as catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol, 2-propylcatechol, 3-propylcatechol, 4-propylcatechol, 2-n-butylcatechol, 3-n-butylcatechol, 4-n-butylcatechol, 2-tert-butylcatechol, 3-tert-butylcatechol, 4-tert-butylcatechol, and 3,5-di-tert-butylcatechol; 2-methylresorcinol, 4-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2-propylresorcinol, 4-propylresorcinol, and 2-n-butylcatechol. Examples of such compounds include alkyl resorcinol compounds such as n-butyl resorcinol, 4-n-butyl resorcinol, 2-tert-butyl resorcinol, and 4-tert-butyl resorcinol; alkyl hydroquinone compounds such as methyl hydroquinone, ethyl hydroquinone, propyl hydroquinone, tert-butyl hydroquinone, and 2,5-di-tert-butyl hydroquinone; phosphine compounds such as tributyl phosphine, trioctyl phosphine, tricyclohexyl phosphine, triphenyl phosphine, and tribenzyl phosphine; phosphine oxide compounds such as trioctyl phosphine oxide and triphenyl phosphine oxide; phosphite compounds such as triphenyl phosphite and trisnonylphenyl phosphite; pyrogallol; and phloroglucin.

The content of the polymerization inhibitor is preferably 0.01 to 0.4 parts by mass based on 100% by mass of the nonvolatile content of the photosensitive coloring composition. 0.01 to 0.4 parts by mass is preferred. When an appropriate amount is included, it is possible to suppress the linearity of the coating cross section and wrinkles on the surface after development.

<Ultraviolet absorbing agent>
The photosensitive coloring composition may contain an ultraviolet absorbing agent. Examples of the ultraviolet absorbing agent include benzotriazole-based compounds, triazine-based compounds, benzophenone-based compounds, salicylic acid ester-based compounds, cyanoacrylate-based compounds, and salicylate-based compounds.

The content of the UV absorber is preferably 5 to 70% by mass, with the total of the photopolymerization initiator and the UV absorber being 100% by mass. If an appropriate amount is included, the resolution after development will be further improved.

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

Benzotriazole compounds include, for example, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, 5% 2-methoxy-1-methylethyl acetate and 95% benzenepropanoic acid, 3-(2H-benzotriazol-2-yl)-(1,1-dimethylethyl)-4-hydroxy, C7-9 side chain and linear alkyl esters. mixture of teres, 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, reaction products of methyl 3-(3-(2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxyphenyl)propionate/polyethylene glycol 300, 2-(2 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-hydroxyphenol), nyl)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, and 2-ethylhexyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate.

Examples of triazine compounds include 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine, 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol, and the reaction product of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and (2-ethylhexyl)-glycidic acid ester. Examples of such compounds include 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, and 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine.

Examples of benzophenone compounds include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid-3-water, 2-hydroxy-4-n-octoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2'dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, and 2-hydroxy-4-methoxy-2'-carboxybenzophenone.

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

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

I have added some additional information.
The content of the ultraviolet absorber is preferably 5 to 70% by mass, based on 100% by mass of the total of the photopolymerization initiator and the ultraviolet absorber. When an appropriate amount is contained, a good pattern shape is easily obtained. When the photosensitive coloring composition contains a sensitizer, the content of the photopolymerization initiator includes the content of the sensitizer.

In addition, the total content of the photopolymerization initiator and the UV absorber is preferably 1 to 20% by mass based on 100% by mass of the non-volatile content of the photosensitive coloring composition. When an appropriate amount is contained, the adhesion of the coating 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 can prevent the photopolymerization initiator or thermosetting compound contained in the photosensitive coloring composition from yellowing due to oxidation during the thermal process during heat curing or ITO annealing, and 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, so that the coating is likely to yellow when the amount of the photopolymerization initiator is increased or the thermosetting compound is blended. Therefore, by including an antioxidant, yellowing due to oxidation during the heating process can be prevented, and the decrease in the transmittance of the coating can be suppressed.

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

Examples of the hindered phenol compounds include 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)stearyl propionate, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 3,9-bis[2-[3-(3-t-butyl-4-hydroxy-5 -methylphenyl)propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, 1,3,5-tris(3,5-di-t-butyl-4-hydroxyphenylmethyl)-2,4,6-trimethylbenzene, 1,3,5-tris(3-hydroxy-4-t-butyl-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2,2'-methylenebis (6-t-butyl-4-ethylphenol), 2,2'-thiodiethyl bis-(3,5-di-t-butyl-4-hydroxyphenyl)-propionate, N,N-hexamethylene bis(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, 3,5-di-t-butyl-4-hydroxybenzyl calcium salt of benzylphosphonic acid monoethyl ester, 4,6-bis(octylthiomethyl)-o-cresol, bis[3-(3-methyl-4-hydroxy-5-t-butylphenyl)propionic acid]ethylene bisoxybisethylene, 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, and the like.

Examples of hindered amine compounds include tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)1,2,3,4-butane tetracarboxylate, 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, polycondensation product 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]], ester of 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol and 3,5,5-trimethylhexanoic acid, N,N'-4,7-tetrakis[ 4,6-Bis{N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino}-1,3,5-triazin-2-yl]-4,7-diazadecane-1,10-diamine, decanedioic acid bis(2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidinyl)ester, reaction products of 1,1-dimethylethyl hydroperoxide with octane, bis(1,2,2,6,6-pentamethyl-4-pyridyl)[[3,5-bis(1,1dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate methyl 1,2,2,6,6-pentamethyl-4-pyridyl 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, etc.

Examples of phosphorus compounds include di(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, 2,2'-methylenebis(4,6-di-t-butylphenyl)2-ethylhexyl phosphite, tris(2,4-di-t-butylphenyl)phosphite, tris(nonylphenyl)phosphite, tetra(C12-C15 alkyl)-4,4'-isopropylidenediphenyl diphosphite, diphenyl mono(2- ethylhexyl) phosphite, diphenyl isodecyl phosphite, tris(isodecyl) phosphite, triphenyl phosphite, tetrakis(2,4-di-t-butylphenyl)-4,4-biphenyl diphosphonate, tris(tridecyl) phosphite, phenyl isooctyl phosphite, phenyl isodecyl phosphite, phenyl di(tridecyl) phosphite, diphenyl isooctyl phosphite, diphenyl tridecyl phosphite, 4,4'-isopropylidene Diphenol alkyl phosphite, trisnonylphenyl phosphite, trisdinonylphenyl phosphite, tris(biphenyl)phosphite, di(2,4-di-t-butylphenyl)pentaerythritol diphosphite, di(nonylphenyl)pentaerythritol diphosphite, phenyl bisphenol 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-hydroxybenzyl phosphite diethyl ester, sodium bis(4-t-butylphenyl)phosphite, sodium-2,2-methylene-bis(4,6-di-t-butylphenyl)-phosphite, 1,3-bis(diphenoxyphosphonyloxy)-benzene, ethyl bis(2,4-ditert-butyl-6-methylphenyl) phosphite, etc.

Examples of sulfur-based compounds include 2,2-bis{[3-(dodecylthio)-1-oxopropoxy]methyl}propane-1,3-diylbis[3-(dodecylthio)propionate], 3,3'-thiobisditridecylpropionate, 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,4-bis[(octylthio)methyl]-o-cresol, and 2,4-bis[(laurylthio)methyl]-o-cresol.

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

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

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

Examples of silicone surfactants include chain polymers with siloxane bonds and modified siloxane polymers with organic groups introduced into the side chains or ends.

