JP7375330B2 - Colored compositions, photosensitive coloring compositions, color filters, and liquid crystal display devices - Google Patents

Description

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

Color filters used in liquid crystal display devices, solid-state image sensors, etc. are manufactured by forming fine patterns using photosensitive coloring compositions using photolithography. Further improvements in image quality and high definition are required, and color filters are also required to be further refined.

Patent Document 1 discloses a colored composition using a block polymer having a quaternary ammonium base as a dispersant.

Japanese Patent Application Publication No. 2002-31713

However, conventional coloring compositions have problems in that their viscosity has low stability over time and that foreign matter is generated in the film after development.

An object of the present invention is to provide a coloring composition, a photosensitive coloring composition, a color filter, and a liquid crystal display device, which have low viscosity and good stability over time, and can suppress foreign matter in a film after development. do.

The colored composition of the present invention includes a red pigment (A), a resin-type dispersant (B), and a binder resin (C),
The resin type dispersant includes the following dispersant (B1) or (B2).
(B1) A resin-type dispersant containing a basic resin-type dispersant (b1), a phosphoric acid-based resin-type dispersant (b2), and a carboxylic acid-based resin-type dispersant (b4).
(B2) A salt (b3) of a compound represented by the following general formula (1) or a compound represented by general formula (2) and a basic resin type dispersant (b1), and a carboxylic acid resin type dispersant (b4) resin type dispersant containing.

However, in the general formula (1) and the general formula (2), R ¹ and R ² each independently represent a hydrogen atom, a hydroxyl group, a straight chain, branched chain or cyclic alkyl group having 1 to 20 carbon atoms, vinyl group, a phenyl group to a benzyl group which may have a substituent, or -O-R ⁴ , and R ⁴ is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a substituted It represents a phenyl group to a benzyl group which may have a group, or a (meth)acryloyl group via an alkylene group having 1 to 4 carbon atoms. However, at least one of R ¹ and R ² contains a carbon atom. R ³ represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group or benzyl group which may have a substituent, or -O-R ⁴ .

ADVANTAGE OF THE INVENTION According to the above-mentioned present invention, it is possible to provide a colored composition which has a low viscosity, has good viscosity stability over time, and can suppress foreign substances in a film after development.

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

Define terms used herein. When expressed as "(meth)acryloyl", "(meth)acrylic", "(meth)acrylic acid", "(meth)acrylate", or "(meth)acrylamide", unless otherwise specified, each , "acryloyl and/or methacryloyl", "acrylic and/or methacrylic", "acrylic acid and/or methacrylic acid", "acrylate and/or methacrylate" or "acrylamide and/or methacrylamide". "C.I." mentioned herein means color index (C.I.). Colorants include pigments and dyes.

The colored composition of the present invention includes a red pigment (A), a resin-type dispersant (B), and a binder resin (C),
The resin-type dispersant includes the following dispersant (B1) or (B2).
(B1) A resin-type dispersant containing a basic resin-type dispersant (b1), a phosphoric acid-based resin-type dispersant (b2), and a carboxylic acid-based resin-type dispersant (b4).
(B2) A salt (b3) of a compound represented by the following general formula (1) or a compound represented by general formula (2) and a basic resin type dispersant (b1), and a carboxylic acid resin type dispersant (b4) resin type dispersant containing.

However, in the general formula (1) and the general formula (2), R ¹ and R ² each independently represent a hydrogen atom, a hydroxyl group, a straight chain, branched chain or cyclic alkyl group having 1 to 20 carbon atoms, vinyl group, a phenyl group to a benzyl group which may have a substituent, or -O-R ⁴ , and R ⁴ is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a substituted It represents a phenyl group to a benzyl group which may have a group, or a (meth)acryloyl group via an alkylene group having 1 to 4 carbon atoms. However, at least one of R ¹ and R ² contains a carbon atom. R ³ represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group or benzyl group which may have a substituent, or -O-R ⁴ .

The colored composition of the present invention greatly improves the dispersion stability of the red pigment (A) by including the dispersant (B1) or (B2). Therefore, the stability of the viscosity over time is good, and furthermore, the dispersion state of the red pigment (A) can be maintained in the film after development by photolithography, and the generation of foreign matter due to aggregation of the red pigments can be suppressed.

<Red pigment (A)>
As the red pigment (A), known pigments can be used. It is preferable to use a yellow pigment in the coloring composition in order to adjust the color tone of the coating. Note that the coloring composition may contain other organic pigments, inorganic pigments, dyes, etc. in order to obtain desired optical properties.
A red pigment (A), for example C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53: 3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81: 3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, 287, 291295, 296, and the like. Among these, from the viewpoint of heat resistance, light resistance, and transmittance of the filter segment, C.I. I. Pigment Red 48:1, 122, 177, 224, 242, 269, 254, 291, 295, 296, more preferably C.I. I. Pigment Red 177, 254, 291, 295, and 296.

(yellow pigment)
Yellow pigments include, for example, C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 192, 193, 194, 196, 198, 199, 213, 214, 231, 233 and the like. Among these, C. I. Pigment Yellow 138, 139, 150, 185, 231, and 233 are preferred.

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

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

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

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

The chemical structures of dyes include, for example, azo dyes, disazo dyes, azomethine dyes (indoaniline dyes, indophenol dyes, etc.), dipyrromethene dyes, quinone dyes (benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, etc.). dyes, anthrapyridone dyes, etc.), carbonium dyes (diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, etc.), quinone imine dyes (oxazine dyes, thiazine dyes, etc.), azine dyes , polymethine dyes (oxonol dyes, merocyanine dyes, arylidene dyes, styryl dyes, cyanine dyes, squarylium dyes, croconium dyes, etc.), quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes, perinone dyes Examples include dyes, indigo dyes, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, and rhodamine dyes. Among these, from the viewpoint of color characteristics such as hue, color separation, and color unevenness, azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, squarylium dyes, Quinophthalone dyes, phthalocyanine dyes, and subphthalocyanine dyes are preferred, and xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, and phthalocyanine dyes are more preferred. The specific structure of dyes can be found in the ``New Edition Dye Handbook'' (edited by the Organic Synthetic Chemistry Society; Maruzen, 1970), ``Color Index'' (The Society of Dyers and Colourists), and ``Pigment Handbook'' (edited by Okawara et al.; Kodansha, 1986). etc. are listed.

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

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

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

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

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

In this specification, the red pigment (A) is essential, and other pigments and dyes can be used in appropriate combinations.

<Resin type dispersant (B)>
The resin-type dispersant (B) includes the following dispersant (B1) or (B2).
(B1) A resin-type dispersant containing a basic resin-type dispersant (b1), a phosphoric acid-based resin-type dispersant (b2), and a carboxylic acid-based resin-type dispersant (b4).
(B2) A salt (b3) of a compound represented by the following general formula (1) or a compound represented by general formula (2) and a basic resin type dispersant (b1), and a carboxylic acid resin type dispersant (b4) resin type dispersant containing.

General formula (1) General formula (2)

However, in the general formula (1) and the general formula (2), R ¹ and R ² each independently represent a hydrogen atom, a hydroxyl group, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, vinyl group, a phenyl group to a benzyl group which may have a substituent, or -O-R ⁴ , and R ⁴ is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a substituted It represents a phenyl group to a benzyl group which may have a group, or a (meth)acryloyl group via an alkylene group having 1 to 4 carbon atoms. However, at least one of R ¹ and R ² contains a carbon atom. R ³ represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group or benzyl group which may have a substituent, or -O-R ⁴ .

The amount of the resin-type dispersant (B) used is preferably about 3 to 200 parts by weight, more preferably 5 to 100 parts by weight, per 100 parts by weight of the red pigment (A). When used in an appropriate amount, dispersion stability is further improved.

<Basic resin type dispersant (b1)>
The basic resin type dispersant (b1) is, for example, a copolymer obtained by radical polymerization of a monomer mixture containing an ethylenically unsaturated monomer having a basic group. The basic resin type dispersant (b1) is a dispersant that has a pigment-affinity site containing a basic group that adsorbs to the pigment and a site that is compatible with the binder resin.

Here, the basic group is a functional group having a nitrogen atom. Examples of the basic group include a primary amino group, a secondary amino group, a tertiary amino group, a quaternary ammonium base, and a nitrogen-containing heterocycle. The basic resin type dispersant (b1) is a nitrogen atom-containing dispersant having a functional group including a primary amino group, a secondary amino group, a tertiary amino group, a quaternary ammonium base, a nitrogen-containing heterocycle, etc. in its side chain. Examples include acrylic block copolymers, random copolymers, and urethane resin type dispersants.

The basic resin type dispersant (b1) preferably has an amide bond. The basic resin type dispersant (b1) is selected from the group consisting of units represented by the following general formula (b1-1), units represented by the following general formula (b1-2), and units represented by the following general formula (b1-3). It is preferable to have one or more selected types.

In general formula (b1-1), R ⁹ to R ¹¹ each independently represent a hydrogen atom or a chain or cyclic hydrocarbon group which may ^{have a} substituent; Two or more of them may be bonded to each other to form a cyclic structure. R ¹² represents a hydrogen atom or a methyl group, X represents a divalent linking group, and Y ⁻ represents a counter anion.

In general formula (b1-2), R ¹³ and R ¹⁴ each independently represent a hydrogen atom or a chain or cyclic hydrocarbon group which may have a substituent, and R ¹³ and R ¹⁴ They may be bonded to each other to form a cyclic structure. R ¹² represents a hydrogen atom or a methyl group, and X represents a divalent linking group.

In general formula (b1-3), R ¹⁵ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an acyl group, an oxyradical group, or OR ²⁰ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms ^{, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an acyl group, and R 16 ,} R ¹⁷ , R ¹⁸ and R ¹⁹ each independently represent a methyl group, an ethyl group, or a phenyl group. R ¹² represents a hydrogen atom or a methyl group, and X represents a divalent linking group.

R ⁹ to R ¹¹ in general formula (b1-1) are an alkyl group having 1 to 4 carbon atoms which may have a substituent, and an aralkyl group having 7 to 16 carbon atoms which may have a substituent. The group is more preferable, and a methyl group, an ethyl group, a propyl group, a butyl group, and a benzyl group are more preferable.

R ¹³ and R ¹⁴ in general formula (b1-2) are more preferably an alkyl group having 1 to 4 carbon atoms which may have a substituent, and more preferably a methyl group, an ethyl group, a propyl group, or a butyl group. preferable.

In R ¹⁵ of general formula (b1-3), examples of the alkyl group having 1 to 18 carbon atoms include linear, branched, and cyclic alkyl groups. Examples include methyl group, ethyl group, normal propyl group, isopropyl group, n-butyl group, t-butyl group, n-hexyl group, cyclohexyl group, n-octyl group, hexadecyl group, and the like.
Examples of the aryl group having 6 to 20 carbon atoms include phenyl group, 1-naphthyl group, and 2-naphthyl group.
Examples of the aralkyl group having 7 to 12 carbon atoms include a group in which an aryl group having 6 to 10 carbon atoms is bonded to an alkyl group having 1 to 8 carbon atoms. Examples include benzyl group, phenethyl group, α-methylbenzyl group, and 2-phenylpropan-2-yl group.
Further, examples of the acyl group include an alkanoyl group having 2 to 8 carbon atoms and an aroyl group. Examples include an acetyl group and a benzoyl group.
Among these, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, and an oxy radical group are particularly preferred, a hydrogen atom and a methyl group are more preferred, and a methyl group is most preferred.

In the general formula (b1-1), the general formula (b1-2) and the general formula (b1-3), the divalent linking group x is, for example, a methylene group, an alkylene group having 2 to 10 carbon atoms, an arylene group, -CONH-R ²¹ - and -COO-R ²² - are preferred. However, R ²¹ and R ²² are a single bond, a methylene group, an alkylene group having 2 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) having 2 to 10 carbon atoms. Among these, -CONH-R ²¹ - and -COO-R ²² - are preferred. Examples of the counter anion Y ⁻ in the general formula (b1-1) include Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ ⁻ , BF ₄ ⁻ , CH ₃ COO ⁻ , PF ₆ ⁻ and the like.

The ethylenically unsaturated monomer forming the unit represented by general formula (b1-1) is, for example, (meth)acryloyloxyethyltrimethylammonium chloride, (meth)acryloyloxyethyltriethylammonium chloride, (meth)acryloyloxyethyldimethyl Alkyl (meth)acrylate quaternary ammonium salts such as benzylammonium chloride, (meth)acryloyloxyethylmethylmorpholinoammonium chloride, (meth)acryloylaminopropyltrimethylammonium chloride, (meth)acryloylaminoethyltriethylammonium chloride, (meth) ) Alkyl (meth)acryloylamide quaternary ammonium salts such as acryloylaminoethyldimethylbenzylammonium chloride, dimethyldiallylammonium methyl sulfate, trimethylvinylphenylammonium chloride, and the like.

The ethylenically unsaturated monomer forming the unit represented by general formula (b1-2) is, for example, N ,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N - (Meth)acrylates having a tertiary amino group such as dimethylaminopropyl (meth)acrylate, N,N-diethylaminopropyl (meth)acrylate; N,N-dimethylaminoethyl (meth)acrylamide, N,N-diethylamino Examples include (meth)acrylamides having a tertiary amino group such as ethyl (meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide, and N,N-diethylaminopropyl (meth)acrylamide.

Examples of the ethylenically unsaturated monomer forming the unit represented by the general formula (b1-3) include compounds represented by the following general formulas (b1-3-1) to (b1-3-11).

In general formulas (b1-3-1) to (b1-3-11), R ¹² represents hydrogen or a methyl group.

