JP7571422B2 - A coloring composition, a color filter, a liquid crystal display device, and a solid-state imaging device. - Google Patents

Description

The present invention relates to a coloring composition for use in color filters, etc.

Generally, color filters are formed on the surface of a transparent substrate such as glass, and consist of fine stripe-shaped filter segments (pixels) made of a red filter layer (R), a green filter layer (G), and a blue filter layer (B) arranged in parallel or crosswise rows, or fine filter segments arranged in a fixed vertical and horizontal array. The filter segments are very fine, ranging from a few microns to a few hundred microns, and are arranged in a regular pattern according to the hue.

In addition to green pigments as colorants, yellow pigments are used as color-adjusting colorants (colorants for toning) for the green filter segments in color filters, and C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 185, etc. are used. Among these, C.I. Pigment Yellow 138, a quinophthalone pigment, is often used because it provides high transmittance. However, C.I. Pigment Yellow 138, a quinophthalone pigment, has the problem of generating foreign matter when heated to 230°C or higher.

Furthermore, green filter segments using C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment Green 58, C.I. Pigment Green 59, C.I. Pigment Green 62, C.I. Pigment Green 63, zinc phthalocyanine pigments described in JP-A-2008-19383, JP-A-2007-320986, JP-A-2004-70342, etc., phthalocyanine pigments described in JP-A-4893859, JP-A-2016-153481, JP-A-2017-197685, etc., which are widely used as green pigments, have problems such as a decrease in brightness when exposed to backlight (see, for example, Non-Patent Document 1) and a decrease in voltage retention rate, which adversely affects the operation of liquid crystal display devices.

Various efforts have been made to solve the above problems. For example, Patent Document 1 discloses a green color paste containing C.I. Pigment Yellow 138 and a sulfonated derivative of C.I. Pigment Yellow 138 as a green color paste with excellent heat resistance and contrast ratio. Patent Document 2 discloses a pigment dispersion composition with improved contrast and brightness, which contains a pigment with an average primary particle size of 10 to 30 nm and a quinophthalone compound having at least one group selected from a hydroxyl group, a carboxylic acid group, a sulfonic acid group, an amino group, and salts thereof.

As an effort to solve the problem of reduced brightness, Patent Document 3 discloses a colorable resin composition that contains a phthalocyanine colorant, a yellow colorant, and a metal compound that is a component different from the colorant.

JP 2002-179979 A JP 2011-122125 A JP 2017-186546 A

Journal of Photopolymer Science and Technology, Volume 7, Number 1 (1994) p. 151-158

However, the coloring compositions of References 1 and 2 were not satisfactory in suppressing the generation of foreign matter, and no consideration was given to the reduction in brightness and the reduction in voltage holding rate. The coloring composition of Reference 3 was not satisfactory in suppressing the reduction in brightness. Also, no consideration was given to the suppression of the generation of foreign matter and the reduction in voltage holding rate.

The present invention aims to provide a coloring composition that can form a color filter that generates little foreign matter, has an excellent voltage retention rate, and has little decrease in brightness.

The coloring composition of the present invention is a coloring composition comprising a colorant (A), a metal salt of a quinophthalone compound having a sulfo group (B), an alkali-soluble resin (C), and a surfactant (D),
The colorant (A) contains a phthalocyanine pigment (A1) and a quinophthalone pigment (A2),
the metal of the metal salt (B) of a quinophthalone compound having a sulfo group is one or more metals selected from the group consisting of copper, silver, zinc, iron, and aluminum;
The surfactant (D) includes a surfactant (D1) which is a copolymer of a monomer (d1) having one or more of a fluorinated alkyl group and a poly(perfluoroalkylene ether) chain and another monomer (d2).

The present invention provides a coloring composition, color filter, liquid crystal display device, and solid-state imaging device that can form a color filter with little generation of foreign matter, excellent voltage retention rate, and little decrease in brightness.

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

The following describes in detail the embodiments for carrying out the present invention. Note that the present invention is not limited to the following embodiments, and can be modified in various ways within the scope of the gist of the present invention.

In this specification, unless otherwise specified, the terms "(meth)acryloyl", "(meth)acrylic", "(meth)acrylic acid", "(meth)acrylate", or "(meth)acrylamide" refer to "acryloyl and/or methacryloyl", "acrylic and/or methacrylic", "acrylic acid and/or methacrylic acid", "acrylate and/or methacrylate", or "acrylamide and/or methacrylamide", respectively. "C.I." means Color Index (C.I.). The monomer is an ethylenically unsaturated group-containing compound.

<Coloring Composition>
One embodiment of the present invention relates to a coloring composition. The coloring composition of the present invention is a coloring composition containing a colorant (A), a metal salt of a quinophthalone compound having a sulfo group (B), an alkali-soluble resin (C), and a surfactant (D),
The colorant (A) contains a phthalocyanine pigment (A1) and a quinophthalone pigment (A2),
the metal of the metal salt (B) of a quinophthalone compound having a sulfo group is one or more metals selected from the group consisting of copper, silver, zinc, iron, and aluminum;
The surfactant (D) includes a surfactant (D1) which is a copolymer of a monomer (d1) (hereinafter also referred to as monomer (d1)) having one or more of a fluorinated alkyl group and a poly(perfluoroalkylene ether) chain and another monomer (d2).

The components that are or can be included in the coloring composition of one embodiment are described in detail below.

[Colorant (A)]
(Phthalocyanine pigment (A1))
The colored composition of the present invention contains a phthalocyanine pigment (A1) as the colorant (A).

Specifically, the phthalocyanine pigment (A1) is a compound classified as a pigment in the Color Index (C.I.; published by the Society of Dyers and Colourists), such as C.I. Pigment Green 7, 10, 36, 37, 58, 59, 62, 63, zinc phthalocyanine pigments described in JP-A-2008-19383, JP-A-2007-320986, JP-A-2004-70342, etc., aluminum phthalocyanine described in JP-A-4893859, JP-A-2016-57635, JP-A-2016-153481, JP-A-2017-197685, etc., C.I. Among these, C.I. Pigment Green 36, 58, 59, 62, 63, and the phthalocyanine pigments described in JP-A-2016-57635, JP-A-2016-153481, and JP-A-2017-197685 are preferred.