Fluorosurfactants are compounds that have a fluorocarbon chain.

Nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyethylene myristyl ether, polyoxyethylene octyldodecyl ether, polyoxyalkylene alkyl ether, polyoxyphenylenedistyrenated phenyl ether, polyoxyethylene tribenzyl phenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyalkylene alkenyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene alkyl ether phosphate ester, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, sorbitan tristearate, Examples of such 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 sorbitan tetraoleate, glycerol monostearate, glycerol monooleate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol monooleate, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkylamine, alkyl alkanolamide, alkyl imidazoline, etc.

Examples of cationic surfactants include alkylamine salts, alkyl quaternary ammonium salts such as lauryl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, and cetyl trimethyl ammonium chloride, and ethylene oxide adducts of these.

Examples of anionic surfactants include polyoxyethylene alkyl ether sulfates, sodium dodecylbenzenesulfonate, alkali salts of styrene-acrylic acid copolymers, sodium alkylnaphthalenesulfonates, sodium alkyldiphenyletherdisulfonates, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine styrene-acrylic acid copolymers, polyoxyethylene alkyl ether phosphates, etc.

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

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

The content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, of the non-volatile content of the photosensitive coloring composition. By being within this range, the balance between the coatability, pattern adhesion, and transmittance of the photosensitive coloring composition is further improved.

<Storage stabilizer>
The photosensitive coloring composition may contain a storage stabilizer to stabilize the viscosity of the composition over time. Examples of the storage stabilizer include quaternary ammonium chlorides such as benzyl trimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, organic phosphines such as t-butylpyrocatechol, tetraethylphosphine and tetraphenylphosphine, and phosphites.

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

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

Examples of silane coupling agents include vinyl silanes such as vinyl trimethoxysilane and vinyl triethoxysilane, (meth)acrylic silanes such as 3-methacryloxypropyl methyl dimethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyl methyl diethoxysilane, 3-methacryloxypropyl triethoxysilane, and 3-acryloxypropyl trimethoxysilane, epoxy silanes such as 2-(3,4-epoxycyclohexyl)ethyl trimethoxysilane, 3-glycidoxypropyl methyl dimethoxysilane, 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl methyl diethoxysilane, and 3-glycidoxypropyl triethoxysilane, N-2-(aminoethyl)-3-aminopropyl methyl dimethoxysilane, N-2-(a aminosilanes such as N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, and N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride; mercaptos such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; styryls such as p-styryltrimethoxysilane; ureidos such as 3-ureidopropyltriethoxysilane; sulfides such as bis(triethoxysilylpropyl)tetrasulfide; and isocyanates such as 3-isocyanatepropyltriethoxysilane.

The content of the adhesion improver is preferably 0.01 to 10 parts by mass, and more preferably 0.05 to 5 parts by mass, per 100 parts by mass of the colorant. When an appropriate amount is included, 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 makes it easier to adjust the viscosity of the photosensitive coloring composition, making it easier to form a coating with a smooth surface. The solvent may be appropriately selected according to the purpose of use, and may be contained in an appropriate amount.

Examples of solvents include ester solvents (solvents that contain -COO- in the molecule and do not contain -O-), ether solvents (solvents that contain -O- in the molecule and do not contain -COO-), ether ester solvents (solvents that contain -COO- and -O- in the molecule), ketone solvents (solvents that contain -CO- in the molecule and do not contain -COO-), alcohol solvents (solvents that contain OH in the molecule and do not contain -O-, -CO-, or -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, etc.

Examples of ester solvents include 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, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, and γ-butyrolactone.

Examples of the ether solvent include 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, 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, phenetole, and methylanisole.

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, ethyl 3-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, ethyl 3-methoxypropionate, Examples include 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, and dipropylene glycol diacetate.

Examples of ketone solvents include 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, and glycerin.

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

Examples of amide solvents include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

Among these, solvents with a boiling point of 120°C or more and 180°C or less at 1 atm are preferred in terms of coatability 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, etc. are more preferred, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate, etc. are even more preferred.

Solvents can be used alone or in combination of two or more types.

<Method for producing photosensitive coloring composition>
The photosensitive coloring composition is prepared by dispersing an organic pigment (A) and a resin-type dispersant (B) to prepare a pigment dispersion (also called a coloring composition). The coloring composition can further contain a binder resin (C). The photosensitive coloring composition can be prepared by mixing a polymerizable compound (D) and a photopolymerization initiator (E) with the coloring composition. The binder resin may be added when preparing the photosensitive coloring composition.

The dispersion process can be carried out using a dispersion device such as 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.

<Dispersed Pigment Particle Diameter>
The average dispersed particle diameter of the pigment in the coloring composition or the photosensitive coloring composition is preferably 30 to 200 nm, more preferably 40 to 120 nm. In this range, the coloring composition is easy to obtain an appropriate viscosity and the dispersion stability is further improved. In addition, the photosensitive coloring composition has high sensitivity and can increase the development speed. Therefore, it is easy to prepare a high-quality color filter.

The average dispersed particle diameter can be measured using Nikkiso's Microtrac UPA-EX150, which employs dynamic light scattering (FFT power spectrum method), with particle transmittance set to absorption mode, particle shape set to non-spherical, and D50 set as the average diameter. The dilution solvent used for measurement is the same as that used to prepare the pigment dispersion. It is also preferable to measure samples that have been ultrasonically treated in advance immediately after sample preparation, as this tends to give results with less variation.

<Removal of coarse particles>
It is preferable that the photosensitive coloring composition is dispersed in beads using zirconium oxide, inorganic glass, or the like in the manufacturing process. Beads of different diameters can be used for the bead dispersion. After the bead dispersion, it is preferable to remove coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably coarse particles of 0.5 μm or more, and mixed dust using a centrifuge with a gravitational acceleration of 3000 to 25000 G, a sintered filter, a membrane filter, or the like.

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

<Color filter>
The color filter of the present specification preferably comprises a filter segment formed from a photosensitive coloring composition, and more preferably further comprises a base material (also referred to as a transparent substrate).
The color filter segment (hereinafter also referred to as the filter segment) preferably has a red filter segment, a green filter segment, and a blue filter segment by appropriately selecting the type of colorant used. The color filter can also have a magenta filter segment, a cyan filter segment, and a yellow filter segment 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 includes a green filter segment formed from a photosensitive coloring composition containing an organic pigment (A).

<Manufacturing method of color filter>
It is preferable to form a color filter by first forming a black matrix on a substrate and then forming filter segments. It is also possible to form thin film transistors (TFTs) on the substrate before forming the black matrix.
The black matrix may be, for example, a multilayer film of chromium or chromium/chromium oxide, an inorganic film such as titanium nitride, or a resin film in which a light-shielding agent is dispersed.

The filter segments can be formed by, for example, a printing method, an electrodeposition method, a transfer method, an ink-jet method, a photolithography method, or the like.
The printing method is excellent in terms of low cost and mass productivity as a method for producing color filters, since a pattern can be formed simply by repeating printing and drying of a photosensitive coloring composition prepared as a printing ink. Furthermore, the development of printing technology has made it possible to print fine patterns with high dimensional accuracy and smoothness. In order to perform printing, it is preferable to have a composition that does not cause the ink to dry or solidify on the printing plate or blanket. In addition, control of the fluidity of the ink on the printing machine is also important, and the ink viscosity can be adjusted by using a dispersant or an extender pigment.