Among these, 2,2,6,6-tetramethylpiperidyl methacrylate (a compound in which R ¹² is a methyl group in the above general formula (b1-3-1)), 1,2,2,6,6-pentamethyl Piperidyl methacrylate (a compound in which R ¹² is a methyl group in the above general formula (b1-3-2)) is preferred, and 1,2,2,6,6-pentamethylpiperidyl methacrylate is particularly preferred.

The unit represented by the general formula (b1-1), the unit represented by (b1-2), and the unit represented by (b1-3) may be contained alone or in two or more kinds.

Units other than the unit represented by general formula (b1-1), the unit represented by (b1-2), and the unit represented by (b1-3) can be formed using the following other monomers.

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

Moreover, a carboxyl group-containing ethylenically unsaturated monomer can also be used in combination. The carboxyl group-containing ethylenically unsaturated monomers include (meth)acrylic acid, (meth)acrylic acid dimer, itaconic acid, maleic acid, fumaric acid, crotonic acid, 2-(meth)acryloyloxyethyl phthalate, 2- (meth)acryloyloxypropyl phthalate, 2-(meth)acryloyloxyethyl hexahydrophthalate, 2-(meth)acryloyloxypropylhexahydrophthalate, β-carboxyethyl (meth)acrylate, ω-carboxypolycaprolactone ( Examples include meth)acrylate.

Furthermore, even if an ethylenically unsaturated monomer containing an amino group other than the structural units represented by general formula (b1-1), general formula (b1-2), and general formula (b1-3) is used in combination, good.

The weight average molecular weight of the basic resin type dispersant (b1) is usually preferably 1,000 to 100,000. An appropriate molecular weight further improves dispersion stability and developability.

<Phosphoric acid resin type dispersant (b2)>
The phosphoric acid resin type dispersant (b2) is a resin having a phosphoric acid bond [(-O) ₃ P=O] in the molecule. The phosphoric acid resin type dispersant (b2) is preferably a resin type dispersant containing the following (b2-1) or (b2-2).

<Phosphoric acid resin type dispersant (b2-1)>
General formula (3) (HO-) _3-n -PO-(OR ⁵ ) _n
(In general formula (3), R ⁵ is a polyester residue with a number average molecular weight of 300 to 10,000, and n represents 1 or 2.)

The dispersant represented by general formula (3) can suppress re-aggregation of the red pigment (A) after dispersion. Therefore, a color filter with excellent transparency can be formed. Furthermore, since the dispersant represented by the general formula (3) has high self-solubility, for example, if the coloring composition solidifies at the tip of the discharge port when a die coating coating device is temporarily stopped, coating may be started again. Then, the solidified material can be dissolved.

The dispersant represented by the general formula (3) is prepared by, for example, producing a polyester having a hydroxyl group at one end by ring-opening addition (first step) of a cyclic ester using a monoalcohol as an initiator, followed by phosphoric acid esterification ( It can be manufactured by performing the second step).

As the monoalcohol, any of primary, secondary, and tertiary alcohols can be used. For example, methanol, ethanol, propanol, isopropanol, butanol, sec-butanol, t-butanol, pentanol, amyl alcohol, hexanol, heptanol, octanol, 2-ethylhexyl alcohol, nonanol, decanol, lauryl alcohol, myristyl alcohol, cetyl alcohol, Examples include stearyl alcohol, oleyl alcohol, hexadecyl alcohol, and the like. Among these, lauryl alcohol, N-hexanol, and hexadecyl alcohol are preferred.

The first step is to perform ring-opening addition polymerization of ε-caprolactone and the like using a monoalcohol as an initiator. The addition reaction of ε-caprolactone can be carried out by a known method, for example, by charging a monoalcohol, ε-caprolactone, and a polymerization catalyst into a reactor connected to a dehydration tube and a condenser under a nitrogen stream. When using a monoalcohol with a low boiling point, the reaction can be carried out under pressure using an autoclave. In the reaction, no solvent or a suitable dehydrated solvent such as toluene or xylene can be used. After the reaction is complete, the solvent used in the reaction can be removed by distillation or other operations, or it can be used as is as part of the product.

The reaction temperature in the first step is 120°C to 220°C, preferably 160°C to 210°C. When the reaction temperature is less than 120°C, the reaction rate is extremely slow, and when it exceeds 220°C, side reactions other than the addition reaction of ε-caprolactone, such as decomposition of the ε-caprolactone adduct into ε-caprolactone monomer, and cyclic ε-caprolactone dimer, occur. generation etc. are likely to occur.
The number of moles of ε-caprolactone added per mole of monoalcohol is 1 to 50 moles, preferably 3 to 20 moles. If the number of moles added is less than 1 mole, it becomes difficult to obtain an effect as a dispersant, and if it is more than 50 moles, the molecular weight of the reactant becomes too large, which tends to cause a decrease in dispersibility and fluidity.

Examples of the polymerization catalyst include tetramethylammonium chloride, tetrabutylammonium chloride, tetramethylammonium bromide, tetrabutylammonium bromide, tetramethylammonium iodine, tetrabutylammonium iodine, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide. Quaternary ammonium salts such as tetramethylphosphonium chloride, tetrabutylphosphonium chloride, tetramethylphosphonium bromide, tetrabutylphosphonium bromide, tetramethylphosphonium iodine, tetrabutylphosphonium iodine, benzyltrimethylphosphonium chloride, benzyltrimethylphosphonium bromide, benzyltrimethylphosphonium In addition to quaternary phosphonium salts such as iodine, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, and tetraphenylphosphonium iodine, phosphorus compounds such as triphenylphosphine, and organic carbonates such as potassium acetate, sodium acetate, potassium benzoate, and sodium benzoate. In addition to acid salts, alkali metal alcoholates such as sodium alcoholate and potassium alcoholate, tertiary amines, organic tin compounds, organic aluminum compounds, organic titanate compounds, and zinc compounds such as zinc chloride can be mentioned. The amount of catalyst used is 0.1 ppm to 3000 ppm, preferably 1 ppm to 1000 ppm. When used in an appropriate amount, just the right polymerization rate can be obtained.

The phosphoric acid esterification (second step) is carried out by reacting one or more phosphoric acid esterifying agents such as phosphorus pentoxide, polyphosphoric acid, orthophosphoric acid, and phosphorus oxychloride. It can be performed. Among these, one or more phosphoric acid esterifying agents selected from the group consisting of orthophosphoric acid, polyphosphoric acid, and phosphorus pentoxide are preferred because they do not produce by-products such as hydrochloric acid gas and do not require special equipment.

The charging ratio of the phosphoric acid esterifying agent is preferably such that the molar ratio of the phosphorus atom in the phosphoric acid esterifying agent to the hydroxyl group of the polyester residue having a hydroxyl group at one end is 0.5 to 1.5, and 1 It is more preferably from .0 to 1.3, and most preferably from 1.05 to 1.2. If the molar ratio of phosphorus atoms to hydroxyl groups is less than 0.5, phosphoric acid esterification of hydroxyl groups tends to be insufficient or the amount of phosphoric diester by-products tends to increase; if it exceeds 1.5, There is a tendency that the effect of increasing the amount commensurate with the amount added cannot be obtained.

The reaction temperature in the second step is not particularly limited, but is preferably 40°C to 130°C, more preferably 50°C to 110°C, and most preferably 60°C to 100°C. If the reaction temperature is lower than these ranges, the esterification reaction may be insufficient and the phosphoric acid esterifying agent may remain; if the reaction temperature is higher than these ranges, by-products are likely to be produced and esters may be decomposition of reaction products tends to occur more easily.

In the present specification, the dispersant represented by the general formula (3) is preferably a combination of a phosphoric ester with n=1 and a phosphoric ester with n=2. The molar ratio of n=1 to n=2 is preferably 100:1 to 100:30. This further improves pigment dispersibility.

Further, in the dispersant represented by the general formula (3), R ⁵ preferably has a structure represented by the following general formula (3-1).
General formula (3-1) -(R ⁵¹ -COO-) _m -R ⁵²
(In general formula (3-1), R ⁵¹ represents a lactone residue, R ⁵² represents a monoalcohol residue, and m represents an integer of 1 to 50.
When m in the structure represented by general formula (3-1) is 2 or more, R ⁵ in the dispersant represented by general formula (3) becomes a polycaprolactone residue. This improves the pigment dispersibility and further improves the solubility of the solidified product.

<Phosphoric acid resin type dispersant (b2-2)>
The phosphoric acid-based resin type dispersant (b2-2) is a resin type dispersant that is a copolymer of an ethylenically unsaturated monomer having a phosphoric acid group and another ethylenically unsaturated monomer. . The dispersant is described in JP-A-2003-253078 and JP-A-2008-161737.

<Salt (b3) of the compound represented by general formula (1) or the compound represented by general formula (2) and basic resin type dispersant (b1)>
(B2) of the resin type dispersant is a salt (b3) of a compound represented by the following general formula (1) or a compound represented by the general formula (2) and a basic resin type dispersant (b1), and a carboxylic acid type Contains a resin type dispersant (b4).

General formula (1) General formula (2)

However, in the general formula (1) and the general formula (2), R ¹ and R ² each independently represent a hydrogen atom, a hydroxyl group, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, vinyl group, a phenyl group to a benzyl group which may have a substituent, or -O-R ³ , and R ³ is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a substituted It represents a phenyl group to a benzyl group which may have a group, or a (meth)acryloyl group via an alkylene group having 1 to 4 carbon atoms. However, at least one of R ¹ and R ² contains a carbon atom.

Examples of the compound represented by the general formula (1) include monobutyl phosphoric acid, dibutyl phosphoric acid, methyl phosphoric acid, dibenzyl phosphoric acid, diphenyl phosphoric acid, phenylphosphinic acid, phenylphosphonic acid, dimethacryloyloxyethyl acid phosphate, and the like.

Examples of the compound represented by the general formula (2) include benzenesulfonic acid, vinylsulfonic acid, methanesulfonic acid, p-toluenesulfonic acid, monomethyl sulfate, monoethyl sulfate, mono-n-propyl sulfate, and the like. Note that a hydrate such as p-toluenesulfonic acid monohydrate may also be used.

As mentioned above, the salt (b3) of the basic resin type dispersant (b1) is a compound represented by the basic resin type dispersant (b1) and the general formula (1), or a compound represented by the general formula (2). ) represents a salt with the exemplified compound.

<Carboxylic acid resin type dispersant (b4)>
The carboxylic acid resin type dispersant (b4) preferably contains the following (b4-1) or (b4-2). Note that in this specification, the carboxylic acid resin is a resin having a carboxyl group.

<Carboxylic acid resin type dispersant (b4-1)>
The carboxylic acid resin type dispersant (b4-1) is a resin type dispersant containing a polyester part having a carboxyl group and a vinyl polymer part,
The carboxyl group-containing polyester portion is a reaction product of a hydroxyl group-containing compound and an acid anhydride compound selected from the group consisting of tetracarboxylic anhydrides and tricarboxylic anhydrides. Note that the acid anhydride group of the acid anhydride compound reacts with the hydroxyl group in the hydroxyl group-containing vinyl polymer.

First, I will explain the polyester part. The polyester portion has a plurality of ester groups derived from a reaction between an acid anhydride group and a hydroxyl group.

[Tetracarboxylic anhydride]
Tetracarboxylic dianhydride is a compound having two acid anhydride groups. Examples of the tetracarboxylic dianhydride include 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1, 2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic dianhydride, 3,5,6 -Tricarboxynorbornane-2-acetic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 5-(2,5-dioxotetrahydrofural)-3-methyl-3-cyclohexene-1 , 2-dicarboxylic dianhydride, aliphatic tetracarboxylic dianhydride such as bicyclo[2.2.2]-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, pyro Mellitic acid dianhydride, ethylene glycol dianhydride trimellitic acid ester, propylene glycol dianhydride trimellitic acid ester, butylene glycol dianhydride trimellitic acid ester, 3,3',4,4'-benzophenonetetracarboxylic dianhydride , 3,3',4,4'-biphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride 3,3',4,4'-biphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3',4,4' -Tetraphenylsilane tetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylsulfide dianhydride, 4, 4'-bis(3,4-dicarboxyphenoxy)diphenylsulfone dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'- Perfluoroisopropylidene diphthalic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, bis(phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis(triphenyl phthalate) acid) dianhydride, m-phenylene-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4'-diphenyl ether dianhydride, bis(triphenylphthalic acid)-4,4 '-diphenylmethane dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl]fluorene dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic dianhydride, or 3,4-dicarboxy-1,2,3,4-tetrahydro-6-methyl-1- Examples include aromatic tetracarboxylic dianhydrides such as naphthalenesuccinic dianhydride. Among these, aromatic tetracarboxylic dianhydride is preferred because it has excellent adsorption to the red pigment (A).

Tetracarboxylic acid anhydrides can be used alone or in combination of two or more.

[Tricarboxylic acid anhydride]
A tricarboxylic acid anhydride is a compound having one acid anhydride group and one carboxyl group. Examples of tricarboxylic anhydrides include aliphatic tricarboxylic anhydrides, aromatic tricarboxylic anhydrides, and the like.

Aliphatic tricarboxylic acid anhydrides include, for example, 3-carboxymethylglutaric anhydride, 1,2,4-butanetricarboxylic acid-1,2-anhydride, cis-propene-1,2,3-tricarboxylic acid-1 , 2-anhydride, 1,3,4-cyclopentanetricarboxylic anhydride, and the like.