The phthalocyanine pigment (A1) can be used alone or in combination of two or more types.

The content of the phthalocyanine pigment (A1) is preferably 20 to 90% by mass, and more preferably 30 to 80% by mass, based on 100% by mass of the colorant (A).

(Quinophthalone Pigment (A2))
The colored composition of the present invention contains a quinophthalone pigment (A2) as the colorant (A).

The quinophthalone pigment (A2) preferably contains a quinophthalone pigment represented by the following general formula (1):

General formula (1)

In general formula (1), R ₁ to R ₁₃ each independently represent a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, or an aryl group which may have a substituent. Adjacent groups of _{R 1} to R ₄ and/or R ₅ to R ₈ may be united to form an aromatic ring which may have a substituent.

The substituents R ₁ to R ₁₃ in the general formula (1) will be described below.

Halogen atoms include fluorine, chlorine, bromine, and iodine.

Alkyl groups which may have a substituent include linear or branched alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, neopentyl, n-hexyl, n-octyl, stearyl, and 2-ethylhexyl, as well as alkyl groups having a substituent such as trichloromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, 2,2-dibromoethyl, 2,2,3,3-tetrafluoropropyl, 2-ethoxyethyl, 2-butoxyethyl, 2-nitropropyl, benzyl, 4-methylbenzyl, 4-tert-butylbenzyl, 4-methoxybenzyl, 4-nitrobenzyl, and 2,4-dichlorobenzyl.

Alkoxyl groups which may have a substituent include linear or branched alkoxyl groups such as methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutyloxy, tert-butyloxy, neopentyloxy, 2,3-dimethyl-3-pentoxy, n-hexyloxy, n-octyloxy, stearyloxy, and 2-ethylhexyloxy, as well as alkoxyl groups having a substituent such as trichloromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 2,2,3,3-tetrafluoropropyloxy, 2,2-ditrifluoromethylpropoxy, 2-ethoxyethoxy, 2-butoxyethoxy, 2-nitropropoxy, and benzyloxy.

In addition, examples of aryl groups that may have a substituent include aryl groups such as phenyl groups, naphthyl groups, and anthranyl groups, as well as aryl groups having a substituent such as p-methylphenyl groups, p-bromophenyl groups, p-nitrophenyl groups, p-methoxyphenyl groups, 2,4-dichlorophenyl groups, pentafluorophenyl groups, 2-aminophenyl groups, 2-methyl-4-chlorophenyl groups, 4-hydroxy-1-naphthyl groups, 6-methyl-2-naphthyl groups, 4,5,8-trichloro-2-naphthyl groups, anthraquinonyl groups, and 2-aminoanthraquinonyl groups.

Adjacent groups of R ₁ to R ₄ and/or R ₅ to R ₈ in general formula (1) together form an aromatic ring which may have a substituent. The aromatic ring mentioned here includes a hydrocarbon aromatic ring and a heteroaromatic ring. Examples of the hydrocarbon aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring. Examples of the heteroaromatic ring include a pyridine ring, a pyrazine ring, a pyrrole ring, a quinoline ring, a quinoxaline ring, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, an oxazole ring, a thiazole ring, an imidazole ring, a pyrazole ring, an indole ring, and a carbazole ring.

The quinophthalone pigment (A2) is preferably any one of C.I. Pigment Yellow 138 and quinophthalone pigments represented by the following general formulas (2 ₎ to ( ₄ ), in which the hydrogen atom, halogen atom, alkyl group which may have a substituent, alkoxyl group which may have a substituent, and aryl group which may have a substituent in _R14 to _R28 , _R29 to R43, and R44 to _R60 have the same meanings as the groups explained in general formula (1).

一般式（４）

General formula (4)

In general formulas (2) to (4), _R to _R , _R to _R , and R to _R each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group which may have a substituent _, an alkoxyl group which may have a substituent, or an aryl group which may have a substituent.

Furthermore, in the quinophthalone pigment (A2) used in the colored composition of the present invention, R ₁₄ to R ₂₈ , R ₂₉ to R ₄₃ , and R ₄₄ to R ₆₀ in the general formulae (2) to (4) are more preferably hydrogen atoms or halogen atoms.

Quinophthalone pigments (A2) can be used alone or in combination of two or more types.

The content of quinophthalone pigment (A2) is preferably 10 to 80 parts by mass, and more preferably 20 to 70 parts by mass, based on 100% by mass of colorant (A).

[Method for producing quinophthalone pigment (A2) represented by formula (1)]
The quinophthalone pigment (A2) represented by the general formula (1) can be synthesized, for example, by the methods described in JP-A-4-226163 and JP-A-2012-226110.

Specific examples of the quinophthalone pigment (A2) represented by general formula (1) include those shown below, but the present invention is not limited to these.

(Other pigments (A3))
The coloring composition of the present invention may contain a pigment (A3) other than the phthalocyanine pigment (A1) and the quinophthalone pigment (A2) as long as the problem can be solved.

Other pigments (A3) include, for example, C.I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 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, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119,120,123,125,126,127,128,129,137,139,147,150,151,152,153,154,155,156,161,162,164,166,167,168,169,170,171,172,173,174,1 75, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, 220, 221, C. I. Pigment Blue 1, 1:2, 9, 14, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 64, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79, C.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, 250,251,253,254,255,256,257,258,259,260,262,263,264,265,266,267,268,269,270,271,272,273,274,275,276,277,278,279,280,281,2 82, 283, 284, 285, 286, 287, 291, 295, 296, C. I. Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50, C.I. Pigment Orange 36, 38, 43, 64, 71, 73, etc.