The electrodeposition method uses a transparent conductive film formed on a transparent substrate, and uses electrophoresis of colloidal particles to electrodeposit filter segments of each color onto the transparent conductive film to produce a color filter. The transfer method forms filter segments on the release-treated surface of a release sheet. These filter segments are then transferred to a transparent substrate to produce the filter.

In the photolithography method, for example, a photosensitive coloring composition containing a colorant of a certain color tone is applied to a transparent substrate so that the dry film thickness is about 0.2 to 5 μm to form a film. The obtained film (hereinafter referred to as the first film) is exposed (irradiated with light) through a mask having a predetermined pattern. Next, the film is developed by immersing it in a solvent or an alkaline developer or spraying the developer with a spray or the like, and the uncured parts are removed to obtain the desired pattern. By carrying out this process in the same manner using a photosensitive coloring composition containing a colorant of another color tone, a color filter having filter segments of each color can be manufactured. In addition, a second film (oxygen barrier film) can be formed on the first film before exposure using polyvinyl alcohol or a water-soluble acrylic resin. This prevents the first film from coming into contact with oxygen, and thus improves the exposure sensitivity. In addition, the color filter can be heated to cure the uncured photopolymerizable compound in the filter segment. The photolithography method is preferable because it can produce color filters with higher accuracy than the printing method.

Examples of coating devices include spray coaters, spin coaters, slit coaters, and roll coaters. A drying process can be carried out during coating. Examples of drying devices include hot air ovens and infrared heaters.

The developer may be an alkaline developer, such as an inorganic alkali such as sodium carbonate or sodium hydroxide; or an organic alkali such as dimethylbenzylamine or triethanolamine. A defoamer or surfactant may also be added to the developer.

The color filter of the present invention is bonded to an opposing substrate using a sealant, liquid crystal is injected through an injection port provided in the seal portion, the injection port is sealed, and a polarizing film or retardation film is bonded to the outside of the substrate as necessary, to produce a color liquid crystal display device. This color liquid crystal display device can be used in liquid crystal display modes that use color filters such as twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), and optically concave bend (OCB).

In this specification, the color filters 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 imaging element>
The solid-state imaging device of this specification includes at least a color filter.
The solid-state imaging element has, for example, a substrate on which a plurality of photodiodes constituting a light receiving area of the solid-state imaging element (such as a CCD sensor, a CMOS sensor, an organic CMOS sensor, etc.) and a transfer electrode made of polysilicon or the like, a light-shielding film made of tungsten or the like with only the light receiving portions of the photodiodes being opened on the photodiodes and the transfer electrodes, a device protection film made of silicon nitride or the like formed on the light-shielding film so as to cover the entire light-shielding film and the light receiving portions of the photodiodes, and a color filter for solid-state imaging elements of the present invention on the device protection film.
Furthermore, the device may have a focusing means (such as a microlens, hereinafter the same) on the device protection layer and below the color filter (on the side closer to the substrate), or the focusing means may be on the color filter.
The organic CMOS sensor is composed of a thin panchromatic organic photoelectric conversion film as a photoelectric conversion layer and a CMOS signal readout substrate, and has a two-layer hybrid structure in which the organic material is responsible for capturing light and converting it into an electrical signal, and the inorganic material is responsible for extracting the electrical signal to the outside, and in principle, the aperture ratio for incident light can be 100%. The organic photoelectric conversion film is a structure-free continuous film that can be laid on the CMOS signal readout substrate, so it does not require expensive microfabrication processes and is suitable for miniaturizing filter segments.
The arrangement of the color filter segments is not particularly limited, and any known method can be used.

<Liquid Crystal Display Device>
The liquid crystal display device of this specification includes a color filter.
The liquid crystal display device includes the color filter of the present invention and a light source. Examples of the light source include a cold cathode fluorescent lamp (CCFL) and a white LED. In the present invention, it is preferable to use a white LED because it widens the red reproduction range. Fig. 1 is a schematic cross-sectional view of a liquid crystal display device 10. The device 10 shown in Fig. 1 includes a pair of transparent substrates 11 and 21 arranged to face each other with a space therebetween, and a liquid crystal LC is sealed between them.

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

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

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

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

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

Specific examples of LED1 include NSSW306D-HG-V1 (manufactured by Nichia Chemicals) and NSSW304D-HG-V1 (manufactured by Nichia Chemicals).

Specific examples of LED2 include NSSW440 (manufactured by Nichia Chemicals) and NSSW304D (manufactured by Nichia Chemicals).

The present invention will be described below with reference to examples. In the examples, "parts" and "%" respectively represent "parts by mass" and "% by mass". It goes without saying that the present invention is not limited to the examples.
In addition, Examples 1 to 42, 101 to 154, 201 to 209, 211 to 213, 248 to 252, 254 to 256, and 291 to 302 are reference examples.

First, we will explain each measurement method.

(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. The apparatus used was an HLC-8220GPC (manufactured by Tosoh Corporation), with two separation columns connected in series, both of which were packed with "TSK-GEL SUPER HZM-N" in series, and the measurements were performed at an oven temperature of 40°C, a THF solution as the eluent, and a flow rate of 0.35 ml/min.
The sample was dissolved in a solvent containing 1 wt % of the above eluent, and 20 microliters was injected. The molecular weights are all polystyrene equivalent values.

(Acid value of resin (mgKOH/g))
80 ml of acetone and 10 ml of water were added to 0.5 to 1 g of the resin solution, and the solution was stirred to dissolve uniformly, and titrated with an automatic titrator ("COM-555", Hiranuma Sangyo Co., Ltd.) using a 0.1 mol/L KOH aqueous solution as a titrant to measure the acid value (mg KOH/g) of the resin solution. The acid value per unit of non-volatile content of the resin was calculated from the acid value of the resin solution and the concentration of the non-volatile content of the resin solution.

(Amine value of basic resin type dispersant)
The amine value of the basic resin-type dispersant is a value calculated by converting the total amine value (mg KOH/g) measured in accordance with the method of ASTM D 2074 into the non-volatile content.

<Production of finely divided phthalocyanine pigment>
(Fine Phthalocyanine Pigments A-1 to A-5)
According to the examples of JP 2017-111398 A, the fine phthalocyanine pigments (A-1) to (A-5) represented by the following chemical formulas (51) to (55) were produced.

(Fine Phthalocyanine Pigment (A-6))
Phthalocyanine pigment C.I. Pigment Green 58 (DIC Corporation "FASTGEN
A stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) was charged with 100 parts of ethyl acetate ("Pentazoline GREEN A110"), 1,200 parts of sodium chloride, and 120 parts of diethylene glycol, and the mixture was kneaded at 70° C. for 6 hours. The kneaded mixture was poured into 3,000 parts of warm water, and stirred for 1 hour while heating to 70° C. to form a slurry. The slurry was filtered and washed with water repeatedly to remove the sodium chloride and diethylene glycol, and then dried at 80° C. for one day to obtain 97 parts of a finely divided zinc phthalocyanine pigment (A-6).

(Fine Phthalocyanine Pigment (A-7))
The fine phthalocyanine pigment (A-1) and the fine phthalocyanine pigment (A-6) were mixed in equal amounts to obtain a fine phthalocyanine pigment (A-7).