Aromatic tricarboxylic acids include, for example, benzenetricarboxylic anhydride (1,2,3-benzenetricarboxylic anhydride, trimellitic anhydride [1,2,4-benzenetricarboxylic anhydride], etc.), naphthalenetricarboxylic acid Anhydrides (1,2,4-naphthalenetricarboxylic anhydride, 1,4,5-naphthalenetricarboxylic anhydride, 2,3,6-naphthalenetricarboxylic anhydride, 1,2,8-naphthalenetricarboxylic anhydride etc.), 3,4,4'-benzophenonetricarboxylic anhydride, 3,4,4'-biphenyl ethertricarboxylic anhydride, 3,4,4'-biphenyltricarboxylic anhydride, 2,3,2'- Examples include biphenyltricarboxylic anhydride, 3,4,4'-biphenylmethanetricarboxylic anhydride, and 3,4,4'-biphenylsulfonetricarboxylic anhydride. Among these, aromatic tricarboxylic acid anhydrides are preferred in view of their excellent adsorption to the red pigment (A).

In the synthesis of the carboxylic acid resin type dispersant (b4-1), the molar ratio of the acid anhydride group to the hydroxyl group in the acid anhydride compound and the hydroxyl group in the hydroxyl group-containing vinyl polymer is determined as follows: Group/hydroxyl group=0.5 to 1.5 is preferable. When used at the above molar ratio, if it is less than 0.5 or greater than 1.5, there will be a large amount of unreacted portion, and the desired dispersant will often not be obtained.

[Hydroxyl group-containing compound]
Examples of the hydroxyl group-containing compound include monoalcohols having one hydroxyl group and polyols having two or more hydroxyl groups, with polyols being preferred. The hydroxyl group-containing compound serves as a starting point for bonding to the vinyl polymer portion.
Examples of the hydroxyl group-containing compound include a compound having two hydroxyl groups and one thiol group, and a vinyl polymer containing a hydroxyl group at one end. Examples of the hydroxyl group-containing compound include 1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, 3-mercapto-1,2-propanediol (thioglycerin or 1-thioglycerol), 2 -Mercapto-1,2-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol, 1-mercapto-2,2-propanediol , 2-mercaptoethyl-2-methyl-1,3-propanediol, or 2-mercaptoethyl-2-ethyl-1,3-propanediol.

The carboxylic acid resin type dispersant (b4-1) is preferably (b4-1-1) or (b4-1-2).

<Carboxylic acid resin type dispersant (b4-1-1)>
The vinyl polymer moiety of the carboxylic acid resin type dispersant (b4-1-1) contains one or more thermally crosslinkable functional groups selected from the group consisting of hydroxyl group, oxetane group, tert-butyl group, and blocked isocyanate group. and a carboxyl group. The vinyl polymer portion is obtained by polymerizing an ethylenically unsaturated monomer containing a thermally crosslinkable functional group and an ethylenically unsaturated monomer having a carboxyl group.

(Ethylenically unsaturated monomer having hydroxyl group)
Ethylenically unsaturated monomers having a hydroxyl group are, for example, 2-hydroxyethyl (meth)acrylate, 2 (or 3)-hydroxypropyl (meth)acrylate, 2 (or 3 or 4)-hydroxybutyl (meth)acrylate N-(2- Contains a hydroxyl group such as N-(hydroxyalkyl)(meth)acrylamide such as hydroxyethyl)(meth)acrylamide, N-(2-hydroxypropyl)(meth)acrylamide, N-(2-hydroxybutyl)(meth)acrylamide, etc. (Meth)acrylamide; vinyl ethers with hydroxyl groups such as hydroxyalkyl vinyl ethers such as 2-hydroxyethyl vinyl ether, 2-(or 3-) hydroxypropyl vinyl ether, and 2-(or 3- or 4-) hydroxybutyl vinyl ether; 2-hydroxy Examples include allyl ethers having a hydroxyl group, such as hydroxyalkyl allyl ethers such as ethyl allyl ether, 2-(or 3-) hydroxypropyl allyl ether, and 2-(or 3- or 4-) hydroxybutyl allyl ether.

Additionally, ethylene obtained by adding alkylene oxide and/or lactone to hydroxyalkyl (meth)acrylate, alkyl-α-hydroxyalkyl acrylate, N-(hydroxyalkyl)(meth)acrylamide, hydroxyalkyl vinyl ether or hydroxyalkyl allyl ether The ethylenically unsaturated monomer is also an ethylenically unsaturated monomer having a hydroxyl group. Examples of the alkylene oxide to be added include ethylene oxide, propylene oxide, 1,2-, 1,4-, 2,3-, or 1,3-butylene oxide. Note that when two or more types of alkylene oxides are used together, the bonding format may be either random or block. Examples of the lactone to be added include δ-valerolactone, ε-caprolactone, and ε-caprolactone substituted with an alkyl group having 1 to 6 carbon atoms. Note that both alkylene oxide and lactone can be added.

(Ethylenically unsaturated monomer having oxetane group)
Examples of the ethylenically unsaturated monomer having an oxetane group include (vinyloxyalkyl)alkyloxetane, (meth)acryloyloxyalkyloxetane, and [(meth)acryloyloxyalkyl]alkyloxetane. Among these, (3-ethyloxetan-3-yl)methyl methacrylate is preferred. Examples of commercially available products include ETERNACOLL OXMA ((3-ethyloxetan-3-yl)methyl methacrylate) (manufactured by Ube Industries, Ltd.).

(Ethylenically unsaturated monomer having tert-butyl group)
Examples of the ethylenically unsaturated monomer having a tert-butyl group include tert-butyl methacrylate and tert-butyl acrylate.

(Ethylenically unsaturated monomer having blocked isocyanate group)
Ethylenically unsaturated monomers having blocked isocyanate groups include 2-(0-[1'-methylpropylideneamino]carboxyamino)ethyl methacrylate, 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl Examples include methacrylate.
Commercially available products include, for example, Karenz MOI-BM (2-(0-[1'-methylpropylideneamino]carboxyamino)ethyl methacrylate) (manufactured by Showa Denko), Karenz MOI-BP (2-[(3, Examples include 5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate (manufactured by Showa Denko).

The content of the ethylenically unsaturated monomer containing a thermally crosslinkable functional group is preferably 5 to 90% by mass, more preferably 20 to 60% by mass, based on the entire ethylenically unsaturated monomer. When contained in an appropriate amount, durability and dispersion stability are further improved.

ethylenically unsaturated monomer having a carboxyl group)
Examples of the ethylenically unsaturated monomer having a carboxyl group include (meth)acrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid. Among these, (meth)acrylic acid is preferred in terms of copolymerizability.

[Other ethylenically unsaturated monomers]
Other ethylenically unsaturated monomers can be used in the synthesis of the vinyl polymer portion.
Other ethylenically unsaturated monomers include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, and isobutyl (meth)acrylate. Alkyl (meth)acrylates such as acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, trimethylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate; phenyl Aromatic (meth)acrylates such as (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, and phenoxydiethylene glycol (meth)acrylate; Heterocyclic (meth)acrylates such as tetrahydrofurfuryl (meth)acrylate alkoxypolyalkylene glycol (meth)acrylates such as methoxypolypropylene glycol (meth)acrylate and ethoxypolyethylene glycol (meth)acrylate; (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N,N-diethyl ( N-substituted (meth)acrylamides such as meth)acrylamide, N-isopropyl (meth)acrylamide, diacetone (meth)acrylamide, and acryloylmorpholine; N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl Amino group-containing (meth)acrylates such as (meth)acrylate; Nitriles such as (meth)acrylonitrile; Styrenes such as styrene, α-methylstyrene, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether , vinyl ethers such as isobutyl vinyl ether, and fatty acid vinyls such as vinyl acetate and vinyl propionate.

<Carboxylic acid resin type dispersant (b4-1-2)>
The vinyl polymer portion of the carboxylic acid resin type dispersant (b4-1-2) preferably contains an ethylenically unsaturated group. Examples of the ethylenically unsaturated group include a vinyl group, an allyl group, and a (meth)acryloyl group, with a (meth)acryloyl group being preferred from the viewpoint of reactivity.
The method for producing the carboxylic acid resin type dispersant (b4-1-2) includes, for example, synthesizing a vinyl polymer containing a reactive functional group, and then synthesizing a vinyl polymer having a functional group (meth) capable of reacting with the reactive functional group. ) A method of reacting acrylate is mentioned. Examples of the combination of functional groups include (1) a combination of glycidyl methacrylate and a polymer having a hydroxyl group or a carboxyl group, and (2) a combination of methacryloyloxyethyl isocyanate and a polymer having a hydroxyl group or a carboxyl group. .
A polymer having a hydroxyl group or a carboxyl group can be synthesized by subjecting a polymer having a glycidyl group or an acid anhydride group to a ring-opening reaction. Such a dispersant is described, for example, in JP-A No. 2011-157416.

<Carboxylic acid resin type dispersant (b4-2)>
The carboxylic acid resin type dispersant (b4-2) is a dispersant represented by the following general formula (4). The dispersant is described, for example, in JP-A No. 2007-140487.
General formula (4) (HOOC-) _m -R ⁶ -(-COO-[-R ⁸ -COO-] _n -R ⁷ ) _t
(In the formula, R ⁶ is a tetravalent aromatic tetracarboxylic acid residue, R ⁷ is a monoalcohol residue, R ⁸ is a lactone residue, m is 2 or 3, and n is an integer from 1 to 50. , t represents (4-m).)

<Commercially available resin type dispersant>
The coloring composition of this specification can also be used in combination with other resin-type dispersants. Other commercially available resin-type dispersants include, for example, Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165 manufactured by BYK Chemie Japan, 166, 167, 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 2163, SOLSPERSE-3000, 9000, 13000, 13240, 1365 manufactured by Lubrizol Japan, such as 2164 or Anti-Terra-U, 203, 204, or BYK-P104, P104S, 220S, or Lactimon, Lactimon-WS or Bykumen. 0, 13940 , 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 56000, 76500 etc., EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, manufactured by BASF, etc. 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc., Ajinomoto Fine Techno Examples include Ajisper PA111, PB711, PB821, PB822, and PB824 manufactured by Co., Ltd.

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

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

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

The binder resin (C) 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 mass, more preferably 50 to 250 parts by mass, based on 100 parts by mass of the colorant containing the red pigment. When contained in an appropriate amount, a film can be easily formed and good color properties can be easily obtained.

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

<Active energy ray-curable alkali-soluble resin>
It is preferable that the active energy ray-curable alkali-soluble resin has an ethylenically unsaturated double bond. Ethylenically unsaturated double bonds can be introduced, for example, by methods (i) and (ii) shown below. The resin is three-dimensionally crosslinked due to the effect of active energy rays, thereby increasing the crosslinking density and improving chemical resistance.

[Method (i)]
In method (i), for example, an ethylenically unsaturated monomer having an epoxy group is added to the side chain epoxy group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer with another monomer. The carboxyl group of an unsaturated monobasic acid having a heavy bond is subjected to an addition reaction. Next, the generated hydroxyl group is reacted with a polybasic acid anhydride, thereby introducing an ethylenically unsaturated double bond and a carboxyl group.

Ethylenically unsaturated monomers having an epoxy group include, for example, glycidyl (meth)acrylate, methylglycidyl (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 with unsaturated monobasic acids.

Unsaturated monobasic acids include monobasic acids such as (meth)acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, and α-haloalkyl, alkoxyl, halogen, nitro, and cyano substituted products of (meth)acrylic acid. Examples include carboxylic acids.

Examples of the polybasic acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, and the like. In addition, if necessary, such as increasing the number of carboxyl groups, use a tricarboxylic acid anhydride such as trimellitic anhydride or a tetracarboxylic dianhydride such as pyromellitic dianhydride to reduce the remaining amount. It is also possible to hydrolyze the anhydride group.

As a method similar to method (i), for example, a part of the side chain carboxyl groups of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a carboxyl group with another monomer may be used. , is a method in which an ethylenically unsaturated monomer having an epoxy group is subjected to an addition reaction to introduce an ethylenically unsaturated double bond and a carboxyl group.

[Method (ii)]
Method (ii) involves adding an ethylenically unsaturated monomer having an isocyanate group to the side chain hydroxyl group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a hydroxyl group with another monomer. This is a method in which the isocyanate groups of monomers are reacted.

The ethylenically unsaturated monomer having a hydroxyl group is, for example, 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2- or 3- or 4-hydroxybutyl (meth)acrylate, Examples include hydroxyalkyl methacrylates such as glycerol mono(meth)acrylate and cyclohexanedimethanol mono(meth)acrylate. In addition, polyether mono(meth)acrylate obtained by addition polymerizing ethylene oxide, propylene oxide, and/or butylene oxide, etc. to hydroxyalkyl (meth)acrylate, polyγ-valerolactone, polyε-caprolactone, and/or polyester Also included are polyester mono(meth)acrylates to which 12-hydroxystearic acid and the like are added. From the viewpoint of suppressing coating film foreign matter, 2-hydroxyethyl methacrylate or glycerol mono(meth)acrylate is preferable, and from the viewpoint of sensitivity, it is preferable to use one having 2 to 6 hydroxyl groups. Among them, glycerol mono(meth)acrylate is more preferable.

Examples of the ethylenically unsaturated monomer having an isocyanate group include 2-(meth)acryloyl ethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, or 1,1-bis[methacryloyloxy]ethyl isocyanate. It will be done.

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

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

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

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

The weight average molecular weight (Mw) of the alkali-soluble resin in the present invention is 2,000 or more and 40,000 or less, preferably 3,000 or more and 300,00 or less, and 4,000 or more, in order to impart alkaline development solubility. It is more preferably 20,000 or less. Moreover, it is preferable that the value of Mw/Mn is 10 or less. If the weight average molecular weight (Mw) is less than 2,000, the adhesion to the substrate will be lowered and the exposed pattern will be less likely to remain. If it exceeds 40,000, the solubility in alkali development decreases, a residue is generated, and the linearity of the pattern deteriorates.
The acid value of the alkali-soluble resin in the present invention is 50 or more and 200 or less (KOHmg/g) in order to impart alkaline development solubility, preferably 70 or more and 180 or less, and more preferably 90 or more and 170 or less. range. If the acid value is less than 50, the solubility in alkaline development will decrease, a residue will be generated, and the linearity of the pattern will deteriorate. When it exceeds 200, the adhesion to the substrate decreases, making it difficult for the exposed pattern to remain.