(dye)
The colorant (A) can contain a dye.
Dyes include, for example, C.I. Solvent Green 1, 4, 5, 7, 34, 35, C.I. Acid Green 1, 3, 5, 9, 16, 50, 58, 63, 65, 80, 104, 105, 106, 109, C.I. Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82, C.I. Mordant Green 1, 3, 4, 5, 10, 15, 26, 29, 33, 34, 35, 41, 43, 53, C.I. Acid Yellow 2, 3, 4, 5, 6, 7, 8, 9, 9:1, 10, 11, 11:1, 12, 13, 14, 15, 16, 17, 17:1, 18, 20, 21, 22, 23, 25, 26, 27, 29, 30, 31, 33, 34, 36, 38, 39, 40, 40:1, 41, 42, 42:1, 43, 44, 46, 48, 51, 53, 55, 56, 60, 63, 65, 66, 67, 6 8,69,72,76,82,83,84,86,87,90,94,105,115,117,122,127,131,132,136,141,142,143,144,145,146,149,153,159,166,168,169,172,174,1 75, 178, 180, 183, 187, 188, 189, 190, 191, 192, 199, C. I. Direct Yellow 1, 2, 4, 5, 12, 13, 15, 20, 24, 25, 26, 32, 33, 34, 35, 41, 42, 44, 44: 1, 45, 46, 48, 49, 50, 51, 61, 66, 67, 69, 70, 71, 72, 73, 74, 81, 84, 86, 90, 91, 92, 95, 107, 110, 117, 118, 119, 120, 121, 126, 127, 129, 132, 133, 134, C.I. Basic Yellow 1, 2, 5, 11, 13, 14, 15, 19, 21, 24, 25, 28, 29, 37, 40, 45, 49, 51, 57, 79, 87, 90, 96, 103, 105, 106, C.I. Solvent Yellow 2, 7, 28, 29, 30, 32, 33, 34, 40, 42, 43, 44, 45, 47, 48, 56, 62, 64, 68, 69, 71, 72, 73, 77, 79, 81, 82, 83, 85, 88, 89, 90, 93, 94, 98, 104, 107, 114, 116, 117, 124, 1 30,131,133,135,138,141,143,145,146,147,157,160,162,163,167,172,174,175,176,177,179,181,182,183,184,185,186,187,188,190,19 1,192,194,195, C. I. Disperse Yellow 1, 2, 3, 5, 7, 8, 10, 11, 13, 13, 23, 27, 33, 34, 42, 45, 48, 51, 54, 56, 59, 60, 63, 64, 67, 70, 77, 79, 82, 85, 88, 93, 99, 114, 118, 119, 122, 123, 124, 126, 163, 184, 184:1, 202, 211, 229, 231, 232, 233, 241, 245, 246, 247, 248, 249, 250, 251, and the like.

The content of colorant (A) is preferably 5 to 70 mass %, and more preferably 10 to 60 mass %, based on 100 mass % of the nonvolatile content of the coloring composition.

(Micronization of pigments)
In the present invention, the pigment is preferably micronized before use. The method of micronization is not particularly limited, and for example, any of wet grinding, dry grinding, and solution precipitation can be used. Among these, salt milling treatment using a kneader method, which is a type of wet grinding, is preferred. The average primary particle size of the micronized pigment determined by TEM (transmission electron microscope) is preferably 5 to 90 nm. From the viewpoints of dispersibility and contrast ratio, the average primary particle size is more preferably 10 to 70 nm.

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

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

The water-soluble organic solvent is a solvent that moistens the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (is miscible with) water and does not substantially dissolve the inorganic salt used. However, since the temperature rises during salt milling and the solvent becomes prone to evaporate, a high-boiling solvent with a boiling point of 120°C or higher is preferred from the standpoint of safety. For example, 2-methoxyethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol, etc. may be used. The amount of the water-soluble organic solvent used is preferably 5 to 1,000 parts by mass, more preferably 50 to 500 parts by mass, per 100 parts by mass of the pigment.

For the salt milling treatment, the resin may be changed as necessary. The type of resin is not particularly limited, and examples include natural resins, modified natural resins, synthetic resins, and synthetic resins modified with natural resins. Among these, it is preferable that the resin is solid at room temperature, insoluble in water, and partially soluble in the organic solvent. The amount of resin used is preferably 2 to 200 parts by weight per 100 parts by weight of the pigment.

[Metal Salt of Quinophthalone Compound Having a Sulfo Group (B)]
The coloring composition of the present invention contains a metal salt (B) of a quinophthalone compound having a sulfo group, the metal being one or more selected from the group consisting of copper, silver, zinc, iron, and aluminum.
By using the quinophthalone compound having a sulfo group and the metal salt (B), it is possible to obtain a colored composition which generates less foreign matter, has an excellent voltage holding ratio, and exhibits little decrease in brightness.

Quinophthalone compounds are compounds having a structure represented by the following chemical formula (2). Specific examples include commercially available dyes such as C.I. Acid Yellow 3 and 5, and commercially available pigments and dyes such as C.I. Pigment Yellow 138, C.I. Solvent Yellow 33, 114, and 157, and C.I. Disperse Yellow 54, 64, and 67.

Chemical formula (2)

Quinophthalone compounds having a sulfo group are compounds obtained by sulfonating a compound having a structure represented by chemical formula (2) using a known method. Specific examples include those shown below, but the present invention is not limited to these.

The metal salt of the quinophthalone compound having a sulfo group (B) can be obtained by counter-exchanging the _--SO.sub.3H of the above-mentioned exemplary compound with a metal salt by a known method.

The metal constituting the metal salt is one or more selected from the group consisting of copper, silver, zinc, iron, and aluminum. Among these, when the metal is copper, the decrease in brightness can be more effectively suppressed. Furthermore, when the metal is either zinc or aluminum, the voltage retention rate is excellent and the generation of foreign matter can be more effectively suppressed.