(Fine Phthalocyanine Pigment (A-8))
Phthalocyanine pigment C.I. Pigment Green 36, 200 parts, sodium chloride 1
In a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho), 400 parts of sodium chloride and 360 parts of diethylene glycol were charged and kneaded for 6 hours at 80° C. Next, this kneaded mixture was poured into 8 liters of warm water, and stirred for 2 hours while heating to 80° C. to form a slurry, which was then repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 85° C. for one day to obtain 190 parts of a finely divided copper phthalocyanine pigment (A-8).

(Fine Phthalocyanine Pigment (A-9))
In a 300 mL flask, 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 were charged. The mixture was heated to 130°C over 40 hours, taken out in water, and filtered to obtain a green crude 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 charged in a 1 L double-arm kneader and kneaded at 100°C for 6 hours. After kneading, the mixture was taken out in 2 kg of water at 80°C, stirred for 1 hour, filtered, washed with hot water, dried, and pulverized to obtain a fine phthalocyanine pigment (A-9). The resulting finely divided phthalocyanine pigment (A-9) was found to be a zinc phthalocyanine halide pigment having an average of 13.97 halogen atoms per molecule, including an average of 11.46 bromine atoms and an average of 2.51 chlorine atoms, as determined by fluorescent X-ray analysis using a Rigaku ZSX100E.

(Fine Phthalocyanine Pigment (A-10))
In a 300 mL flask, 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 were charged. The mixture was heated to 130°C over 40 hours, taken out in water, and then filtered to obtain a green crude 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 charged in a 1 L double-arm kneader and kneaded at 100°C for 6 hours. After kneading, the mixture was taken out in 2 kg of water at 80°C, stirred for 1 hour, filtered, washed with hot water, dried, and pulverized to obtain a fine phthalocyanine pigment (A-10). The obtained fine phthalocyanine pigment (A-10) was found to have an average of 12.71 halogen atoms per molecule from fluorescent X-ray analysis, of which the average number of bromine atoms was 10.22, and the average number of chlorine atoms was 2.49, making it a halogenated zinc phthalocyanine pigment.

(Fine Phthalocyanine Pigment (A-11))
In a 300 mL flask, 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 were charged. The mixture was heated to 130°C over 40 hours, taken out in water, and then filtered to obtain a green crude 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 charged in a 1 L double-arm kneader and kneaded at 100°C for 6 hours. After kneading, the mixture was taken out in 2 kg of water at 80°C, stirred for 1 hour, filtered, washed with hot water, dried, and pulverized to obtain a fine phthalocyanine pigment (A-11). The obtained fine phthalocyanine pigment (A-11) was a halogenated zinc phthalocyanine pigment having an average of 11.98 halogen atoms per molecule from fluorescent X-ray analysis, an average of 9.00 bromine atoms, and an average of 2.98 chlorine atoms.

(Fine Phthalocyanine Pigment (A-12))
In a 300 mL flask, 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 were charged. The mixture was heated to 130°C over 40 hours, taken out in water, and then filtered to obtain a green crude 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 charged in a 1 L double-arm kneader and kneaded at 100°C for 6 hours. After kneading, the mixture was taken out in 2 kg of water at 80°C, stirred for 1 hour, filtered, washed with hot water, dried, and pulverized to obtain a fine phthalocyanine pigment (A-12). The obtained fine phthalocyanine pigment (A-12) was a halogenated zinc phthalocyanine pigment having an average of 12.69 halogen atoms per molecule from fluorescent X-ray analysis, an average of 8.54 bromine atoms, and an average of 4.16 chlorine atoms.

(Fine Phthalocyanine Pigment (A-13))
In a 300 mL flask, 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 were charged. The mixture was heated to 130°C over 40 hours, taken out in water, and then filtered to obtain a green crude 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 charged in a 1 L double-arm kneader and kneaded at 100°C for 6 hours. After kneading, the mixture was taken out in 2 kg of water at 80°C, stirred for 1 hour, filtered, washed with hot water, dried, and pulverized to obtain a fine phthalocyanine pigment (A-13). The obtained fine phthalocyanine pigment (A-13) was a halogenated zinc phthalocyanine pigment with an average number of halogen atoms in one molecule of 8.88 from fluorescent X-ray analysis, of which the average number of bromine atoms was 6.90 and the average number of chlorine atoms was 1.98.

<Production of finely divided yellow pigment>
(Fine Yellow Pigments (a-1) to (a-3))
According to the examples of JP 2012-226110 A, fine phthalocyanine pigments (a-1) to (a-3) of quinophthalone pigments represented by the following chemical formulas (56) to (58) were prepared. The structures are shown below.

(Fine Yellow Pigment (a-4))
100 parts of C.I. Pigment Yellow 138 (PY138) (BASF "Paliotol Yellow K0960-HD"), 700 parts of sodium chloride, and 180 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (Inoue Seisakusho) and kneaded for 6 hours at 80 ° C. This mixture was added to 2000 parts of hot water, heated to 80 ° C. and stirred for 1 hour to form a slurry, filtered and washed with water repeatedly to remove salt and solvent, and then dried at 80 ° C. for 24 hours to obtain 95 parts of finely divided yellow pigment (a-4).

(Fine Yellow Pigment (a-5))
100 parts of isoindoline yellow pigment C.I. Pigment Yellow 139 ("Irgaphor Yellow 2R-CF" manufactured by Ciba Japan Co., Ltd.), 1600 parts of sodium chloride, and 190 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader and kneaded for 10 hours at 60 ° C. Next, this mixture was put into 3 liters of warm water, heated to about 80 ° C. and stirred with a high-speed mixer for about 1 hour to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and the solvent, and then dried at 80 ° C. for one day and night to obtain a finely divided yellow pigment (a-5).

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

(Fine Yellow Pigment (a-7))
Yellow pigment C.I. Pigment Yellow 185 (Ciba Japan Co., Ltd. "Paliotol Yellow D1155"): 500 parts, sodium chloride: 500 parts, and diethylene glycol: 250 parts were charged into a stainless steel 1 gallon kneader and kneaded for 8 hours at 120 ° C. Next, this kneaded product was put into 5 liters of warm water, heated to 70 ° C. and stirred for 1 hour to make a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for a day and night to obtain a fine yellow pigment (a-7).

(Fine Yellow Pigment (a-8))
95 parts of C.I. Pigment Yellow 185 (BASF "Paliogen Yellow D1155"), 5 parts of dye derivative b-2, 10 parts of rosin maleic acid resin (Arakawa Chemical Industries "Marukid 32"), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (Inoue Seisakusho Co., Ltd.) and kneaded for 8 hours at 60 ° C. Next, this kneaded product was put into 8000 parts of hot water, heated to about 70 ° C. and stirred for 1 hour to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. 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-type dispersant (B1) having an aromatic carboxylic acid structure and a (meth)acryloyl group>
(Preparation of Resin-Type Dispersant (B1-1) Solution)
A reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer was charged with 3-mercapto-
1,2-propanediol 108 parts, pyromellitic dianhydride 174 parts, propylene glycol monomethyl ether acetate 650 parts, monobutyltin oxide 0.
2 parts of the compound obtained in the first step were charged, and the atmosphere was replaced with nitrogen gas, and the mixture was reacted at 120 ° C. for 5 hours (first step). It was confirmed that 95% or more of the acid anhydride groups were half-esterified by measuring the acid value. Next, 160 parts of the compound obtained in the first step were charged 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, and the inside of the reaction vessel was heated to 80 ° C., and 1.2 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) were added, and the mixture was reacted for 12 hours (second step). It was confirmed that 95% had reacted by measuring the non-volatile content. 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 parts of hydroquinone were charged, and the reaction was carried out until the disappearance of the peak at 2270 cm-1 due to the isocyanate group was confirmed by IR (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 with a non-volatile content of 30%. The acid value of the obtained dispersant was 68, the unsaturated double bond equivalent was 1593, and the weight average molecular weight was 13,000.