Each raw material used in the synthesis of the binder resin (C) can be used alone or in combination of two or more.

<Thermosetting compound (CE)>
The coloring composition can contain a thermosetting compound (CE) together with the binder resin (C). For example, when producing a color filter using a color filter coloring composition, by including a thermosetting compound, the thermosetting compound (CE) reacts during firing of the filter segment and increases the crosslinking density of the film. This improves the heat resistance of the filter segment, suppresses pigment aggregation during firing of the filter segment, and improves the contrast ratio.

Examples of the thermosetting compound include low molecular weight compounds and high molecular weight compounds such as resins.
Examples of thermosetting compounds include epoxy compounds, oxetane compounds, benzoguanamine compounds, rosin-modified maleic acid compounds, rosin-modified fumaric acid compounds, melamine compounds, urea compounds, and phenol compounds. In addition, in the coloring composition for color filters, epoxy compounds and oxetane compounds are preferable.

(Epoxy compound (CE-1))
Epoxy compounds include, for example, bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted Polycondensates of dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.), phenol and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.), phenols and ketones. (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.), phenols and aromatic dimethanols (benzenedimethanol, α, α, α', α'-benzenedimethanol, 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-based epoxy resins obtained by glycidylating alcohols, etc., alicyclic epoxy resins, heterocyclic epoxy resins, aliphatic epoxy resins, glycidylamine-based epoxy resins, glycidyl ester-based epoxy resins Examples include epoxy resin.

Commercially available epoxy compounds include, for example, Epicote 807, Epicote 815, Epicote 825, Epicote 827, Epicote 828, Epicote 190P, Epicote 191P (trade names; manufactured by Yuka Shell Epoxy Co., Ltd.), Epicote 1004, Epicote 1256 (trade names) (Product name: Japan Epoxy Resin Co., Ltd.), TECHMORE VG3101L (Product name: Mitsui Chemicals Co., Ltd.), EPPN-501H, 502H (Product name: Nippon Kayaku Co., Ltd.), JER 1032H60 (Product name: Japan Epoxy Resin Co., Ltd.) ), JER 157S65, 157S70 (product name; made by Japan Epoxy Resin Co., Ltd.), EPPN-201 (product name; made by Nippon Kayaku Co., Ltd.), JER152, JER154 (the above are product names; made by Japan Epoxy Resin Co., Ltd.), EOCN-102S , EOCN-103S, EOCN-104S, EOCN-1020 (trade names; manufactured by Nippon Kayaku Co., Ltd.), Celoxide 2021, EHPE-3150 (trade names; manufactured by Daicel Chemical Industries, Ltd.), Denacol EX-211, 212, 252, 313, 314, 321, 411, 421, 512, 521, 611, 612, 614, 614B, 622, 711, 721, (the above are product names; manufactured by Nagase ChemteX), TEPIC-L, TEPIC-H , TEPIC-S (manufactured by Nissan Chemical Industries, Ltd.).

The blending amount of the epoxy compound is preferably 0.5 to 300 parts by weight, more preferably 1.0 to 50 parts by weight, per 100 parts by weight of the colorant. When blended in an appropriate amount, heat resistance is further improved.

(Oxetane compound (CE-2))
An oxetane compound is a compound having one or more oxetane groups.

Compounds having one oxetane group are, for example, (3-ethyloxetan-3-yl)methyl acrylate, (3-ethyloxetan-3-yl)methyl methacrylate, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl- 3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(phenoxymethyl)oxetane, 3-ethyl-3-(2-methacryloxymethyl)oxetane, 3-ethyl-3-{[3-( Examples include triethoxysilyl)propoxy]methyl}oxetane. Commercially available products include OXE-10 and OXE-30 manufactured by Osaka Organic Chemical Industry Co., Ltd., and OXT-101 and OXT-212 manufactured by Toagosei Co., Ltd.

Compounds having two oxetane groups are, for example, 4,4'-bis[(3-ethyl-3-oxetanyl)methoxymethyl]biphenyl), 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl] Benzene, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, di[1-ethyl(3-oxetanyl)]methyl ether, di[1-ethyl(3-oxetanyl)]methyl Ether-3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(2-phenoxymethyl)oxetane, 3,7-bis(3- oxetanyl)-5-oxanonane, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3-bis[(3-ethyl-3-oxetanylmethoxy)methyl]propane, ethylene Glycose bis(3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyl bis(3-ethyl-3-oxetanylmethyl) ether, triethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis (3-ethyl-3-oxetanylmethyl)ether, 1,4-bis(3-ethyl-3-oxetanylmethoxy)butane, 1,6-bis(3-ethyl-3-oxetanylmethoxy)hexane, polyethylene glycol bis( 3-ethyl-3-oxetanylmethyl) ether, ethylene oxide (EO) modified bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, propylene oxide (PO) modified bisphenol A bis(3-ethyl-3-oxetanylmethyl) Ether, EO-modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, PO-modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol F (3-ethyl-3) -oxetanylmethyl) ether and the like. Commercially available products include OXBP, OXTP manufactured by Ube Industries, and OXT-121 and OXT-221 manufactured by Toagosei.

Examples of compounds having three or more oxetane groups 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, caprolactone-modified dipentaerythritol hexa(3-ethyl) -3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropane tetrakis (3-ethyl-3-oxetanylmethyl) ether, oxetane group-containing resin ( Examples include polymers obtained by radical polymerization of (meth)acrylic monomers such as oxetane-modified phenol novolac resin described in Japanese Patent No. 3783462) and the above-mentioned OXE-30.

The content of the oxetane compound is usually preferably 0.5 to 50% by weight, more preferably 1 to 40% by weight based on 100% by weight of nonvolatile content of the coloring composition. When contained in an appropriate amount, water stains on the film are improved and chemical resistance is further improved.

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

(melamine compound)
A melamine compound is a compound having a melamine ring structure. Examples include low molecular weight compounds and high molecular weight compounds such as resins. In this specification, methylol type and ether type are preferred, and melamine compounds having an average number of methylol groups and/or ether groups per melamine ring of 5.0 or more are more preferred. When the number of methylol groups and/or ether groups is moderate, a good crosslinked structure is easily obtained, and the contrast ratio and solvent resistance are further improved.

Commercially available products include, for example, Nikarac MW-30HM, MW-390, MW-100LM, MX-750LM, MW-30M, MW-30, MW-22, MS-21, MS-11, MW-24X, MS- 001, MX-002, MX-730, MX-750, MX-708, MX-706, MX-042, MX-45, MX-500, MX-520, MX-43, MX-417, MX-410 ( (manufactured by Sanwa Chemical Co., Ltd.), Cymel 232, 235, 236, 238, 285, 300, 301, 303, 350, 370 (manufactured by Nippon Cytec Industries), and the like. Among these, Nikarak MW-30HM, MW-390, MW-100LM, MX-750LM, MW-30M, MW-30 have an average number of methylol groups and/or ether groups per melamine ring of 5.0 or more. , MW-22, MS-21, MS-11, MW-24X, MX-45 (manufactured by Sanwa Chemical Co., Ltd.) Cymel 232, 235, 236, 238, 300, 301, 303, 350 (manufactured by Nihon Cytec Industries Co., Ltd.) is preferred.

(hardening agent)
The coloring composition can contain a curing agent (curing accelerator) to assist in curing the thermosetting compound. Effective curing agents include amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds, etc., but are not particularly limited to these, and those that can react with thermosetting compounds. Any curing agent may be used. The curing agent is, for example, an amine compound (for example, dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N, N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (e.g., triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (e.g., dimethylamine, etc.), imidazole derivatives, bicyclic amidine compounds and their salts (e.g., imidazole, -Methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4 -methylimidazole, etc.), phosphorus compounds (e.g., triphenylphosphine, etc.), S-triazine derivatives (e.g., 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino- S-triazine, 2-vinyl-4,6-diamino-S-triazine/isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine/isocyanuric acid adduct, etc.) can be used. can. These may be used alone or in combination of two or more. The content of the curing accelerator is preferably 0.01 to 15 parts by weight based on 100 parts by weight of the thermosetting compound.

<Polymerizable compound (D)>
The photosensitive colored composition of the present invention includes a colored composition, a polymerizable compound (D), and a photopolymerization initiator (E). The polymerizable compound (D) includes a monomer or oligomer that is cured by ultraviolet rays, heat, etc. to produce 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, and 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, 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 , various acrylic esters and methacrylic esters such as (meth)acrylic ester of methylolated melamine, epoxy (meth)acrylate, urethane acrylate, (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether , pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-vinylformamide, acrylonitrile and the like.

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

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

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

Commercially available photopolymerizable monomers having acid groups include Viscoat #2500P manufactured by Osaka Organic Co., Ltd., and Aronix M-5300, M-5400, M-5700, M-510, M-520 manufactured by Toagosei Co., Ltd. can be mentioned.

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

(Meth)acrylates having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, and ditrimethylolpropane tri(meth)acrylate. ) 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, a reaction product of an epoxy group-containing compound and carboxy(meth)acrylate, a hydroxyl group-containing polyol polyacrylate, and the like.

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

Commercial products of polymerizable compounds having urethane bonds include AH-600, AT-600, UA-306H, UA-306T, UA-306I, UA-510H, UF-8001G, DAUA-167, and New manufactured by Kyoeisha Chemical Co., Ltd. Examples include UA-160TM manufactured by Nakamura Chemical Industry Co., Ltd., and UV-4108F and UV-4117F manufactured by Osaka Organic Chemical Industry Co., Ltd.

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

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

<Photopolymerization initiator (E)>
The photoinitiator (E) is, for example, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1- one, 1-hydroxycyclohexyl phenylketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-1-[4-(4-morpholino) ) phenyl]-2-(phenylmethyl)-1-butanone, or 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1- Acetophenone compounds such as butanone; Benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyl dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, Benzophenone compounds such as acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone; thioxanthone, 2-chlorothioxanthone, 2 - Thioxanthone compounds such as methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloro methyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s- Triazine, 2-piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4, 6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy-naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl) -6-triazine or triazine compounds such as 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine; 1,2-octanedione, 1-[4-(phenylthio)phenyl-,2- (O-benzoyloxime)], or oxime esters such as ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime) Compounds: Phosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide or diphenyl-2,4,6-trimethylbenzoylphosphine oxide; 9,10-phenanthrenequinone, camphorquinone, ethyl anthraquinone Examples include quinone compounds such as; borate compounds; carbazole compounds; imidazole compounds; and titanocene compounds. Among these, oxime ester compounds are preferred.

Commercially available photopolymerization initiators (E) include acetophenone compounds such as "Omnirad 907" (2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1) manufactured by IGM Resins. -one), “Omnirad 369E” (2-(dimethylamino)-1-[4-(4-morpholino)phenyl]-2-(phenylmethyl)-1-butanone), “Omnirad 379EG” (2-(dimethyl (amino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone), phosphine-based compounds were all manufactured by IGM Resins, and were manufactured using “Omnirad 819” (bis (2,4,6-trimethylbenzoyl)-phenylphosphine oxide), "Omnirad TPO" (diphenyl-2,4,6-trimethylbenzoylphosphine oxide), and the like.

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

(oxime ester compound)
When an oxime ester compound absorbs ultraviolet light, the N—O bond of the oxime is cleaved to generate iminyl radicals and alkyloxy radicals. Since these radicals generate highly active radicals by further decomposition, a pattern can be formed with a small amount of exposure. If the colorant concentration of the photosensitive coloring composition is high, the ultraviolet transmittance of the coating film may be low and the degree of curing of the coating film may be low, but oxime ester compounds are preferably used because they have high quantum efficiency. Ru.

Commercially available oxime ester compounds include 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)] (IRGACURE OXE-01), and ethanone, 1 from BASF. -[9-Ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime) (IRGACURE OXE 02), N-1919 (manufactured by ADEKA), TRONLY TR -PBG-304, TRONLY TR-PBG-305, TRONLY TR-PBG-309 (all manufactured by Changzhou Strong New Materials Co., Ltd.), etc. In addition, oxime ester photopolymerization described in JP-A No. 2007-210991, JP-A 2009-179619, JP-A 2010-037223, JP-A 2010-215575, JP-A 2011-020998, etc. Also included are initiators.

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

<Sensitizer (H)>
The photosensitive coloring composition can contain a sensitizer (H).
Examples of the sensitizer (H) include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, and naphthoquinone. Derivatives, polymethine dyes such as anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrin derivatives Radin derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organic ruthenium complexes, or Michler ketone derivatives, α-alpha Siloxy ester, acyl oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl anthraquinone, 4,4'-diethylisophthalophenone, 3,3' or 4,4'- Examples include tetra(t-butylperoxycarbonyl)benzophenone and 4,4'-bis(diethylamino)benzophenone. Among these, thioxanthone derivatives, Michler's ketone derivatives, and carbazole derivatives are mentioned. 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. Also edited by Shin Okawara et al., "Pigment Handbook" (1986, Kodansha), Shin Okawara et al., ed., "Chemistry of Functional Pigments" (1981, CMC), Tadazaburo Ikemori et al., ed., and "Special Functional Materials". (1986, CMC).

Commercial products of the sensitizer (H) include "KAYACURE DETX-S" (2,4-diethylthioxanthone manufactured by Nippon Kayaku Co., Ltd.) and "CHEMARK DEABP" (4,4'-bis(diethylamino)benzophenone manufactured by Chemical Co., Ltd.). ) etc.