It is preferable to use two or more kinds of metal salts (B) of a quinophthalone compound having a sulfo group in combination. Among these, it is preferable to use at least a copper salt of a quinophthalone compound having a sulfo group, and more preferable are a copper salt and an aluminum salt of a quinophthalone compound having a sulfo group, or the copper salt and a zinc salt of the above-mentioned compound.

The content of the metal salt of the quinophthalone compound having a sulfo group (B) is preferably 1 to 40 parts by mass, and more preferably 5 to 30 parts by mass, per 100 parts by mass of the phthalocyanine pigment (A1), from the viewpoints of suppressing the generation of foreign matter, voltage holding rate, and suppressing a decrease in brightness.

The content of the copper salt of the quinophthalone compound having a sulfo group is preferably 20 to 100% by mass, more preferably 20 to 80% by mass, and even more preferably 20 to 60% by mass, based on 100% by mass of the metal salt of the quinophthalone compound having a sulfo group (B).

[Dispersion resin (F)]
The colored composition of the present invention may contain a dispersing resin (F) as necessary.
The dispersing resin (F) has an adsorptive group having a high affinity for the pigment, and the adsorptive group is preferably one or more of a cationic group and an anionic group.

Examples of resins having cationic groups include cationic groups such as primary amino groups, secondary amino groups, tertiary amino groups, quaternary ammonium bases, and groups containing nitrogen atoms such as nitrogen-containing heterocycles.

Examples of resins having anionic groups include carboxyl groups, phosphate groups, and sulfonic acid groups. Of these, carboxyl groups and phosphate groups are preferred from the viewpoint of adsorption to pigments.

Examples of the resin type of the dispersion resin (F) include urethane resins, polycarboxylates such as polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylate (partial) amine salts, polycarboxylate ammonium salts, polycarboxylate alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl-containing polycarboxylates, and modified products thereof, amides formed by the reaction of poly(lower alkylene imines) with polyesters having free carboxyl groups, and salts thereof, water-soluble resins and water-soluble polymer compounds such as (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohols, and polyvinylpyrrolidone, polyesters, modified polyacrylates, ethylene oxide/propylene oxide adducts, and phosphates.

The structure of the dispersion resin (F) may be, for example, a random structure, a block structure, a graft structure, a comb structure, or a star structure. Among these, the block structure or the comb structure is preferred from the viewpoint of dispersion stability.

Commercially available dispersion resins (F) include, for example, Disperbyk-101, 103, 107, 108, manufactured by BYK Japan Co., Ltd. 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 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, 2164, or Anti-Terra-U203, 204, or BYK-P104, P104S, 220S, Lactimon, Lactimon-WS, Bykumen, etc., SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 3660 manufactured by Lubrizol Japan Co., Ltd. EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc., Ajisuper PA111, PB711, PB821, PB822, PB824, etc. manufactured by Ajinomoto Fine-Techno Co., Ltd., and resins described in JP-A-2008-029901, JP-A-2009-155406, JP-A-2010-185934, JP-A-2011-157416, etc. are included.

Dispersion resin (F) can be used alone or in combination of two or more types.

From the viewpoint of dispersion stability, the content of the dispersing resin (F) is preferably 3 to 200 parts by mass, and more preferably 5 to 100 parts by mass, per 100 parts by mass of the colorant (A).

[Dispersing Aid (G)]
The colored composition of the present invention may contain a dispersing aid (G) as necessary.

The dispersing aid (G) is not particularly limited, and examples thereof include compounds having an acidic group, a basic group, a neutral group, etc. in the organic dye residue. Specific examples of the dispersing aid (G) include compounds having an acidic substituent such as a sulfo group, a carboxy group, or a phosphate group, and amine salts thereof, compounds having a basic substituent such as a sulfonamide group or a tertiary amino group at the end, and compounds having a neutral substituent such as a phenyl group or a phthalimidoalkyl group.
Examples of organic pigments include diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone-based pigments, perylene-based pigments, thiazine indigo pigments, triazine pigments, benzimidazolone pigments, indole pigments such as benzoisoindole, isoindoline-based pigments, isoindolinone pigments, naphthol pigments, threne pigments, metal complex-based pigments, and azo-based pigments such as azo, disazo, and polyazo.

Dispersing agents (G) can be used alone or in combination of two or more types.

The content of the dispersing aid (G) is preferably 1 to 15 parts by mass, and more preferably 2 to 10 parts by mass, per 100 parts by mass of the colorant (A).

[Alkali-soluble resin (C)]
The coloring composition of the present invention contains an alkali-soluble resin (C).
The alkali-soluble resin (C) is a resin that dissolves in an alkali developer, and is preferably a resin that has a transmittance of 80% or more over the entire wavelength range of 400 to 700 nm when a coating having a thickness of 2 μm is formed. The transmittance is preferably 95% or more.
The alkali-soluble resin (C) can be classified into a non-photosensitive alkali-soluble resin and a photosensitive alkali-soluble resin. Examples of the alkali-soluble group include a carboxyl group, a phosphoric acid group, a sulfonic acid group, a hydroxyl group, and a phenolic hydroxyl group. Among these, a carboxyl group is preferred. The alkali-soluble resin (C) can also contain a thermosetting group such as an epoxy group or an oxetanyl group.

(Non-photosensitive alkali-soluble resin)
Examples of the non-photosensitive alkali-soluble resin include an acrylic resin having an acidic group, an α-olefin/maleic acid (anhydride) copolymer, a styrene/styrene sulfonic acid copolymer, an ethylene/(meth)acrylic acid copolymer, an isobutylene/maleic acid (anhydride) copolymer, etc. Among these, an acrylic resin having an acidic group and a styrene/styrene sulfonic acid copolymer are preferred.

(Photosensitive alkali-soluble resin)
The photosensitive alkali-soluble resin has photosensitivity due to the presence of a polymerizable unsaturated group. The photosensitive alkali-soluble resin may be any known resin as long as it is alkali-soluble and photosensitive, but resins synthesized by the following methods (i) and (ii) are preferred. When the alkali-soluble photosensitive resin is used, it undergoes three-dimensional crosslinking by light irradiation, increasing the crosslink density, improving the chemical resistance of the coating.