(Preparation of Solutions of Resin-Type Dispersants (B1-2) to (B1-10))
The synthesis was carried out in the same manner as in the production of the resin-type dispersant (B1-1), except that the raw materials and the amounts charged were used as shown in Table 1, to obtain solutions of resin-type dispersants (B1-2) to (B1-10) with a non-volatile content of 30%.

The 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'-biphenyltricarboxylic anhydride TMEG: ethylene glycol ditrimellitic anhydride ester (manufactured by New Japan Chemical Co., Ltd.: Rikacid 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: hydroxyl-terminated polycaprolactone-modified methacrylate (manufactured by Daicel Chemical Industries, Ltd.: 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 (Karenz MOI, manufactured by Showa Denko K.K.)
AOI: 2-acryloyloxyethyl isocyanate (Karenz AOI: manufactured by Showa Denko K.K.)
BEI: 1,1-bis(acryloyloxymethyl)ethyl isocyanate (Karens BEI, manufactured by Showa Denko K.K.)
MOI-EG: 2-methacryloyloxyethoxyethyl isocyanate (manufactured by Showa Denko K.K.: Karenz MOI-EG)

<Preparation of a solution of a resin-type dispersant (B2) having an aromatic carboxylic acid structure and a vinyl polymer moiety having no (meth)acryloyl group>
(Preparation of Resin-Type Dispersant (B2-1) Solution)
A reaction vessel equipped with a gas inlet tube, a temperature controller, a condenser, and a stirrer was charged with 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, 20 parts of tert-butyl acrylate, and 50 parts of propylene glycol monomethyl ether acetate, and substituted with nitrogen gas. The reaction vessel was heated to 50°C and stirred while adding 12 parts of 3-mercapto-1,2-propanediol. The temperature was raised to 90°C, and the reaction was continued for 7 hours while adding a solution in which 0.1 parts of 2,2'-azobisisobutyronitrile was added to 90 parts of propylene glycol monomethyl ether acetate. It was confirmed that 95% of the monomer had reacted by measuring the nonvolatile content.
Next, 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 the mixture was reacted for 7 hours at 100° C. The reaction was terminated after confirming that 98% or more of the acid anhydride groups had been half-esterified by measuring the acid value, and propylene glycol monomethyl ether acetate was added so that the nonvolatile content was 30% by measuring the nonvolatile content, thereby obtaining a resin-type dispersant (B2-1) solution having an acid value of 62 mgKOH/g and a weight average molecular weight of the vinyl polymer moiety of 8,500.

(Preparation of Solutions of Resin-Type Dispersants (B2-2) to (B2-6))
Resin-type dispersants (B2-2) to (B2-6) were obtained by synthesizing the resin-type dispersants in the same manner as in the production of the resin-type dispersant (B2-1) solution, except that the raw materials and the amounts charged were changed as shown in Table 2.

(Preparation of Resin-Type Dispersant (B2-7) Solution)
A reaction vessel equipped with a gas inlet tube, a temperature controller, a condenser, and a stirrer was charged with 10 parts of methacrylic acid, 100 parts of methyl methacrylate, 70 parts of i-butyl methacrylate, 20 parts of benzyl methacrylate, and 50 parts of PGMAc, and substituted with nitrogen gas. The reaction vessel was heated to 50°C and stirred, and 12 parts of 3-mercapto-1,2-propanediol was added. The temperature was raised to 90°C, and a solution of 0.1 parts of 2,2'-azobisisobutyronitrile added to 90 parts of PGMAc was added and reacted for 7 hours. It was confirmed that 95% had reacted by measuring the non-volatile content. 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 the reaction was carried out at 100°C for 7 hours. The reaction was terminated after confirming that 98% or more of the acid anhydride groups had been half-esterified by measuring the acid value, and the reaction solution was diluted with PGMAc so that the nonvolatile content was 30% by measuring the nonvolatile content, thereby obtaining a resin-type dispersant (B2-7) solution having an acid value of 70 mgKOH/g and a weight average molecular weight of 8,500.

(Preparation of resin-type dispersant (B2-8) solution)
In a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 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 KK), 20 parts of ETERNACOLLOXMA (manufactured by Ube Industries), and 100 parts of propylene glycol monomethyl ether acetate were charged and replaced with nitrogen gas. The inside of the reaction vessel was heated to 80°C, and a solution in which 0.1 parts of 2,2'-azobisisobutyronitrile was dissolved in 14 parts of 2-mercapto-2-methyl-1,3-propanediol was added and reacted for 10 hours. It was confirmed that 95% had reacted by measuring the nonvolatile content. Next, BPAF: 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride (manufactured by JFE Chemical Co., Ltd.) 39 parts, C-1015N (bifunctional polycarbonate polyol, trade name Kuraray Polyol C-1015N (hydroxyl value 112 mg KOH / 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 were added and reacted at 100 ° C. for 7 hours. The reaction was terminated after confirming that 98% or more of the acid anhydride group was half-esterified by measuring the acid value. The nonvolatile content was adjusted to 30% with propylene glycol monomethyl ether acetate, and a resin-type dispersant (B2-8) liquid having an acid value of 94 mg KOH / g and a weight average molecular weight of 25,000 was obtained.

(Preparation of resin-type dispersant (B2-9) solution)
In a reaction vessel equipped with a gas inlet tube, a condenser, an agitator, and a thermometer, 3 parts of trimellitic anhydride, 1 part of 3-mercapto-1,2-propanediol, 50 parts of PGMAc, and 0.1 parts of dimethylbenzylamine were charged. After replacing 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. Furthermore, 30 parts of tertiary butyl acrylate, 20 parts of ETERNACOLL OXMA (methacrylate (3-ethyloxetan-3-yl) methyl, manufactured by Ube Industries, Ltd.), 5 parts of methacrylic acid, 40 parts of ethyl acrylate, and 10 parts of PGMAc were charged, and 0.2 parts of 2,2'-azobisisobutyronitrile were added in 15 portions every 30 minutes while maintaining the inside of the reaction vessel at 80°C. The nonvolatile content was measured 1 hour after the final addition, and it was confirmed that 95% of the monomer had reacted. The solution was diluted with PGMAc so that the nonvolatile content was 30% by nonvolatile content measurement, to obtain a resin-type dispersant (B2-9) solution having an acid value of 51 mgKOH/g and a weight average molecular weight (Mw) of 24,000 per nonvolatile content.

<Preparation of Basic Resin-Type Dispersant (B3) Solution>
(Basic resin type dispersant (B3-1) solution)
In a reaction apparatus equipped with a gas inlet tube, a condenser, an agitator, and a thermometer, 40 parts of methyl methacrylate, 10 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine as a catalyst were charged, and the mixture was stirred at 50° C. for 1 hour while flowing nitrogen, and 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 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 nonvolatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more based on the nonvolatile 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 charged into the reaction apparatus, and the mixture was stirred while maintaining 110° C. under a nitrogen atmosphere, and the reaction was continued. Two hours after the addition, the polymerization solution was sampled and the nonvolatile content was measured, and it was confirmed that the polymerization conversion rate of the second block (A block) was 98% or more calculated from the nonvolatile content, and the reaction solution was cooled to room temperature to stop the polymerization. As a result of GPC measurement, the mass average molecular weight of the polymer was 20,000, the molecular weight distribution Mw/Mn was 1.4, and the reaction conversion rate was 98.5%. In this way, a basic resin type dispersant (B3-1) having an amine value of 169.8 mgKOH/g per nonvolatile content 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 nonvolatile content, and propylene glycol monomethyl ether acetate (PGMAc) was added to the previously synthesized basic resin type dispersant (B3-1) so that the nonvolatile content was 30% by mass, to prepare a basic resin type dispersant (B3-1) solution of an A-B-A block polymer.