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

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

<Thiol chain transfer agent (I)>
The photosensitive coloring composition can contain a thiol chain transfer agent as a chain transfer agent. By using thiol together with a photopolymerization initiator, thiyl radicals that act as chain transfer agents and are less susceptible to polymerization inhibition by oxygen are generated in the radical polymerization process after light irradiation, so the resulting colored composition has high sensitivity. .

Further, polyfunctional aliphatic thiols having two or more thiol groups bonded to aliphatic groups such as methylene and ethylene groups are preferred. More preferred is a polyfunctional aliphatic thiol having four or more thiol groups. By increasing the number of functional groups, the polymerization initiation function is improved, and it is possible to cure from the surface of the pattern to the vicinity of the base material.

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

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

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

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

Examples of the polymerization inhibitor (J) include 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-t-butylcatechol, 3-t-butylcatechol, Alkylcatechol compounds such as 4-t-butylcatechol and 3,5-di-t-butylcatechol, 2-methylresorcinol, 4-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2-propylresorcinol, 4 - Alkylresorcinol compounds such as propylresorcinol, 2-n-butylresorcinol, 4-n-butylresorcinol, 2-t-butylresorcinol, 4-t-butylresorcinol, methylhydroquinone, ethylhydroquinone, propylhydroquinone, t-butyl Hydroquinone, alkylhydroquinone compounds such as 2,5-di-t-butylhydroquinone, phosphine compounds such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, tribenzylphosphine, trioctylphosphine oxide, triphenylphosphine Examples include phosphine oxide compounds such as 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 nonvolatile content of the photosensitive coloring composition. In this range, the effect of the polymerization inhibitor becomes large, and the linearity of the taper, the wrinkles of the coating film, the pattern resolution, etc. become good.

<Ultraviolet absorber (K)>
The photosensitive coloring composition can contain an ultraviolet absorber (K). The ultraviolet absorber is an organic compound having an ultraviolet absorption function, and examples thereof include benzotriazole compounds, triazine organic compounds, benzophenone compounds, salicylic acid ester compounds, cyanoacrylate compounds, and salicylate compounds.

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

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

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

Triazine compounds include 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine, 2-[4,6- Bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol, 2-(2,4-dihydroxyphenyl) -2,4-bis(2,4-dimethylphenyl)-1,3,5-triazine and (2-ethylhexyl)-glycidic acid ester reaction product, 2,4-bis(2-hydroxy-4-butoxy) phenyl”-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-(hexyloxy ) Phenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, 2,4,6-tris( Examples include 2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine.

Examples of benzophenone compounds include 2,4-di-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid-3, 2-hydroxy-4-n- Octoxybenzophenone, 2,2'-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, 2-hydroxy-4-methoxy-2'-carboxybenzophenone and the like.

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

<Antioxidant (L)>
The photosensitive coloring composition can contain an antioxidant. The antioxidant prevents the photopolymerization initiator and thermosetting compound contained in the photosensitive coloring composition from oxidizing and yellowing due to heat curing or the thermal process during ITO annealing, and prevents the penetration of the coating film. rate can be improved.

Examples of antioxidants include hindered phenol-based, hindered amine-based, phosphorus-based, sulfur-based, and hydroxylamine-based compounds. In this specification, the antioxidant is preferably a compound that does not contain a halogen atom.

Among these, hindered phenol antioxidants, hindered amine antioxidants, phosphorus antioxidants, and sulfur antioxidants are preferred from the viewpoint of achieving both transmittance and sensitivity of the coating film.

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

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

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

Sulfur-based antioxidants include, for example, 2,2-bis{[3-(dodecylthio)-1-oxopropoxy]methyl}propane-1,3-diylbis[3-(dodecylthio)propionate], 3,3'- Ditridecyl thiobispropionate, 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,4-bis[(octylthio)methyl]-o- Examples include cresol, 2,4-bis[(laurylthio)methyl]-o-cresol, and the like. Other oligomer type and polymer type compounds having a thioether structure can also be used.

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

Further, the content of the antioxidant is preferably 0.5 to 5.0% by mass based on 100% by mass of the nonvolatile content of the coloring composition because transmittance, spectral characteristics, and sensitivity are good.

<Leveling agent (M)>
The photosensitive coloring composition can contain a leveling agent. This further improves the coating properties of the composition on the transparent substrate and the drying properties 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 linear polymers consisting of siloxane bonds and modified siloxane polymers having organic groups introduced into side chains or terminals.

Examples of the fluorosurfactant include compounds having a fluorocarbon chain.

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

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

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

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

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

The content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the nonvolatile components of the photosensitive coloring composition. Within this range, the balance between the coating properties, pattern adhesion, and transmittance of the photosensitive coloring composition is further improved.

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

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

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

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

The content of the adhesion improver is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the colorant. When contained in an appropriate amount, the photosensitivity of the photosensitive coloring composition is improved, the adhesion of the film is further improved, and the resolution of the pattern is also further improved.
<Solvent>
The photosensitive coloring composition can contain a solvent. This makes it easier to adjust the viscosity of the photosensitive coloring composition, making it easier to form a film with a smooth surface. The solvent may be appropriately selected depending on the purpose of use and may be contained in an appropriate amount.

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

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

Ether solvents include, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, 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 Examples include ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl-n-propyl ether, anisole, phenetol, and methylanisole.

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

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

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

Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, mesitylene, and the like.

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

Among these, solvents having a boiling point of 120° C. or higher and 180° C. or lower at 1 atm are preferred in terms of coating properties and drying properties. For example, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2- Pentanone, N,N-dimethylformamide, N-methylpyrrolidone and the like are more preferred, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate and the like are even more preferred.

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

<Method for producing photosensitive coloring composition>
The photosensitive coloring composition is prepared by performing a dispersion treatment using, for example, a red pigment (A), a resin-type dispersant (B), and the like to prepare a pigment dispersion. Next, the pigment dispersion, the binder resin (C), the photopolymerizable compound (D), and the photopolymerizable initiator (E) can be mixed to produce the composition. Note that it is preferable to use a dispersion aid (dye derivative or surfactant) when preparing the pigment dispersion.
The photosensitive coloring composition is preferably prepared as a solvent-developable coloring composition or an alkali-developable coloring composition.

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

<Dispersed particle size of pigment>
The average dispersed particle diameter of the red pigment (A) is preferably 30 to 200 nm, more preferably 40 to 120 nm. Within this range, the viscosity can be suppressed and the dispersion stability can be further improved.

As a method for measuring the dispersed particle diameter of the pigment, it is preferable to use Microtrac UPA-EX150 manufactured by Nikkiso Co., Ltd., which employs a dynamic light scattering method (FFT power spectrum method). The settings of the device include setting the particle permeability to absorption mode, the particle shape to non-spherical, and D50 to the average diameter. When the diluting solvent for measurement is the same as the solvent used for the dispersion, and the ultrasonic-treated sample is measured immediately after sample preparation, results with less variation can be obtained.

<Removal of coarse particles>
In this specification, it is preferable to remove the coarse particles contained at the pigment dispersion stage or after producing the photosensitive coloring composition. This allows foreign matter to be removed from the coating, making it easier to form fine patterns.
The removal is preferably carried out by, for example, centrifugation, a sintered filter, a membrane filter, or the like. Thereby, foreign substances such as coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more can be removed. As described above, the photosensitive coloring composition preferably does not substantially contain particles of 0.5 μm or more, and preferably does not contain particles of 0.3 μm or less.

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

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

The filter segments can be formed by, for example, a printing method, an electrodeposition method, a transfer method, an inkjet method, a photolithography method, or the like.
The printing method allows pattern formation by simply repeating printing and drying of a photosensitive coloring composition prepared as a printing ink, so it is a low-cost and excellent method for producing color filters in mass production. Furthermore, advances in printing technology have made it possible to print fine patterns with high dimensional accuracy and smoothness. In order to perform printing, it is preferable to use a composition that prevents the ink from drying or solidifying on the printing plate or blanket. It is also important to control the fluidity of the ink on the printing press, and the viscosity of the ink can also be adjusted using a dispersant or extender pigment.

In the electrodeposition method, a color filter is produced by using a transparent conductive film formed on a transparent substrate and electrodepositing filter segments of each color on the transparent conductive film by electrophoresis of colloidal particles. Furthermore, in the transfer method, filter segments are formed on the release-treated surface of the release sheet. This filter segment is then transferred to a transparent substrate to produce it.

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

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

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

The color filter of the present invention is attached to a counter substrate using a sealant, liquid crystal is injected through an injection port provided in the sealing part, the injection port is sealed, and a polarizing film or a retardation film is attached to the substrate as necessary. A color liquid crystal display device is manufactured by pasting it on the outside. This color liquid crystal display device supports twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), and optically convensed bend (OCB). ) can be used in a liquid crystal display mode that performs colorization using color filters.

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

<Liquid crystal display device>
The liquid crystal display device of this specification includes a color filter.
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, but in the present invention, it is preferable to use a white LED because the red reproduction area is expanded. FIG. 1 is a schematic cross-sectional view of a liquid crystal display device 10 equipped with a color filter of the present invention. The device 10 shown in FIG. 1 includes a pair of transparent substrates 11 and 21 that are spaced apart and facing each other, and a liquid crystal LC is sealed between them.

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

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

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

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

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

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

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

EXAMPLES Hereinafter, the present invention will be explained with reference to Examples, but the present invention is not limited thereto. In addition, in the production examples and examples, "parts" mean "parts by mass" and "%" mean "% by mass" unless otherwise specified.

Prior to Examples, each measurement method will be explained.

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

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

(Acid value of resin (mgKOH/g))
Add 80 ml of acetone and 10 ml of water to 0.5 to 1 g of the resin solution, stir to dissolve uniformly, and use an automatic titration device ("COM-555" manufactured by Hiranuma Sangyo) with 0.1 mol/L KOH aqueous solution as the titrant. ) to measure the acid value (mgKOH/g) of the resin solution. Then, the acid value per nonvolatile content of the resin was calculated from the acid value of the resin solution and the nonvolatile content concentration of the resin solution.

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

<Production method of finely divided pigment>
<Method for producing diketopyrrolopyrrole pigment>
(Diketopyrrolopyrrole pigment 1)
In a stainless steel reaction vessel equipped with a reflux tube, under a nitrogen atmosphere, 200 parts of tert-amyl alcohol dehydrated with a molecular sieve and 140 parts of sodium-tert-amyl alkoxide were added, and the mixture was heated to 100°C with stirring to dissolve the alcoholate solution. Prepared. On the other hand, 88 parts of diisopropyl succinate and 153.6 parts of 4-bromobenzonitrile were added to a glass flask and heated to 90° C. with stirring to dissolve them, thereby preparing a solution of the mixture thereof. The heated solution of this mixture was slowly dropped into the alcoholate solution heated to 100° C. at a constant rate over 2 hours while stirring vigorously. After completion of the dropwise addition, heating and stirring were continued at 90° C. for 2 hours to obtain an alkali metal salt of a diketopyrrolopyrrole compound. Furthermore, 600 parts of methanol, 600 parts of water, and 304 parts of acetic acid were added to a glass jacketed reaction vessel, and the mixture was cooled to -10°C. This cooled mixture was cooled to 75°C using a high-speed stirring disperser while rotating a shear disk with a diameter of 8 cm at 4000 rpm.The alkali metal salt of the previously obtained diketopyrrolopyrrole compound The solution was added in portions. At this time, the alkali metal salt of the diketopyrrolopyrrole compound is added at a rate of 75°C while cooling so that the temperature of the mixture consisting of methanol, acetic acid, and water is always kept below -5°C. It was added in small portions over approximately 120 minutes while adjusting the amount. After addition of the alkali metal salt, red crystals precipitated and a red suspension was formed. Subsequently, the obtained red suspension was washed with an ultrafiltration device at 5° C., and then filtered to obtain a red paste. This paste was redispersed in 3,500 parts of methanol cooled to 0°C to form a suspension with a methanol concentration of approximately 90%, and stirred at 5°C for 3 hours to perform particle sizing and washing accompanied by crystal transition. Subsequently, the water paste of the diketopyrrolopyrrole compound obtained by filtration with an ultrafilter was dried at 80° C. for 24 hours and pulverized to obtain 150.8 parts of diketopyrrolopyrrole pigment 1. Obtained.

(Diketopyrrolopyrrole pigment 2)
220 parts of tert-amyl alcohol was placed in reaction vessel 1, and while cooling in a water bath, 32 parts of 60% NaH was added, and the mixture was heated and stirred at 90°C. Next, in reaction vessel 2, 100 parts of tert-amyl alcohol, 85.0 parts of a compound of the following chemical formula (20) synthesized by the method of Tetrahedron, 58 (2002) 5547-5565, and 60.9 parts of 4-cyanobiphenyl were heated. The solution was dissolved and added dropwise to reaction vessel 1 over 2 hours. After reacting at 120°C for 10 hours, it was cooled to 60°C, 400 parts of methanol and 50 parts of acetic acid were added, and the mixture was filtered and washed with methanol to obtain 88.1 parts of diketopyrrolopyrrole pigment 2. .

Chemical formula (20)

(Diketopyrrolopyrrole pigment 3)
The process was repeated in the same manner as in the production of diketopyrrolopyrrole pigment 2, except that 60.9 parts of 4-cyanobiphenyl was changed to 54.1 parts of 4-tert-butylbenzonitrile, and 83.9 parts of diketopyrrolopyrrole pigment 3 was used. Obtained.

(Diketopyrrolopyrrole pigment 4)
The process was repeated in the same manner as in the production of diketopyrrolopyrrole pigment 2, except that 60.9 parts of 4-cyanobiphenyl was changed to 68.7 parts of N-butyl-4-cyanobenzamide. I got it.

(Diketopyrrolopyrrole pigment 5)
The process was repeated in the same manner as in the production of diketopyrrolopyrrole pigment 2, except that 60.9 parts of 4-cyanobiphenyl was changed to 75.5 parts of N-phenyl-4-cyanobenzamide. I got it.