[Method (i)]
Method (i) is, for example, a method in which a polymer of an epoxy group-containing monomer and other monomers is first synthesized. Next, a monocarboxyl group-containing monomer is added to the epoxy group of the polymer, and the resulting hydroxyl group is reacted with a polybasic acid anhydride to obtain an alkali-soluble photosensitive resin. The monocarboxyl group-containing monomer is a monomer having one carboxyl group.

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

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

Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, maleic anhydride, etc. In addition, polybasic acid anhydrides may have a carboxyl group that does not form an acid anhydride.

Examples of other monomers include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, and methoxypolypropylene glycol (meth)acrylate. or (meth)acrylates such as ethoxy polyethylene glycol (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, EO-modified cresol acrylate, n-nonylphenoxy polyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl acrylate, ethylene oxide (EO)-modified (meth)acrylate of phenol, EO- or propylene oxide (PO)-modified (meth)acrylate of paracumylphenol, EO-modified (meth)acrylate of nonylphenol, and PO-modified (meth)acrylate of nonylphenol;
Alternatively, examples of the vinyl monomer include (meth)acrylamides such as (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, and acryloylmorpholine; styrenes such as styrene and α-methylstyrene; vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether; and fatty acid vinyls such as vinyl acetate and vinyl propionate.

Also, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimideethane 1,6-bismaleimidehexane, 3-maleimidopropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimidocoumarin, 4,4'-bismaleimidediphenylmethane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, N,N'-1,3-phenylenedimaleimide, N,N'-1,4-phenylenedimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-trichlorophenyl) N-substituted maleimides such as N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-3-maleimide propionate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl-6-maleimide hexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, and 9-maleimide acridine are included.

Other examples include phosphate ester group-containing monomers such as 2-(meth)acryloyloxyethyl acid phosphate and compounds in which the hydroxyl group of a hydroxyl group-containing monomer described below is reacted with a phosphate esterifying agent such as phosphorus pentoxide or polyphosphoric acid.

[Method (ii)]
In the method (ii), for example, a polymer of a hydroxyl group-containing monomer, a carboxyl group-containing monomer, and other monomers is synthesized, and then the hydroxyl group of the polymer is reacted with an isocyanate group of an isocyanate group-containing monomer to synthesize an alkali-soluble photosensitive resin.

Examples of the hydroxyl group-containing monomer include hydroxyalkyl methacrylates such as 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2-, 3- or 4-hydroxybutyl (meth)acrylate, glycerol mono(meth)acrylate, and cyclohexanedimethanol mono(meth)acrylate. Other examples include polyether mono(meth)acrylates obtained by addition polymerization of ethylene oxide, propylene oxide, and/or butylene oxide to hydroxyalkyl (meth)acrylates, and polyester mono(meth)acrylates obtained by addition of poly(γ-valerolactone), poly(ε-caprolactone, and/or poly(12-hydroxystearic acid). Among these, 2-hydroxyethyl methacrylate and glycerol mono(meth)acrylate are preferred, and glycerol mono(meth)acrylate is more preferred.

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

The carboxyl group-containing monomer and other monomers can be the monomers already described.

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

From the viewpoint of developability, the weight average molecular weight (Mw) of the alkali-soluble resin (C) is 2,000 to 40,000, preferably 3,000 to 300,000, and more preferably 4,000 to 20,000. The value of Mw/Mn is preferably 10 or less. An appropriate weight average molecular weight (Mw) improves adhesion to the substrate and solubility in alkaline development.

The acid value of the alkali-soluble resin (C) is preferably 50 to 200 mgKOH/g, more preferably 70 to 180 mgKOH/g, and even more preferably 90 to 170 mgKOH/g. A moderate acid value improves adhesion to the substrate and solubility in alkaline development.

The content of the alkali-soluble resin (C) is preferably 20 to 400 parts by mass, and more preferably 50 to 250 parts by mass, per 100 parts by mass of the colorant (A).

[Surfactant (D)]
(Surfactant (D1))
The coloring composition of the present invention contains, as a surfactant (D), a surfactant (D1) which is a copolymer of a monomer (d1) having one or more of a fluorinated alkyl group and a poly(perfluoroalkylene ether) chain and another ethylenically unsaturated group-containing monomer (d2).
The combined use of the surfactant (D1) and the metal salt of a quinophthalone compound having a sulfo group (B) can significantly suppress the generation of foreign matter.

The content of the monomer (d1) is preferably 5 to 95 mass % of the total monomer units constituting the surfactant (D1), and more preferably 10 to 50 mass %.

The method for producing the surfactant (D1) includes, for example, a method of solution polymerization using a polymerization initiator. The solvent used for the solution polymerization is preferably ketones, esters, amides, sulfoxides, ethers, or hydrocarbons. Specific examples include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, toluene, and xylene. These can be appropriately selected in consideration of boiling point, compatibility, and polymerizability. Examples of the polymerization initiator include peroxides such as benzoyl peroxide, and azo compounds such as azobisisobutyronitrile. Furthermore, chain transfer agents such as lauryl mercaptan, 2-mercaptoethanol, thioglycerol, ethyl thioglycolic acid, and octyl thioglycolic acid can be used as necessary.

The monomer (d1) having a fluorinated alkyl group that constitutes the surfactant (D1) can be, for example, a monomer represented by the following general formula (5).

General formula (5)

In general formula (5), R represents a hydrogen atom or a methyl group, X represents any one of the groups represented by the following formulae (X-1) to (X-10), and Z represents any one of the groups represented by the following formulae (Z-1) to (Z-7).

In the above formulas (X-1), (X-3) to (X-7), n represents an integer of 1 to 8. In the above formulas (X-8) to (X-10), m represents an integer of 1 to 8, and n represents an integer of 0 to 8. In the above formulas (X-6) and (X-7), Z'' represents any one of the groups in the following formulas (Z-1) to (Z-7).