(Basic resin type dispersant (B3-2) solution)
A reaction vessel equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer was charged with 133 parts of PGMAc, and the temperature was raised to 110 ° C. while replacing with nitrogen. A dropping vessel was charged with 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), and after stirring until uniform, the mixture was dropped into the reaction vessel over 2 hours, and the reaction was continued at the same temperature for 3 hours. In this way, a basic resin-type dispersant (B3-2) having an amine value of 345 mg KOH / g per nonvolatile content and a number average molecular weight (Mn) of 3000 was obtained. The solution was diluted in the same manner as the resin-type dispersant (B3-1) solution to prepare a basic resin-type dispersant (B3-2) solution of a random polymer.

(Basic resin type dispersant (B3-3) solution)
A reaction vessel equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer was charged with 133 parts of PGMAc, 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 6 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) were charged into a dropping vessel, stirred until uniform, and then dropped into the reaction vessel over 2 hours, and the reaction was continued at the same temperature for 3 hours. In this way, a basic resin type dispersant (B3-3) with an amine value of 201 mg KOH / g per nonvolatile content and a number average molecular weight of 3,800 (Mn) was obtained. The solution was diluted in the same manner as the basic resin type dispersant (B3-1) solution to prepare a basic resin type dispersant (B3-3) solution of a random polymer.

(Basic resin type dispersant (B3-4) solution)
A flask equipped with a cooling tube and a stirrer was charged with 1.0 part 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, 16 parts by mass of benzyl methacrylate, 16 parts by mass of triethylene glycol ethyl ether methacrylate, and 3.6 parts by mass of cumyl dithiobenzoate, and substituted with nitrogen for 30 minutes. Thereafter, the temperature of the reaction solution was raised to 60° C. with gentle stirring, and this temperature was maintained for 24 hours to carry out living radical polymerization.
Next, to this reaction solution was added a solution in which 1.0 part by mass of AIBN and 54 parts by mass of dimethylaminoethyl methacrylate were dissolved in 108 parts by mass of propylene glycol monomethyl ether acetate and the atmosphere was replaced with nitrogen for 30 minutes, and living radical polymerization was carried out at 60°C for 24 hours. Thereafter, the mixture was diluted in the same manner as the basic resin type dispersant (B3-1) solution to prepare a basic resin type dispersant (B3-4) solution of a random polymer.

(Basic resin type dispersant (B3-5) solution)
In a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 500 parts of methyl methacrylate, 22 parts of thioglycerol, and 511 parts of propylene glycol monomethyl ether acetate were charged, and the atmosphere was replaced with nitrogen gas. The reaction vessel was heated to 90°C, and 0.50 parts of AIBN were added, followed by reaction for 7 hours. After confirming that 95% had reacted by measuring the non-volatile content, the mixture was cooled to room temperature to obtain a 50% non-volatile solution of a vinyl polymer having a weight average molecular weight of 5200 and two free hydroxyl groups at one end region. Then, 90.4 parts of isophorone diisocyanate, 45.1 parts of propylene glycol monomethyl ether acetate, and 0.11 parts of dibutyltin dilaurate as a catalyst were charged, and the atmosphere was replaced with nitrogen gas. The reaction vessel was heated to 100°C, reacted for 3 hours, and then cooled to 40°C to obtain a prepolymer solution having an isocyanate group. 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 30 minutes, and the reaction was continued for another hour, after which the reaction was terminated by cooling to room temperature. If necessary, a portion of the solvent was removed by distillation under reduced pressure, and then the mixture was diluted in the same manner as the basic resin type dispersant (B3-1) solution to prepare a basic resin type dispersant (B3-5) solution.

(Basic resin type dispersant (B3-6) solution)
In a reaction apparatus equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer, 30 parts of methyl methacrylate, 30 parts of n-butyl methacrylate, 20 parts of hydroxyethyl methacrylate, and 13.2 parts of tetramethylethylenediamine were charged, and the mixture was stirred at 50° C. for 1 hour while flowing nitrogen, and 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 nonvolatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more based on the nonvolatile content.
Next, 61 parts of PGMAc and 20 parts of 1,2,2,6,6-pentamethylpiperidyl methacrylate (Fancryl FA-711MM, manufactured by Hitachi Chemical Co., Ltd.) as a second block (A block) monomer were added to this reaction apparatus, and the reaction was continued by stirring while maintaining a nitrogen atmosphere at 110° C. Two hours after the addition of 1,2,2,6,6-pentamethylpiperidyl methacrylate, a sample was taken from the polymerization solution and the nonvolatile content was measured. It was confirmed that the polymerization conversion rate of the second block (A block) was 98% or more calculated from the nonvolatile content, and the reaction solution was cooled to room temperature to terminate the polymerization.
In this way, a basic group resin-type dispersant (B3-6) having a piperidyl skeleton and an amine value per nonvolatile content of 57 mgKOH/g and a number average molecular weight of 4,500 (Mn) was obtained.
The resin-type dispersant (B3-1) solution was diluted in the same manner as above to prepare a basic group resin-type dispersant (B3-6) solution of an ABA block polymer.

(Basic resin type dispersant (B3-7) solution)
A [quaternized product of 3-(N,N-dimethylamino)propylacrylamide/methoxypolyethylene glycol methacrylate copolymer (23/77% by weight); quaternization rate: 27 mol%)] was synthesized by the production method of pigment dispersant (1) described in Production Example 1 of Japanese Patent No. 5513691, and diluted in the same manner as the resin-type dispersant (B3-1) solution to prepare a basic-base resin-type dispersant (B3-7) solution.

<Production Example of Binder Resin (C)>
(Preparation of binder resin (C-1) liquid)
A separable 4-neck flask was fitted with a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube and a stirrer to prepare a reaction vessel. 196 parts of cyclohexanone were charged, and the temperature was raised to 80 ° C., and the inside of the reaction vessel was replaced with nitrogen. From the dropping 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 (Toagosei Co., Ltd. "Aronix M110"), and 1.1 parts of 2,2'-azobisisobutyronitrile were added dropwise over 2 hours. After the dropping was completed, the reaction was continued for another 3 hours to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution were sampled and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and PGMAc was added to the resin solution synthesized earlier so that the nonvolatile content was 20% to prepare a binder resin (C-1) liquid. The weight average molecular weight (Mw) was 26,000.