(Diketopyrrolopyrrole pigment 6)
The process was repeated in the same manner as in the production of diketopyrrolopyrrole pigment 2, except that 60.9 parts of 4-cyanobiphenyl was changed to 87.8 parts of N,N-dibutyl-4-cyanobenzamide. .I got 1 copy.

(Diketopyrrolopyrrole pigment 7)
220 parts of tert-amyl alcohol was placed in reaction vessel 1, and while cooling in a water bath, 32 parts of 60% NaH was added, and the mixture was heated and stirred at 90°C. Next, in reaction vessel 2, 100 parts of tert-amyl alcohol, 99.2 parts of a compound of the following chemical formula (21) synthesized by the method of Tetrahedron, 58 (2002) 5547-5565, and 60.9 parts of 4-cyanobiphenyl were heated. The solution was dissolved and added dropwise to reaction vessel 1 over 2 hours. After reacting at 120°C for 10 hours, it was cooled to 60°C, 400 parts of methanol and 50 parts of acetic acid were added, and then filtered and washed with methanol to obtain 87.8 parts of diketopyrrolopyrrole pigment 7. .

Chemical formula (21)

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

(Manufacture of finely divided pigment (A-2))
The process was carried out in the same manner as in the production of finely divided pigment (A-1), except that 100 parts of diketopyrrolopyrrole pigment 1 was changed to 100 parts of diketopyrrolopyrrole pigment 2. A-2) 96.5 parts were obtained.

(Manufacture of finely divided pigment (A-3))
The production of the diketopyrrolopyrrole-based finely divided pigment (A-1) was carried out in the same manner as in the production of the finely divided pigment (A-1), except that 100 parts of diketopyrrolopyrrole pigment 1 was changed to 100 parts of diketopyrrolopyrrole pigment 3. A-3) 98.1 parts were obtained.

(Manufacture of finely divided pigment (A-4))
The process was carried out in the same manner as in the production of finely divided pigment (A-1), except that 100 parts of diketopyrrolopyrrole pigment 1 was changed to 100 parts of diketopyrrolopyrrole pigment 4. A-4) 98.0 parts were obtained.

(Manufacture of finely divided pigment (A-5))
The process was repeated in the same manner as in the production of finely divided pigment (A-1), except that 100 parts of diketopyrrolopyrrole pigment 5 was changed to 100 parts of diketopyrrolopyrrole pigment 5. A-5) 98.4 parts were obtained.

(Manufacture of finely divided pigment (A-6))
The process was carried out in the same manner as in the production of finely divided pigment (A-1), except that 100 parts of diketopyrrolopyrrole pigment 6 was changed to 100 parts of diketopyrrolopyrrole pigment 6. A-6) 97.5 parts were obtained.

(Manufacture of finely divided pigment (A-7))
The process was carried out in the same manner as in the production of finely divided pigment (A-1), except that 100 parts of diketopyrrolopyrrole pigment 1 was changed to 100 parts of diketopyrrolopyrrole pigment 7. A-7) 97.5 parts were obtained.

(Manufacture of finely divided pigment (A-8))
Diketopyrrolopyrrole pigment 1 was prepared from commercially available C.I. I. Pigment Red 254 (BASF's "Irgazin Red D3656 HD") was manufactured in the same manner as for the finely divided pigment (A-1), and the diketopyrrolopyrrole finely divided pigment (A-8) 97 was used. .I got 3 copies.

(Manufacture of finely divided pigment (A-9))
Anthraquinone red pigment C. I. Pigment Red 177 ("Sinilex Red SR3C" manufactured by Shinic): 500 parts, sodium chloride: 500 parts, and diethylene glycol: 250 parts were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 120°C for 8 hours. . Next, this kneaded material was poured into 5 liters of warm water, heated to 70°C and stirred for 1 hour to form a slurry. After repeated filtration and water washing to remove sodium chloride and diethylene glycol, it was dried at 80°C overnight. A finely divided pigment (A-9) was obtained.

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

(Manufacture of finely divided pigment (A-11))
Commercially available C. I. 100 parts of Pigment Red 269 (PR269) ("Toner Magenta F8B" manufactured by Clariant), 800 parts of sodium chloride, and 180 parts of diethylene glycol were placed in a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho) and kneaded at 70° C. for 5 hours. This mixture was poured into 4000 parts of warm water, heated to about 80°C and stirred with a high-speed mixer for about 1 hour to form a slurry. After repeated filtration and water washing to remove the salt and solvent, the mixture was heated to about 80°C for 24 hours. It was dried to obtain 100 parts of finely divided pigment (A-11).

<Production of finely divided yellow pigment>
(Finely refined yellow pigment (a-1 to 3))
According to the examples of JP-A-2012-226110, finely divided quinophthalone pigments (a-1 to a-3) were prepared using quinophthalone pigments represented by the following chemical formula (56) to quinophthalone pigments represented by chemical formula (58) as raw materials.

(Finely refined yellow pigment a-1) (Finely refined yellow pigment a-2)
Formula (56) Formula (57)

(Finely refined yellow pigment a-3)
Formula (58)

(Finely refined yellow pigment (a-4))
C. I. 100 parts of Pigment Yellow 138 (“Paliotol Yellow K0960-HD” manufactured by BASF Japan), 700 parts of sodium chloride, and 180 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80° C. for 6 hours. . This mixture was poured into 2,000 parts of warm water, stirred for 1 hour while heating to 80°C to form a slurry, filtered and washed repeatedly to remove salt and solvent, dried overnight at 80°C, and made into a slurry of 95 parts of fine powder. A colored yellow pigment (a-4) was obtained.

(Finely refined yellow pigment (a-5))
Isoindoline yellow pigment C. I. 100 parts of Pigment Yellow 139 ("Irgafore Yellow 2R-CF" manufactured by BASF Japan), 1,600 parts of sodium chloride, and 190 parts of diethylene glycol were placed in a 1-gallon stainless steel kneader and kneaded at 60° C. for 10 hours. Next, this mixture was poured into 3 liters of warm water, heated to about 80°C and stirred with a high-speed mixer for about 1 hour to form a slurry, and after repeated filtration and water washing to remove sodium chloride and solvent, It was dried at ℃ for one day and night to obtain a finely divided yellow pigment (a-5).

(Finely refined yellow pigment (a-6))
100 parts of a metal complex yellow pigment (C.I. Pigment Yellow 150, "Yellow Pigment E4GN" manufactured by LANXESS), 1600 parts of sodium chloride, and 190 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho). The mixture was kneaded at 60°C for 10 hours. Next, this mixture was poured into 3 liters of warm water, heated to about 80°C and stirred with a high-speed mixer for about 1 hour to form a slurry, and after repeated filtration and water washing to remove sodium chloride and solvent, It was dried at ℃ for one day and night to obtain a finely divided yellow pigment (a-6). The average primary particle diameter was 36.6 nm.

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

色素誘導体（ｂ０-２）
<Dye derivative (b0)>
The dye derivatives as described below were used.
Pigment derivative (b0-1)

Pigment derivative (b0-2)

Pigment derivative (b0-3)
A dye derivative (b0-3) was obtained using the same manufacturing method as the quinophthalone compound (QL-c-1) described in Examples of JP-A-2015-172732.

Pigment derivative (b0-4)
A dye derivative (b0-4) was obtained using the same manufacturing method as the quinophthalone compound (QL-f-1) described in Examples of JP-A-2015-172732.

Pigment derivative (b0-3) Pigment derivative (b0-4)

Pigment derivative (b0-5)
According to the synthesis method described in Japanese Patent No. 4585781, the dye derivative (b0-5)
An Al salt was obtained.

Pigment derivative (b0-5)

<Production of basic resin type dispersant (b1) solution>
(Basic resin type dispersant (b1-1) solution)
40 parts of methyl methacrylate, 10 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine as a catalyst were charged into a reaction apparatus equipped with a gas introduction pipe, a condenser, a stirring blade, and a thermometer, and the mixture was heated at 50°C while flowing nitrogen. The mixture was stirred for 1 hour, and the atmosphere in the system was replaced with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate as an initiator, 5.6 parts of cuprous chloride and 133 parts of PGMAc as a catalyst were charged, and the temperature was raised to 110°C under a nitrogen stream to form the first block (B block). Polymerization started. After 4 hours of polymerization, the polymerization solution was sampled and the nonvolatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more as calculated from the nonvolatile content. Next, 61 parts of PGMAc, 40 parts of dimethylaminoethyl methacrylate as a second block (A block) monomer, and 10 parts of methacryloyloxyethylbenzyldimethylammonium chloride were added to this reactor, and the temperature was maintained at 110°C under a nitrogen atmosphere. The reaction was continued with stirring. Two hours after the addition, the polymerization solution was sampled and the non-volatile content was measured, and it was confirmed that the polymerization conversion rate of the second block (A block) was 98% or more in terms of non-volatile content, and the reaction solution was cooled to room temperature. Polymerization was stopped by cooling. 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 (b1-1) having an amine value per nonvolatile content of 169.8 mgKOH/g was obtained. After cooling to room temperature, about 2 g of the resin-type dispersant solution was sampled and dried by heating at 180°C for 20 minutes to measure the non-volatile content. A basic resin type dispersant (b1-1) solution was prepared by adding propylene glycol monomethyl ether acetate (PGMAc) so that the amount was 30% by mass.

(Basic resin type dispersant (b1-2) solution)
133 parts of PGMAc was charged into a reaction tank equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, and the temperature was raised to 110° C. while purging with nitrogen. Charge 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) into a dropping tank until uniform. After stirring, it was added dropwise to the reaction tank over 2 hours, and then the reaction was continued at the same temperature for 3 hours. In this way, a basic resin type dispersant (b1-2) having an amine value per nonvolatile content of 345 mgKOH/g and a number average molecular weight (Mn) of 3000 was obtained.
A basic resin-type dispersant (b1-2) solution was prepared by diluting in the same manner as the resin-type dispersant (b1-1) solution.

(Basic resin type dispersant (b1-3) solution)
133 parts of PGMAc was charged into a reaction tank equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, and the temperature was raised to 110° C. while purging with nitrogen. In a dropping tank were placed 177 parts of 1,2,2,6,6-pentamethylpiperidyl methacrylate, 3 parts of methyl acrylate, 20 parts of 2-hydroxyethyl methacrylate, 61 parts of PGMAc, and 2,2'-azobis(2,4-dimethylvalero). After charging 6 parts of nitrile and stirring until uniform, the mixture was added dropwise to the reaction tank over 2 hours, and the reaction was then continued at the same temperature for 3 hours. In this way, a basic resin type dispersant (b1-3) having an amine value per nonvolatile content of 201 mgKOH/g and a number average molecular weight of 3,800 (Mn) was obtained. A basic resin type dispersant (b1-3) solution was prepared by diluting in the same manner as the basic resin type dispersant (b1-1) solution.

(Basic resin type dispersant (b1-4) solution)
A flask equipped with a cooling tube and a stirrer was charged with 1.0 part of AIBN and 186 parts of propylene glycol monomethyl ether acetate, followed by 27 parts of methyl methacrylate, 27 parts of butyl methacrylate, 19 parts of 2-ethylhexyl methacrylate, 16 parts of benzyl methacrylate, and triethylene. 16 parts of glycol ethyl ether methacrylate and 3.6 parts of cumyl dithiobenzoate were charged, and the mixture was purged with nitrogen for 30 minutes. Thereafter, the temperature of the reaction solution was raised to 60° C. by gentle stirring, and this temperature was maintained for 24 hours to perform living radical polymerization.
Next, a solution prepared by dissolving 1.0 part of AIBN and 54 parts of dimethylaminoethyl methacrylate in 108 parts of propylene glycol monomethyl ether acetate and purging with nitrogen for 30 minutes was added to this reaction solution, and living radical polymerization was carried out at 60°C for 24 hours. , and then diluted in the same manner as the basic resin type dispersant (b1-1) solution to prepare a basic resin type dispersant (b1-4) solution.

(Basic resin type dispersant (b1-5) solution)
A reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer was charged with 500 parts of methyl methacrylate, 22 parts of thioglycerol, and 511 parts of propylene glycol monomethyl ether acetate, and the mixture was replaced with nitrogen gas. The inside of the reaction vessel was heated to 90°C, and 0.50 part of AIBN was added thereto, followed by a reaction for 7 hours. After confirming that 95% had reacted by measuring non-volatile content, it was cooled to room temperature to obtain a 50% non-volatile solution of a vinyl polymer having a weight average molecular weight of 5,200 and having two free hydroxyl groups at one end region. Next, 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 mixture was replaced with nitrogen gas. The inside of the reaction vessel was heated to 100°C and reacted for 3 hours, and then cooled to 40°C to obtain a prepolymer solution having isocyanate groups. 22.2 parts of methyliminobispropylamine, 13.2 parts of dibutylamine, and 304.6 parts of propylene glycol monomethyl ether acetate were charged into a reaction vessel 2 equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer and heated to 100°C. . The prepolymer solution was added dropwise there over 30 minutes, and after reacting for an additional hour, the reaction was completed by cooling to room temperature. If necessary, remove a portion of the solvent by distillation under reduced pressure, and then dilute in the same manner as the basic resin type dispersant (b1-1) solution to obtain the basic resin type dispersant (b1-5) solution. Prepared.