In the above formulas (Z-1) to (Z-4), n is, for example, an integer of 1 to 6, and preferably an integer of 4 to 6. In the above formula (Z-5), m is, for example, an integer of 1 to 18, n is an integer of 0 to 5, and the sum of m and n is 1 to 23. Preferably, m is an integer of 1 to 5, n is an integer of 0 to 4, and the sum of m and n is 4 to 5. In the above formula (Z-6), m is, for example, an integer of 1 to 6, n is an integer of 1 to 3, l is an integer of 1 to 20, p is an integer of 0 to 5, and the sum of m, p, and the product of n and l is 2 to 71. Preferably, m is an integer of 1 to 3, n is an integer of 1 to 3, l is an integer of 1 to 6, p is an integer of 0 to 2, and the sum of m, p, and the product of n and l is 2 to 23.

Among the monomers (d1) having a fluorinated alkyl group, from the viewpoint of suppressing the generation of foreign matter, a monomer having a fluorinated alkyl group in which the number of carbon atoms directly bonded to a fluorine atom is 1 to 6 is preferred, and a monomer having a fluorinated alkyl group in which the number of carbon atoms directly bonded to a fluorine atom is 4 to 6 is more preferred.

The monomer (d1) having a poly(perfluoroalkylene ether) chain constituting the surfactant (D1) may be a monomer having a structure in which a divalent carbon fluoride group having 1 to 3 carbon atoms and an oxygen atom are alternately linked. The divalent carbon fluoride group having 1 to 3 carbon atoms may be one type or a mixture of multiple types, and specific examples include a linking group represented by the following formula (Y).

In the above formula (Y), A is one of the following formulas (Y-1) to (Y-5). All A in formula (Y) may have the same structure, or multiple structures may exist randomly or in a block form. Also, n is an integer of 1 or more that represents a repeating unit.

Among these, from the viewpoint of suppressing the generation of foreign matter, it is particularly preferable that the perfluoromethylene structure represented by the formula (Y-1) and the perfluoroethylene structure represented by the formula (Y-2) coexist. The value of n in the formula (Y) is preferably in the range of 3 to 100, more preferably in the range of 6 to 70, and even more preferably in the range of 12 to 50.

The other monomer (d2) constituting the surfactant (D1) is not limited as long as it is a monomer (e.g., various monomers described in the photosensitive alkali-soluble resin) that can be copolymerized with the monomer (d1) having one or more of a fluorinated alkyl group and a poly(perfluoroalkylene ether) chain, and is not limited thereto. Among them, from the viewpoint of suppressing the generation of foreign matter, a polycyclic alicyclic structure-containing monomer is preferred.

Examples of polycyclic alicyclic structure-containing monomers include adamantyl group-containing monomers and dicyclopentanyl group-containing monomers. Among these, adamantyl group-containing monomers are preferred in terms of suppressing the generation of foreign matter.

A monomer having an adamantyl group is a compound having an adamantane structure and a (meth)acryloyl group as shown in the following general formula (6). The (meth)acryloyl group may be bonded to any carbon atom in the adamantane structure. In addition, some or all of the hydrogen atoms bonded to the carbon atoms constituting the adamantane structure may be substituted with hydroxyl groups, alkyl groups, etc.

General formula (6)

In general formula (6), R represents a hydrogen atom or a methyl group.

Commercially available surfactants (D1) include Surflon S-242, S-243, S-420, S-611, S-651, and S-386 manufactured by AGC Seimi Chemical Co., Ltd., Megafac F-253, F-477, F-551, F-552, F-555, F-558, F-560, F-570, F-575, F-576, R-40-LM, R-41, RS-72-K, and DS-21 manufactured by DIC Corporation, FC-4430 and FC-4432 manufactured by Sumitomo 3M Limited, EF-PP31N09, EF-PP33G1, and EF-PP32C1 manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd., and Futergent 602A manufactured by Neos Corporation.

The surfactant (D1) can be used alone or in combination of two or more.

From the viewpoint of suppressing the generation of foreign matter, the content of surfactant (D1) is preferably 0.01 to 2 parts by mass, and more preferably 0.1 to 1 part by mass, per 100 parts by mass of colorant (A).

(Other Surfactants (D2))
The surfactant (D) may contain another surfactant (D2) other than the surfactant (D1). Examples of the other surfactant (D2) include silicone surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants.

Silicone surfactants include, for example, linear polymers consisting of siloxane bonds and modified siloxane polymers with organic groups introduced into the side chains or ends. Commercially available products include BYK-300, 306, 310, 313, 315N, 320, 322, 323, 330, 331, 333, 342, 345, 346, 347, 348, 349, 370, 377, 378, 3455, UV3510, and 3570 manufactured by BYK-Chemie Co., Ltd., and FZ-7002, 2110, and 2120 manufactured by Dow Corning Toray Co., Ltd. 122, 2123, 2191, 5609, Shin-Etsu Chemical Co., Ltd.'s X-22-4952, X-22-4272, X-22-6266, KF-351A, KF-354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-4515, KF-6004, KP-341, etc.