(Preparation of binder resin (C-2) liquid)
A separable 4-neck flask was fitted with a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube and a stirrer. 207 parts of cyclohexanone was charged into the reaction vessel, which was then heated to 80°C and substituted with nitrogen in the reaction vessel. From the dropping tube, a mixture of 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 1.33 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropping, the reaction was continued for another 3 hours to obtain a copolymer resin solution. Next, the total amount of the copolymer solution obtained was stirred while stopping the nitrogen gas and injecting dry air for 1 hour, and then cooled to room temperature, and a mixture of 6.5 parts of 2-methacryloyloxyethyl isocyanate (Karenz MOI manufactured by Showa Denko K.K.), 0.08 parts of dibutyltin laurate, and 26 parts of cyclohexanone was dropped at 70 ° C. for 3 hours. After the dropwise addition, the reaction was continued for another 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, and cyclohexanone was added to the resin solution previously synthesized so that the non-volatile content was 20% 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-neck flask equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube and a stirrer was charged with 370 parts of cyclohexanone, and the temperature was raised to 80 ° C., and the inside of the flask was replaced with nitrogen, and then a mixture of 18 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toa Gosei Co., Ltd.), 10 parts of benzyl methacrylate, 18.2 parts of glycidyl methacrylate, 25 parts of methyl methacrylate, and 2.0 parts of 2,2'-azobisisobutyronitrile was dropped over 2 hours from the dropping tube. After the dropping, the mixture was further reacted at 100 ° C. for 3 hours, and then a solution of 1.0 part of azobisisobutyronitrile in 50 parts of cyclohexanone was added, and the reaction was continued at 100 ° C. for 1 hour. Next, the inside of the vessel was replaced with air, and 9.3 parts of acrylic acid (100% of glycidyl groups), 0.5 parts of trisdimethylaminophenol, and 0.1 parts of hydroquinone were added to the vessel, and the reaction was continued for 6 hours at 120° C., and the reaction was terminated when the non-volatile acid value reached 0.5, to obtain an acrylic resin solution. Furthermore, 19.5 parts of tetrahydrophthalic anhydride (100 mol% of the generated hydroxyl groups) and 0.5 parts of triethylamine were added, and the reaction was continued for 3.5 hours at 120° C., to obtain an acrylic resin solution.
After cooling to room temperature, about 2 g of the resin solution was sampled and dried at 180 ° C for 20 minutes to measure the non-volatile content, and PGMAc was added to the previously synthesized resin solution so that the non-volatile content was 20 mass % 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 tube was prepared as a reaction vessel. Meanwhile, a thoroughly stirred mixture of 40 parts of dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, 40 parts of methacrylic acid, 120 parts of methyl methacrylate, 4 parts of t-butylperoxy-2-ethylhexanoate ("Perbutyl O" manufactured by Nippon Oil & Fats), and 40 parts of PGMAc was prepared as a monomer dropping vessel. A thoroughly stirred mixture of 8 parts of n-dodecanethiol and 32 parts of PGMAc was prepared as a chain transfer agent dropping vessel.
395 parts of PGMAc was charged into the reaction vessel, and after replacing with nitrogen, the temperature of the reaction vessel was raised to 90 ° C. by heating in an oil bath while stirring. After the temperature of the reaction vessel was stabilized at 90 ° C., dropping was started from the monomer dropping vessel and the chain transfer agent dropping vessel. Dropping was carried out over 135 minutes while maintaining the temperature at 90 ° C. 60 minutes after the end of dropping, the temperature was raised to 110 ° C. After maintaining 110 ° C. for 3 hours, a gas inlet tube was attached to the separable flask, and bubbling of a mixed gas of oxygen / nitrogen = 5 / 95 (volume ratio) was started. Next, 70 parts of glycidyl methacrylate, 0.4 parts of 2,2'-methylenebis (4-methyl-6-t-butylphenol), and 0.8 parts of triethylamine were charged into the reaction vessel, and the reaction was carried out at 110 ° C. for 12 hours. Then, 150 parts of PGMAc was added and cooled to room temperature, and about 2 g of the resin solution was sampled and dried at 180°C for 20 minutes to measure the non-volatile content, and PGMAc was added to the previously synthesized resin solution so that the non-volatile content was 20% by mass to obtain a binder resin (C-4) solution. The weight average molecular weight of the resin was 18,000, and the acid value per non-volatile content was 2 mgKOH/g.

<Method for producing colored composition (single color)>
[Example 1]
(Preparation of Colored Composition (R-1))
The mixture below was stirred and mixed to be homogeneous, and then dispersed for 3 hours in an Eiger mill ("Mini Model M-250 MKII" manufactured by Eiger Japan Co., Ltd.) using zirconia beads having a diameter of 0.5 mm. The mixture was then filtered through a filter having a pore size of 5.0 μm to prepare a colored composition (R-1) having a pigment content of 80% in the nonvolatile matter and a nonvolatile matter 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 Compositions (R-2 to R-54))
Colored compositions (R-2 to R-54) having a pigment content of 80% in the nonvolatile matter were prepared in the same manner as in Example 1, except that the material types and masses were changed as shown in Table 3.

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

[Examples 102 to 154, Comparative Example 101]
(Preparation of Colored Compositions (X-2 to 55))
Colored compositions (X-2 to 55) were prepared in the same manner as in Example 101, except that the material types and masses were changed as shown in Table 4.

<Evaluation of Colored Composition>
The obtained colored compositions (R-1 to 44, X-1 to 55) were subjected to tests for viscosity and storage stability by the following methods. The test results are shown in Table 5.
The evaluation is as follows:
◎: Very good, ◯: Good, △: Practical, ×: Not suitable for practical use

(Measurement of Viscosity Characteristics)
The viscosity was measured at a rotation speed of 20 rpm using an E-type viscometer ("ELD type viscometer" manufactured by Toki Sangyo Co., Ltd.) and the evaluation ranks are as follows.
○: Viscosity 4.0 or more and less than 20.0 ×: Viscosity 20 or more

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

(Foreign matter evaluation)
The foreign matter evaluation was carried out by applying the coloring composition to a transparent substrate so that the dried film was about 2.0 μm thick, and then heat-treating the coated substrate at 230° C. for 1 hour, and counting the number of foreign matters in the film. The evaluation was carried out by observing the surface using a metal microscope "BX60" (manufactured by Olympus Systems Co., Ltd.). The magnification was set to 500 times, and the number of foreign matters observable in any five visual fields in transmission was counted. The evaluation criteria were as follows.
◎: The number of foreign objects is less than 5. ◯: The number of foreign objects is 5 or more and less than 20. △: The number of foreign objects is 21 or more and less than 100. ×: The number of foreign objects is 100 or more.

<Method for producing photosensitive coloring composition>
[Example 201]
(Photosensitive coloring composition (Y-1))
The following raw materials were mixed and 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 monomer (D): 2.0 parts Photopolymerization initiator (E): 1.8 parts Sensitizer (H): 0.2 parts Thiol-based chain transfer agent (I): 0.4 parts Polymerization inhibitor (J): 0.1 parts Ultraviolet absorber (K): 0.1 parts Antioxidant (L): 0.1 parts Leveling agent (M: non-volatile content 3%): 1.0 parts Storage stabilizer (N): 0.1 parts Silane coupling agent (O): 0.2 parts Solvent (P): 13.0 parts

[Examples 202 to 302, Comparative Examples 201 to 203]
(Preparation of Photosensitive Coloring Compositions (Y-2 to 105))
Except for changing the coloring composition and binder resin solution of Example 201 as shown in Table 6, the same procedure as in Example 201 was carried out to prepare photosensitive coloring compositions (Y-2 to 105). The raw materials for each are 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)],
(CE-1-2) Glycidyl etherified epoxy compounds of sorbitol
[Denacol EX611 (Nagase Chemtex)],
(CE-1-3) Triglycidyl isocyanurate (CE-1-1) to (CE-1-3) were mixed in equal amounts to prepare 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)]

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

(D-5) Multifunctional urethane acrylate prepared as follows: Pentaerythritol triacrylate (432 g) and hexamethylene diisocyanate (84 g) were charged into a 1-liter five-necked reaction vessel and reacted at 60° C. for 8 hours to obtain a product containing a multifunctional urethane acrylate (D-5) having a (meth)acryloyl group. The proportion of the multifunctional urethane acrylate (D-5) in the product was 70 mass%, with the remainder being other photopolymerizable monomers. It was confirmed by IR analysis that no isocyanate groups were present in the reaction product.