(Basic resin type dispersant (b1-6) solution)
30 parts of methyl methacrylate, 30 parts of n-butyl methacrylate, 20 parts of hydroxyethyl methacrylate, and 13.2 parts of tetramethylethylenediamine were charged into a reaction apparatus equipped with a gas inlet pipe, a condenser, a stirring blade, and a thermometer, and the mixture was flushed with nitrogen. The mixture was stirred at 50° C. for 1 hour while purging the system with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate, 5.6 parts of cuprous chloride, and 133 parts of PGMAc were charged, and the temperature was raised to 110° C. under a nitrogen stream to start polymerization of the first block (B block). After 4 hours of polymerization, the polymerization solution was sampled and the nonvolatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more calculated from the nonvolatile content.
Next, 61 parts of PGMAc and 20 parts of 1,2,2,6,6-pentamethylpiperidyl methacrylate (manufactured by Hitachi Chemical Co., Ltd., Fancryl FA-711MM) were added to this reactor. The reaction was continued by stirring while maintaining the temperature at 110° C. and nitrogen atmosphere. Two hours after adding 1,2,2,6,6-pentamethylpiperidyl methacrylate, the polymerization solution was sampled and the non-volatile content was measured, and the polymerization conversion rate of the second block (A block) was 98 in terms of non-volatile content. % or more, and the reaction solution was cooled to room temperature to stop the polymerization.
In this way, a basic resin type dispersant (b1-6) having a piperidyl skeleton with an amine value per nonvolatile content of 57 mgKOH/g and a number average molecular weight of 4,500 (Mn) was obtained.
A basic group resin type dispersant (b1-6) solution was prepared by diluting in the same manner as the resin type dispersant (b1-1) solution.

(Basic resin type dispersant (b1-7) solution)
In the method for producing pigment dispersant (1) described in Production Example 1 of Japanese Patent No. 5513691, [(3-(N,N-dimethylamino)propylacrylamide/methoxypolyethylene glycol methacrylate copolymer (23/77 weight) %); quaternization rate 27 mol%)] was diluted in the same manner as the resin-type dispersant (b1-1) solution to obtain a basic group resin-type dispersant (b1) having an amide bond. -7) A solution was prepared.

(Production of phosphoric acid resin type dispersant (b2) solution)
(Production of phosphoric acid resin type dispersant (b2-1) solution)
186 g of lauryl alcohol, 571 parts of ε-caprolactone monomer, and 0.6 parts of tetrabutyl titanate were placed in a reaction vessel equipped with a nitrogen gas inlet tube, a condenser, and a stirrer, and after purging with nitrogen gas, heated at 120 ° C. for 3 hours. Stirred. Disappearance of caprolactone monomer was confirmed using an RI detector of GPC (gel permeation chromatography) using tetrahydrofuran as an eluent. After cooling to 40°C or lower, the mixture was mixed with 84.5 parts of polyphosphoric acid having an orthophosphoric acid equivalent content of 116%, the temperature was gradually raised, and the mixture was heated at 80°C for 6 hours with stirring to give a number average molecular weight of R1 of 760. , a phosphoric acid resin type dispersant (b2-1) was obtained in which the abundance ratio of n=1 and 2 was 100:12. By adjusting the nonvolatile content with PGMAc, a phosphoric acid resin type dispersant (b2-1) solution with a nonvolatile content of 30% and an acid value per nonvolatile content of 166 mgKOH/g was obtained.

(Production of phosphoric acid resin type dispersant (b2-2) solution)
A separable 4-necked flask was equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirring device, and 1500 parts of cyclohexanone was charged therein. The temperature was raised to 80°C and the inside of the reaction vessel was replaced with nitrogen. 210 parts of n-butyl methacrylate, 90 parts of 2-hydroxyethyl methacrylate, 60 parts of methacrylic acid, 120 parts of paracumylphenol ethylene oxide modified acrylate ("Aronix M-110" manufactured by Toagosei Co., Ltd.), 6 parts of acid phosphoxyethyl methacrylate, A mixed solution of 30 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After the dropwise addition was completed, the reaction was continued for another 3 hours to obtain a phosphoric acid resin type dispersant (b2-2) solution with a nonvolatile content of 30% and a weight average molecular weight of 24,000.

(Production of salt (b3) solution of basic resin type dispersant)
(Salt (b3-1) solution of phenylphosphonic acid and basic resin type dispersant having an amino group)
In a 100 mL round bottom flask, 12.6 parts of a basic resin type dispersant (methyl methacrylate/dimethylaminoethyl methacrylate: composition ratio 5/3) was dissolved in 35 parts of PGMAc, and phenylphosphonic acid, which is a salt forming component, was dissolved in 35 parts of PGMAc. By adding 2.4 parts (0.5 molar equivalent to dimethylaminoethyl methacrylate) and stirring at a reaction temperature of 40°C for 2 hours, the phenylphosphonic acid and the basic resin type dispersant having an amino group were combined. A solution of salt (b3-1) with a nonvolatile content of 30% by mass was prepared.

(Salt (b3-2) solution of phenylphosphonic acid and a basic resin type dispersant having an amino group and an ammonium salt)
In a 100 mL round bottom flask, add 12.6 parts of a basic resin type dispersant (methyl methacrylate/dimethylaminoethyl methacrylate/dimethylaminoethyl methacrylate methyl chloride salt: composition weight ratio 3/3/2) to 35 parts of PGMAc. , add 2.4 parts of phenylphosphonic acid (0.5 molar equivalent to dimethylaminoethyl methacrylate) as a salt-forming component, and stir at a reaction temperature of 40°C for 2 hours to form phenylphosphonic acid. A 30% by mass solution of non-volatile content of a salt (b3-2) of a basic resin type dispersant having an amino group and an ammonium salt was prepared.

(Production of carboxylic acid resin type dispersant (b4) solution)
(Production of carboxylic acid resin type dispersant (b4-1) solution)
A reaction vessel equipped with a gas inlet tube, temperature, condenser, and stirrer was charged with 10 parts of methacrylic acid, 100 parts of methyl methacrylate, 70 parts of i-butyl methacrylate, 20 parts of benzyl methacrylate, and 50 parts of PGMAc, and the mixture was purged with nitrogen gas. The inside of the reaction vessel was heated and stirred at 50°C, and 12 parts of 3-mercapto-1,2-propanediol was added. The temperature was raised to 90°C, and a reaction was carried out for 7 hours while adding a solution of 0.1 part of 2,2'-azobisisobutyronitrile to 90 parts of PGMAc. It was confirmed by non-volatile content measurement that 95% had reacted. 19 parts of pyromellitic anhydride, 50 parts of PGMAc, 50 parts of cyclohexanone, and 0.4 part of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added and reacted at 100°C for 7 hours. . After confirming that 98% or more of the acid anhydride was half-esterified by measuring the acid value, the reaction was terminated, and the mixture was diluted with PGMAc so that the non-volatile content was 30% by measuring the non-volatile content, and the acid value was 70 mgKOH/g. A resin-type dispersant (b4-1) solution having a weight average molecular weight of 8,500 was obtained.

(Production of carboxylic acid resin type dispersant (b4-1-1) solution)
3 parts of trimellitic anhydride, 1 part of 3-mercapto-1,2-propanediol, 50 parts of PGMAc, and 0.1 part of dimethylbenzylamine were placed in a reaction tank equipped with a gas introduction tube, condenser, stirring blade, and thermometer. I prepared it. After purging with nitrogen gas, the inside of the reaction vessel was heated to 120°C and reacted for 4 hours, and then at 80°C for 2 hours. Furthermore, 30 parts of tert-butyl acrylate, 20 parts of ETERNACOLL OXMA ((3-ethyloxetan-3-yl) methyl methacrylate, manufactured by Ube Industries, Ltd.), 5 parts of methacrylic acid, 40 parts of ethyl acrylate, and 10 parts of PGMAc were added to the reaction vessel. While maintaining the inside at 80°C, 0.2 part of 2,2'-azobisisobutyronitrile was added in 15 portions every 30 minutes. One hour after the final addition, non-volatile content was measured and it was confirmed that 95% of the monomers had reacted. A carboxylic acid resin type dispersant (b4-1- 1) A solution was obtained. Note that the vinyl polymer portion of the carboxylic acid resin type dispersant (b4-1-1) has tert-butyl, oxetane group, and carboxyl group as thermally crosslinkable functional groups.

(Production of carboxylic acid resin type dispersant (b4-1-2) solution)
108 parts of 1-thioglycerol, 174 parts of pyromellitic anhydride, 650 parts of PGMAc, and 0.2 parts of monobutyltin oxide as a catalyst were charged into a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, and the mixture was heated with nitrogen gas. After the substitution, the mixture was reacted at 120° C. for 5 hours (first step). Acid value measurement confirmed that 95% or more of the acid anhydride was half-esterified. Next, 160 parts of the compound obtained in the first step in terms of nonvolatile content, 200 parts of 2-hydroxypropyl methacrylate, 200 parts of ethyl acrylate, 150 parts of t-butyl acrylate, 200 parts of 2-methoxyethyl acrylate, and 200 parts of methyl acrylate. 1 part, 50 parts of methacrylic acid, and 663 parts of PGMAc were charged, the inside of the reaction vessel was heated to 80°C, 1.2 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) was added, and the mixture was reacted for 12 hours. (Second step). It was confirmed by non-volatile content measurement that 95% had reacted. Finally, 500 parts of a 50% PGMAc solution of the compound obtained in the second step, 27.0 parts of 2-methacryloyloxyethyl isocyanate (MOI), and 0.1 part of hydroquinone were charged, and 2270 cm based on the isocyanate group was measured by IR. The reaction was continued until the disappearance of the -1 peak was confirmed (third step). After confirming the disappearance of the peak, the reaction solution was cooled and the nonvolatile content was adjusted with PGMAc to obtain a carboxylic acid resin type dispersant (b4-1-2) solution with a nonvolatile content of 30%. The obtained dispersant had an acid value of 68, an unsaturated double bond equivalent of 1,593, and a weight average molecular weight of 13,000.

(Production of carboxylic acid resin type dispersant (b4-2) solution)
62.6 parts of 1-dodecanol, 287.4 parts of ε-caprolactone, and 0.1 part of monobutyltin(IV) oxide as a catalyst were charged into a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, and nitrogen gas was added. After replacing the mixture with , it was heated and stirred at 120° C. for 4 hours. After confirming that 98% of the reaction had occurred by measuring non-volatile content, 73.3 parts of pyromellitic anhydride was added, and the mixture was reacted at 120° C. for 2 hours. After measuring the acid value, it was confirmed that 98% or more of the acid anhydride had been half-esterified, and the reaction was terminated. A carboxylic acid resin type dispersant (b4-2) solution with a nonvolatile content of 30% was obtained by adjusting the nonvolatile content with PGMAc. The obtained dispersant was a white solid at room temperature and had an acid value of 49 mgKOH/g.

<Production example of binder resin (C)>
(Preparation of binder resin (C-1) liquid)
196 parts of cyclohexanone was placed in a separable 4-neck flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube, and a stirring device. 196 parts of cyclohexanone was then heated to 80°C, the inside of the reaction vessel was replaced with nitrogen, and then added dropwise. From the tube, 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, 20.7 parts of paracumylphenol ethylene oxide modified acrylate ("Aronix M110" manufactured by Toagosei Co., Ltd.) A mixture of 1.1 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After the dropwise addition was completed, the reaction was continued for an additional 3 hours to obtain an acrylic resin solution. After cooling to room temperature, approximately 2 parts of the resin solution was sampled and dried by heating at 180°C for 20 minutes to measure the nonvolatile content, and PGMAc was added to the previously synthesized resin solution so that the nonvolatile content was 20%. A binder resin (C-1) solution was prepared. The weight average molecular weight (Mw) was 26,000.

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

(Preparation of binder resin (C-3) liquid)
370 parts of cyclohexanone was charged into a separable 4-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube, and a stirring device, the temperature was raised to 80°C, and the inside of the flask was replaced with nitrogen. 18 parts of milphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 10 parts of benzyl methacrylate, 18.2 parts of glycidyl methacrylate, 25 parts of methyl methacrylate, and 2.0 parts of 2,2'-azobisisobutyronitrile. part of the mixture was added dropwise over 2 hours. After the dropwise addition, the mixture was further reacted at 100°C for 3 hours, and then a solution of 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 100°C for 1 hour. Next, the inside of the container was replaced with air, and 9.3 parts of acrylic acid (100% of glycidyl groups), 0.5 parts of trisdimethylaminophenol, and 0.1 part of hydroquinone were added to the container, and heated at 120°C. The reaction continued for 6 hours, and when the nonvolatile acid value reached 0.5, the reaction was terminated to obtain an acrylic resin solution. Further, 19.5 parts of tetrahydrophthalic anhydride (100% of the generated hydroxyl groups) and 0.5 parts of triethylamine were added and reacted at 120° C. for 3.5 hours to obtain a solution of acrylic resin.
After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180°C for 20 minutes to measure the nonvolatile content. PGMAc was added to the previously synthesized resin solution so that the nonvolatile content was 20% by mass. A binder resin (C-3) solution was prepared. 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 tank, and on the other hand, as a monomer dropping tank, 40 parts of dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, 40 parts of methacrylic acid, and methacrylic acid were prepared. Prepare a well-stirred mixture of 120 parts of methyl, 4 parts of t-butylperoxy-2-ethylhexanoate ("Perbutyl O" manufactured by NOF Corporation), and 40 parts of PGMAc, and use it as a chain transfer agent dropping tank to add n-dodecane. A mixture of 8 parts of thiol and 32 parts of PGMAc was prepared by stirring thoroughly.
After charging 395 parts of PGMAc into a reaction tank and purging with nitrogen, the temperature of the reaction tank was raised to 90°C by heating in an oil bath while stirring. After the temperature of the reaction tank stabilized at 90°C, dropping was started from the monomer dropping tank and the chain transfer agent dropping tank. Each dropwise addition took 135 minutes while maintaining the temperature at 90°C. Sixty minutes after the dropwise addition was completed, the temperature of the reaction tank was raised to 110°C. After maintaining the temperature at 110°C for 3 hours, a gas introduction tube was attached to the separable flask, and bubbling of a mixed gas of oxygen/nitrogen = 5/95 (volume ratio) was started. Next, 70 parts of glycidyl methacrylate, 0.4 part of 2,2'-methylenebis(4-methyl-6-t-butylphenol), and 0.8 part of triethylamine were placed in a reaction tank, and the mixture was allowed to react at 110°C for 12 hours. Ta. After that, 150 parts of PGMAc was added and cooled to room temperature, and about 2 g of the resin solution was sampled and heated and dried at 180°C for 20 minutes to measure the nonvolatile content, and the nonvolatile content was 20% by mass in the resin solution synthesized earlier. PGMAc was added to obtain a binder resin (C-4) solution. The weight average molecular weight of the resin was 18,000, and the acid value per nonvolatile content was 2 mgKOH/g.