Examples of nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyethylene myristyl ether, polyoxyethylene octyldodecyl ether, polyoxyalkylene alkyl ether, polyoxyphenylenedistyrenated phenyl ether, polyoxyethylene tribenzyl phenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyalkylene alkenyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene alkyl ether phosphate ester, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, and sorbitan tristearate. sorbitan monooleate, sorbitan trioleate, sorbitan sesquioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan triisostearate, polyoxyethylene sorbitan tetraoleate, glycerol monostearate, glycerol monooleate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol monooleate, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkylamines, alkyl alkanolamides, alkyl imidazolines, and the like. Commercially available products include Kao Corporation's Emulgen 103, 104P, 106, 108, 109P, 120, 123P, 130K, 147, 150, 210P, 220, 306P, 320P, 350, 404, 408, 409PV, 420, 430, 705, 707, 709, 1108, 1118S-70, 1135S-70, 1150S-60, 2020G-HA, 2025G, and LS-106. , LS-110, LS-114, MS-110, A-60, A-90, B-66, PP-290, Latemul PD-420, PD-430, PD-430S, PD-450, Leodor SP-L10, SP-P10, SP-S10V, SP-S20, SP-S30V, SP-O10V, SP-O30V, Super SP-L10, AS-10V, AO-10V, AO-15V, T W-L120, TW-L106, TW-P120, TW-S120V, TW-S320V, TW-O120V, TW-O106V, TW-IS399C, Super TW-L120, 430V, 440V, 460V, MS-50, MS-60, MO-60, MS-165V, Emanone 1112, 3199V, 3299V, 3299RV, 4110, CH-25, CH-40, Examples include CH-60(K), Amit 102, 105, 105A, 302, 320, Aminone PK-02S, L-02, Homogenol L-95, ADEKA Corporation's Adeka Pluronic (registered trademark) L-23, 31, 44, 61, 62, 64, 71, 72, 101, 121, TR-701, 702, 704, 913R, and Kyoeisha Chemical Co., Ltd.'s (meth)acrylic acid-based (co)polymer Polyflow No. 75, No. 90, No. 95.

Examples of cationic surfactants include alkylamine salts, alkyl quaternary ammonium salts such as lauryl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, and cetyl trimethyl ammonium chloride, and ethylene oxide adducts thereof. Commercially available products include Acetamine 24, Courtamine 24P, 60W, and 86P Conc., manufactured by Kao Corporation.

Examples of anionic surfactants include polyoxyethylene alkyl ether sulfates, sodium dodecylbenzene sulfonate, alkali salts of styrene-acrylic acid copolymers, sodium alkyl naphthalene sulfonates, sodium alkyl diphenyl ether disulfonates, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine styrene-acrylic acid copolymers, polyoxyethylene alkyl ether phosphates, etc. Commercially available products include Futergent 100 and 150 manufactured by Neos Corporation, and Adeka Hope YES-25, Adekacol TS-230E, PS-440E, and EC-8600 manufactured by ADEKA Corporation.

Examples of amphoteric surfactants include alkyl betaines such as lauric acid amidopropyl betaine, lauryl betaine, cocamidopropyl betaine, stearyl betaine, and alkyl dimethyl amino acetate betaine, and alkyl amine oxides such as lauryl dimethyl amine oxide. Commercially available products include Kao Corporation's Anphythol 20AB, 20BS, 24B, 55AB, 86B, 20Y-B, and 20N.

[Triarylsulfonium compound (E)]
The coloring composition of the present invention preferably contains a triarylsulfonium compound (E). By using the metal salt of a quinophthalone compound having a sulfo group (B) in combination with the triarylsulfonium compound (E), a coating film having a better voltage holding ratio and capable of further suppressing a decrease in brightness can be formed.

The triarylsulfonium compound (E) includes a compound represented by the following general formula (7):

General formula (7)

In general formula (7), R ₁ to R ₃ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, or an aryl group which may have a substituent, and X ⁻ represents a monovalent counter anion.

R ₁ to R ₃ and X ⁻ in general formula (7) will be explained below.

In general formula (7), R ₁ to R ₃ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, or an aryl group which may have a substituent.

Halogen atoms include fluorine, chlorine, bromine, and iodine.

Examples of the alkyl group that may have a substituent include linear or branched alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, neopentyl, n-hexyl, n-octyl, stearyl, and 2-ethylhexyl groups, and cyclic alkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl groups, as well as alkyl groups having a substituent such as trichloromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, 2,2-dibromoethyl, 2,2,3,3-tetrafluoropropyl, 2-ethoxyethyl, 2-butoxyethyl, 2-nitropropyl, benzyl, 4-methylbenzyl, 4-tert-butylbenzyl, 4-methoxybenzyl, 4-nitrobenzyl, and 2,4-dichlorobenzyl groups.

Examples of alkoxyl groups that may have a substituent include linear alkoxyl groups such as methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutyloxy, tert-butyloxy, neopentyloxy, 2,3-dimethyl-3-pentoxy, n-hexyloxy, n-octyloxy, stearyloxy, and 2-ethylhexyloxy, branched alkoxyl groups, and cyclic alkoxyl groups such as cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, and cyclohexyloxy, as well as alkoxyl groups having a substituent such as trichloromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 2,2,3,3-tetrafluoropropyloxy, 2,2-ditrifluoromethylpropoxy, 2-ethoxyethoxy, 2-butoxyethoxy, 2-nitropropoxy, and benzyloxy.

Aryl groups which may have a substituent include aryl groups such as phenyl, naphthyl, and anthranyl groups, as well as aryl groups having a substituent such as p-methylphenyl, p-bromophenyl, p-nitrophenyl, p-methoxyphenyl, 2,4-dichlorophenyl, pentafluorophenyl, 2-aminophenyl, 2-methyl-4-chlorophenyl, 4-hydroxy-1-naphthyl, 6-methyl-2-naphthyl, 4,5,8-trichloro-2-naphthyl, anthraquinonyl, and 2-aminoanthraquinonyl.

Among these, from the viewpoint of suppressing a decrease in brightness, it is preferable that at least two of R ₁ to R ₃ are hydrogen atoms, and it is more preferable that all of them are hydrogen atoms.

In the general formula (7), X ⁻ represents a monovalent counter anion. Examples of X ⁻ include F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , and compounds represented by the following general formulae (8) to (13).

General formula (8) MY _a ^-
In formula (8), M represents a phosphorus atom, a boron atom, or an antimony atom, Y represents a halogen atom, and a represents an integer of 4 to 6.

Examples of the compound represented by the general formula (8) include PF ₆ ^- , BF ₆ ^- and SbF ₆ ^- . Of these, PF ₆ is preferred.