(D-6) Difunctional 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 prepare a photopolymerizable monomer (D).

<Photopolymerization initiator (E)>
(E-1) 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one [Irgacure 907 (BASF Japan)]
(E-2) 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone [Irgacure 379 (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 Chemical Industry Co., Ltd.)]
(E-5) p-Dimethylaminoacetophenone [DMA (manufactured by Daikifine Co., Ltd.)]
(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 (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 prepare 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 Chemark Chemical Co.)]
The above (H-1) and (H-2) were mixed in equal amounts to prepare a sensitizer (H).

<Thiol-Based Chain Transfer Agent (I)>
(I-1) Trimethylolethane tris(3-mercaptobutyrate) [TEMB (Showa Denko)]
(I-2) Trimethylolpropane tris(3-mercaptobutyrate) [TPMB (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 prepare a thiol-based chain transfer agent (I).

<Polymerization inhibitor (J)>
(J-1) 3-methylcatechol (J-2) methylhydroquinone (J-3) t-butylhydroquinone The above (J-1) to (J-3) were mixed in equal amounts to prepare a polymerization inhibitor (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 [TINUVIN 400 (manufactured by BASF Japan)]
(K-2) 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol [TINUVIN 900 (manufactured by BASF Japan)]
The above (K-1) and (K-2) were mixed in equal amounts to prepare 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. The above (L-1) to (L-5) were mixed in equal amounts to give antioxidant (L).

<Leveling Agent (M)>
1 copy of "BYK-330" manufactured by BYK-Chemie,
1 copy of DIC "Megafac F-551"
A mixed solution of 1 part of Kao Corporation's "Emulgen 103" dissolved 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 prepare 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 prepare a silane coupling agent (O).

<Solvent (P)>
(P-1) PGMAc 30 parts (P-2) Cyclohexanone 30 parts (P-3) Ethyl 3-ethoxypropionate 10 parts (P-4) Propylene glycol monomethyl ether 10 parts (P-5) Cyclohexanol acetate 10 parts (P-6) Dipropylene glycol methyl ether acetate 10 parts The above (P-1) to (P-6) were mixed in the above parts by mass to obtain solvent (P).

<Evaluation of Photosensitive Coloring Composition>
Each test was carried out by the following method, and the test results are shown in Tables 7-1 and 7-2.
The meaning of the evaluation rank is as follows:
◎: Very good 〇: Good △: Practical ×: Not suitable for practical use

(Measurement of Viscosity Characteristics)
The viscosity was measured at a rotation speed of 20 rpm using an E-type viscometer ("ELD type viscometer" manufactured by Toki Sangyo Co., Ltd.) and the evaluation ranks are as follows.
Good: Viscosity 2.0 or more and less than 10.0 Bad: Viscosity 10.0 or more (storage stability)
The storage stability of the photosensitive coloring compositions obtained in the Examples and Comparative Examples was evaluated by the following method.
The initial viscosity on the day after the photosensitive coloring composition was prepared and the viscosity over time after aging at 40° C. for one week were measured using an E-type viscometer ("ELD type viscometer" manufactured by Toki Sangyo Co., Ltd.) at 25° C. and a rotation speed of 50 rpm. From the initial viscosity and the viscosity over time, the viscosity change rate over time was calculated using the following formula, and the storage stability was evaluated in two stages.
[Change rate of viscosity over time] = |([initial viscosity] - [viscosity over time]) / [initial viscosity] | x 100
◎: Change rate is less than 5%. ○: Change rate is 5% or more but less than 10%. △: Change rate is 10% or more but less than 15%. ×: Change rate is 15% or more.

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

[Residue evaluation]
A black matrix was patterned on a 100 mm x 100 mm, 0.7 mm thick glass substrate, and the obtained photosensitive coloring composition was applied to the substrate using a spin coater, and the obtained photosensitive coloring composition was dried at 90 ° C for 90 seconds to remove the solvent, to obtain a coating having a thickness of 1.0 μm. The coating was irradiated with 100 mJ / cm ² ultraviolet light using an ultra-high pressure mercury lamp through a photomask having a predetermined pattern, and the uncured parts were removed by spray development using an alkaline developer consisting of a 0.2 mass % aqueous sodium carbonate solution to form a desired pattern. The obtained coating was subjected to a heat treatment for 20 minutes in an oven at 230 ° C to form a filter segment. The thickness of the coating was measured using Dektak 3030 (manufactured by Japan Vacuum Engineering Co., Ltd.). Using the evaluation substrate thus prepared, the parts removed with the developer were observed using an electron microscope, and the presence or absence of residue was evaluated according to the following criteria.
◯: No residue was found. △: Slight residue was found.
×: Residue present

(Foreign matter evaluation)
The foreign matter evaluation was carried out by coating a photosensitive coloring composition on a transparent substrate so that the dry film was about 2.0 μm thick, and then heat-treating the coated substrate at 230° C. for 1 hour in an oven, and counting the number of foreign matters in the film. The evaluation was carried out by observing the surface using a metal microscope "BX60" (manufactured by Olympus Systems Co., Ltd.). The magnification was set to 500 times, and the number of foreign matters observable in any five visual fields in transmission was counted. The evaluation criteria were as follows.
◎: The number of foreign objects is less than 5. ◯: The number of foreign objects is 5 or more and less than 20. △: The number of foreign objects is 21 or more and less than 100. ×: The number of foreign objects is 100 or more.

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

[Evaluation of crystalline foreign matter]
The pattern obtained in the residue evaluation was heated on a hot plate at 230° C. for 300 seconds, and 10 locations of the pixel pattern were observed under a microscope to confirm the presence or absence of crystal precipitates.
◯: No precipitates were observed △: 1 or more but less than 5 precipitates ×: 5 or more precipitates

Claims (5)

A photosensitive coloring composition comprising an organic pigment (A), a resin-type dispersant (B), a binder resin (C) (excluding a resin having a maleimide structure), a polymerizable compound (D), and a photopolymerization initiator (E),
The organic pigment (A) includes at least one pigment selected from the group consisting of a zinc phthalocyanine pigment (A1) and an aluminum phthalocyanine pigment (A2);
The content of the organic pigment (A) is 40 to 90 mass% in 100 mass% of the nonvolatile content 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, a resin type dispersant (B2) having an aromatic carboxylic acid structure and a vinyl polymer moiety not having a (meth)acryloyl group , and a resin type dispersant (B3) having a basic group,
The resin-type dispersant (B) contains 34 to 100 parts by mass of the resin-type dispersant (B1),
A photosensitive coloring composition comprising 0.5 to 50 parts by mass of a binder resin (C) based on 100 parts by mass of a resin-type dispersant (B). The photosensitive coloring composition according to claim 1 , wherein the organic pigment (A) comprises a yellow pigment (a). A color filter formed from the photosensitive coloring composition according to claim 1 or 2 . A solid-state imaging device comprising the color filter according to claim 3 . A liquid crystal display device comprising the color filter according to claim 3 .

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