<Production method of colored composition (single color)>
[Example 1]
(Preparation of colored composition (R-1))
The following mixture was stirred and mixed until it was homogeneous, and then dispersed for 3 hours using an Eiger mill ("Mini Model M-250 MKII" manufactured by Eiger Japan) using zirconia beads with a diameter of 0.5 mm. The mixture was filtered through a 0 μm filter to produce a colored composition (R-1) containing 24.3% by mass of non-volatile components.
Pigment (A-1): 20.5 parts Basic resin type dispersant ((b1-1): 30% nonvolatile liquid): 1.0 part Phosphoric acid resin type dispersant ((b2-1): nonvolatile 30% liquid): 0.5 part Carboxylic acid resin type dispersant ((b4-1): 30% non-volatile liquid): 0.5 part Binder resin (C-1: 20% non-volatile liquid): 16 .0 parts Solvent (P): 61.5 parts

[Examples 2 to 39, Comparative Examples 1 to 4, Production Examples 1 to 9]
(Preparation of colored compositions (R-2 to 52))
Colored compositions (R-2 to R-52) were produced in the same manner as in Example 1, except that the material types and masses were changed as listed in Table 1.

<Production method of colored composition (coloring material mixture)>
[Example 101]
(Preparation of colored composition (X-1))
The following raw materials were mixed, stirred, and filtered through a filter with a pore size of 1.0 μm to obtain a colored composition (X-1).
Coloring composition (R-1: non-volatile content 24.3% liquid): 40 parts Coloring composition (R-44: non-volatile content 24.3% liquid): 16 parts Binder resin (C-1: non-volatile content 20% liquid) ): 32 parts Solvent (P): 12 parts

[Examples 102 to 149, Comparative Example 101]
(Preparation of colored composition (X-2 to 50))
Colored compositions (X-2 to 50) were prepared in the same manner as in Example 101, except that the material type and mass were changed as listed in Table 2.

<Evaluation of colored composition>
The obtained colored compositions (R-1 to 43, X-1 to 50) were tested for viscosity and storage stability in the following manner. The evaluation criteria are as follows.
◎: Very good 〇: Good △: Possible for practical use ×: Not suitable for practical use

(Measurement of viscosity characteristics)
The viscosity at a rotation speed of 20 rpm was measured using an E-type viscometer ("ELD-type viscometer" manufactured by Toki Sangyo Co., Ltd.). The evaluation criteria are as follows.
○: Viscosity 4.0 mPa・s or more and less than 20.0 mPa・s
×: Viscosity 20mPa・s or more
(Storage stability)
The initial viscosity on the next day after preparing the coloring composition and the viscosity after one week at 40°C were measured using an E-type viscometer ("ELD-type viscometer" manufactured by Toki Sangyo Co., Ltd.) at 25°C and the rotational speed. The measurement was performed under the condition of 50 rpm. From the values of the initial viscosity and the viscosity over time, the rate of change in viscosity over time was calculated using the following formula, and the storage stability was evaluated in two stages.
[Viscosity change rate over time] = | ([Initial viscosity] - [Viscosity over time]) / [Initial viscosity] | × 100
○: Rate of change less than 5% ×: Rate of change 5% or more

(Foreign substance evaluation)
The number of foreign substances in the coating film of the coated substrate obtained by applying the colored composition on a 10 cm square glass substrate so that the dry coating film is about 2.0 μm and heat-treating it in an oven at 230°C for 1 hour. was measured. For evaluation, surface observation was performed using a metallurgical microscope "BX60" (manufactured by Olympus Systems). The magnification was set to 500 times, and the number of foreign substances observable in five arbitrary fields of view was measured using transmission. The evaluation criteria are as follows.
◎: Number of foreign objects is less than 5
〇: Number of foreign substances is 5 or more and less than 20
△: Number of foreign substances is 21 or more and less than 100
×: 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, stirred, and filtered through a filter with a pore size of 1.0 μm to obtain a photosensitive coloring composition (Y-1).
Coloring composition (R-1: 20% non-volatile content): 50.0 parts Binder resin (C-2: 20% non-volatile content): 15.0 parts Thermosetting compound (CE-1): 1.0 parts Heat Curable compound (CE-2): 1.0 part Photopolymerizable monomer (D): 3.0 parts Photoinitiator (E): 1.8 parts Sensitizer (H): 0.2 parts Thiol chain transfer agent (I): 0.4 part Polymerization inhibitor (J): 0.1 part Ultraviolet absorber (K): 0.1 part Antioxidant (L): 0.1 part Leveling agent (M) : Nonvolatile content 3%) : 1.0 part Storage stabilizer (N) : 0.1 part Silane coupling agent (O) : 0.2 part Solvent (P) : 26.0 part

[Examples 202 to 290, Comparative Examples 201 to 205]
(Preparation of photosensitive coloring composition (Y-2 to 95))
Photosensitive coloring compositions (Y-2 to 95) were prepared in the same manner as in Example 201, except that the types of the coloring composition and binder resin solution in Example 201 were changed as shown in Table 4. Furthermore, in the table, in Example 289, binder resin (C-2) in Example 240 was changed to (C-3). Further, Example 290 is obtained by changing the binder resin (C-2) of Example 240 to (C-4). In addition, each raw material is as follows.

<Thermosetting compound (CE)>
・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 compound of sorbitol [Denacol EX611 (manufactured by 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 Co., Ltd.)]

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

(D-5) Polyfunctional urethane acrylate as shown below Pentaerythritol triacrylate (432 g, hexamethylene diisocyanate 84 g) was charged into a 5-necked reaction vessel with a content of 1 liter, and reacted at 60°C for 8 hours to form a (meth)acryloyl group. A product containing a polyfunctional urethane acrylate (D-5) having It was confirmed by IR analysis that no isocyanate groups were present in the reaction product.

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

<Photopolymerization initiator (E)>
(E-1) 2-Methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one [Irgacure 907 (manufactured by BASF Japan)]
(E-2) 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone [Irgacure 379 (manufactured by BASF Japan)]
(E-3) 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide [Lucirin TPO (manufactured by BASF Japan)]
(E-4) 2,2'-bis(o-chlorophenyl)-4,5,4',5'-tetraphenyl-1,2'-biimidazole [biimidazole (manufactured by Kurogane Kasei Co., Ltd.)]
(E-5) p-dimethylaminoacetophenone [DMA (manufactured by Daiki Fine Co., Ltd.)]
(E-6) Ethan-1-one, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl], 1-(O-acetyloxime) [Irgacure OXE02 (BASF Japan) company)]
(E-7) 1-[4-(2-hydroxyethoxy)-phenyl] -2-hydroxy-2-methyl-1-propan-1-one [Irgacure 2959 (manufactured by BASF Japan)]
(E-8) Bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide [Irgacure 819 (manufactured by BASF Japan)]
The above (E-1) to (E-8) were mixed in the same amount 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 DEABP (manufactured by Chemark Chemical)]
As described above, (H-1) and (H-2) were mixed in the same amount to prepare a sensitizer (H).

<Thiol chain transfer agent (I)>
(I-1) Trimethylolethane tris (3-mercaptobutyrate) [TEMB (manufactured by Showa Denko)]
(I-2) Trimethylolpropane tris (3-mercaptobutyrate) [TPMB (manufactured by Showa Denko)]
(I-3) Pentaerythritol tetrakis (3-mercaptopropionate) [PEMP (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 the same amount to prepare a thiol chain transfer agent (I).

<Polymerization inhibitor (J)>
(J-1) 3-Methylcatechol (J-2) Methylhydroquinone (J-3) t-Butylhydroquinone Above, (J-1) to (J-3) are mixed in equal amounts, and a polymerization inhibitor is added. (J).

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

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

<Storage stabilizer (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 Hokuko Chemical Industry Co., Ltd.)
The above (N-1) to (N-2) were mixed in the same amount 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.)]
As described above, (O-1) to (O-4) were mixed in the same amount 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 Above, (P-1) to (P-6) were mixed in the above mass parts, respectively, to prepare a solvent (P).

<Evaluation of photosensitive coloring composition>
Each test was conducted in the following manner. The results of the test are shown in Table 5.
The meaning of the evaluation rank is as follows.
◎: Very good 〇: Good △: Possible for practical use ×: Not suitable for practical use

(Development speed evaluation)
The photosensitive coloring composition was spin-coated onto 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 a 2% by mass potassium hydroxide aqueous solution was dropped onto the above coating film, and the time until the coating thickness disappeared was measured. The evaluation criteria are as follows.
○: Less than 10 seconds △: 10 seconds or more, less than 15 seconds ×: 15 seconds or more

(Measurement of viscosity characteristics)
The same procedure as above was carried out.

(Storage stability)
The same procedure as above was carried out.

(Foreign substance evaluation)
The same procedure as above was carried out.

(Solvent resistance evaluation)
The colored composition was spin-coated onto a glass substrate using a spin coater so that the dry film thickness was 2.0 μm, and prebaked at 120° C. for 120 seconds. Next, this substrate was cooled to room temperature, and then exposed to ultraviolet light through a photomask spaced at 100 μm intervals using an ultra-high pressure mercury lamp. Thereafter, this substrate was spray-developed using a sodium carbonate aqueous solution at 23°C, washed with ion-exchanged water, air-dried, and post-baked at 230°C for 30 minutes in a clean oven. Striped colored pixels were formed on the top. Next, the coated substrate was immersed in the N-methylpyrrolidone solution for 30 minutes, washed with ion-exchanged water, air-dried, and observed and evaluated using an optical microscope. The evaluation ranks are as follows.
〇: Good with no change in appearance or color
△: Wrinkles etc. occur in some parts, but the color is good with no change
×: Peeling and discoloration occur

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

Claims (7)

Contains a red pigment (A), a resin-type dispersant (B), and a binder resin (C),
A colored composition, wherein the resin-type dispersant includes the following dispersant (B1) or (B2).
(B1) Basic resin type dispersant (b1), the following phosphoric acid resin type dispersant (b2-1) or (b2-2), and the following carboxylic acid resin type dispersant (b4-1) or (b4) -2) containing a resin-type dispersant (B2) a salt (b3) of a compound represented by the following general formula (1) or a compound represented by the general formula (2) and a basic resin-type dispersant (b1), and the following: Resin-type dispersant containing carboxylic acid-based resin-type dispersant (b4-1) or (b4-2)

(b2-1): Resin-type dispersant represented by the following general formula (3) General formula (3) (HO-) _3-n -PO-(OR ⁵ ) _n
(In the formula, R ⁵ is a polyester residue with a number average molecular weight of 300 to 10,000, and n represents 1 or 2.)
(b2-2): Resin-type dispersant that is a copolymer of an ethylenically unsaturated monomer having a phosphoric acid group and another ethylenically unsaturated monomer

(b4-1): A resin type dispersant containing a polyester part having a carboxyl group and a vinyl polymer part,
The carboxyl group-containing polyester portion is a reaction product of a type of acid anhydride group selected from the group consisting of tetracarboxylic anhydride and tricarboxylic anhydride and a hydroxyl group-containing compound.
(b4-2): Dispersant represented by the following general formula (4)
General formula (4) (HOOC-) _m -R ⁶ -(-COO-[-R ⁸ -COO-] _n -R ⁷ ) _t
(In the formula, R ⁶ is a tetravalent aromatic tetracarboxylic acid residue, R ⁷ is a monoalcohol residue, R ⁸ is a lactone residue, m is 2 or 3, and n is an integer from 1 to 50. , t represents (4-m).)


(However, in the general formulas (1) and (2), R ¹ and R ² are each independently a hydrogen atom, a hydroxyl group, a straight chain, branched chain, or cyclic alkyl group having 1 to 20 carbon atoms, Represents a vinyl group, a phenyl group to a benzyl group which may have a substituent, or -O-R ⁴ , R ⁴ is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, Represents a phenyl group to a benzyl group which may have a substituent, or a (meth)acryloyl group via an alkylene group having 1 to 4 carbon atoms.However, at least one of R ¹ and R ² contains a carbon atom. (R ³ represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group or benzyl group which may have a substituent, or -O-R ^4. ) The colored composition according to claim 1, wherein the basic resin type dispersant (b1) has an amide bond. The colored composition according to claim 1 or 2 , wherein the carboxylic acid resin type dispersant (b4-1) is the following (b4-1-1) or (b4-1-2).
(b4-1-1): The vinyl polymer portion contains one or more thermally crosslinkable functional groups selected from the group consisting of a hydroxyl group, an oxetane group, a tert-butyl group, and a blocked isocyanate group, and a carboxyl group. A resin-type dispersant.
(b4-1-2): Resin-type dispersant in which the vinyl polymer portion contains an ethylenically unsaturated group The colored composition according to any one of claims 1 to 3 , further comprising a yellow pigment (a). A photosensitive colored composition comprising the colored composition according to any one of claims 1 to 4 , a polymerizable compound (D), and a photopolymerization initiator (E). A color filter comprising a filter segment formed from the photosensitive coloring composition according to claim 5 . A liquid crystal display device comprising the color filter according to claim 6 .