General formula (9) (Rf) _b PF _6-b ^-
In the general formula (9), Rf represents an alkyl group having 1 to 8 carbon atoms in which 80 mol % or more of the hydrogen atoms are substituted with fluorine atoms. The alkyl group may be linear, branched, or cyclic. represents an integer of 1 to 5.

Examples of compounds represented by general formula (9) include ( _{CF3CF2 ) 2PF} ^- ₄ , _{( CF3CF2} ⁾ _{3PF3- , ( CF3CF2CF2} ⁾ _{2PF4- , ( ( CF3 ) 2CF} ) _3PF3- , ( _CF3CF2CF2 ) _{2PF4- , and} ^{the like} .

General formula (10) R ⁴ _c LY _c ^-
In formula (10), ^R4 represents a phenyl group in which at least one hydrogen atom is substituted with a halogen atom, L represents a boron atom or a gallium atom, and c represents an integer of 1 to 4.

Examples of compounds represented by general formula (10) include (C ₆ F ₅ )B ⁻ , ((CF ₃ ) ₂ C ₆ H ₃ )B ⁻ , (CF ₃ C ₆ H ₄ ) ₄ B ⁻ , (C ₆ F ₅ ) ₄ Ga ⁻ , and (C ₆ H ₃ F ₂ ) ₄ Ga ⁻ .

General formula (11) R ⁵ SO ₃ ⁻
In the general formula (11), R ⁵ represents an alkyl group having 1 to 12 carbon atoms, a perfluoroalkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms; The alkyl group may be linear, branched or cyclic, and the aryl group may be unsubstituted or may have a substituent.

Examples of the compound represented by general formula (11) include trifluoromethanesulfonate anion, pentafluoroethanesulfonate anion, heptafluoropropanesulfonate anion, nanofluorobutanesulfonate anion, pentafluorophenylsulfonate anion, p-toluenesulfonate anion, benzenesulfonate anion, camphorsulfonate anion, butanesulfonate anion, etc.

General formula (12) (R ⁶ SO ₂ ) ₃ C ^-
In the general formula (12), R ⁶ represents an alkyl group having 1 to 20 carbon atoms, a perfluoroalkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms; may be linear, branched or cyclic, and the aryl group may be unsubstituted or may have a substituent.

Examples of the compound represented by the general formula (12) include (CF ₃ SO ₂ ) ₃ C ^-- , (C ₂ F ₅ SO ₂ ) ₃ C ^-- , (C ₃ F ₇ SO ₂ ) ₃ C ^-- , (C ₄ F ₉ SO ₂ ) ₃ C ^--, and the like.

General formula (13) (R ⁷ SO ₂ ) ₂ N ⁻
In the general formula (13), R ⁷ represents an alkyl group having 1 to 20 carbon atoms, a perfluoroalkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms; may be linear, branched or cyclic, and the aryl group may have a substituent.

Examples of the compound represented by the general formula (13) include (CF ₃ SO ₂ ) ₂ N ^- , (C ₂ F ₅ SO ₂ ) ₂ N ^- , (C ₃ F ₇ SO ₂ ) ₂ N ^- , (C ₄ F ₉ SO ₂ ) ₂ N ^{- ,} and the like.

In addition to the above anions, perhalogen acid ions (ClO ₄ ^- , BrO ₄ ^- , etc.), halogenated sulfonate ions (FSO ₃ ^- , ClSO ₃ ^{- ,} etc.), sulfate ions (CH ₃ SO ₄ ^- , CF ₃ SO ₄ ^- , HSO ₄ ^{- ,} etc.), carbonate ions (HCO ₃ ^- , CH ₃ CO ₃ ^{- ,} etc.), aluminate ions (AlCl ₄ ^- , AlF ₄ ^{- ,} etc.), carboxylate ions (CHCOO ^- , CF ₃ COO ^- , C ₆ H ₅ COO ^- , CH ₃ C ₆ H ₄ COO ^- , C ₆ F ₅ COO ^{- ,} etc.), aryl borate ions (B(C ₆ H ₅ ) ₄ - , etc.), ^-, etc.), anions described in JP-A-2013-092657, JP-A-2013-080245, JP-A-2013-080240, JP-A-2013-047211, JP-A-2013-033161, etc.

Among these, from the viewpoint of suppressing a decrease in brightness, X ⁻ is preferably Cl ⁻ , Br ⁻ , PF ₆ ⁻ , BF ₆ ⁻ , a trifluoromethanesulfonate anion, or a nonafluorobutanesulfonate anion.

Examples of triarylsulfonium compounds (E) represented by general formula (7) include the following compounds:

Commercially available triarylsulfonium compounds (E) include, for example, WPAG-336, 367, 370, 469, and 638 (all manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), SP-056 and 066 (manufactured by ADEKA Corporation), TS-91 (manufactured by Sanwa Chemical Co., Ltd.), and T1608 and 1609 (both manufactured by Tokyo Chemical Industry Co., Ltd.).

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

From the viewpoint of suppressing the voltage holding rate and the decrease in brightness, the content of the triarylsulfonium compound (E) is preferably 0.1 to 15 parts by mass, more preferably 1 to 12 parts by mass, and particularly preferably 2 to 10% by mass, relative to 100 parts by mass of the phthalocyanine pigment (A1).

[Polymerizable compound (H)]
The coloring composition of the present invention may contain a polymerizable compound (H). The polymerizable compound (H) is a monomer or oligomer containing a polymerizable unsaturated group. The polymerizable unsaturated group may be, for example, Examples of the polymerizable compound (H) include an acid group-containing monomer (H1), a urethane bond-containing monomer (H2), a vinyl group, a (meth)allyl group, a (meth)acryloyl group, and a (meth)acryloyloxy group. monomers, and other monomers.

(Acid Group-Containing Monomer (H1))
Examples of the acid group of the acid group-containing monomer (H1) include a sulfonic acid group, a carboxyl group, a phosphoric acid group, etc. When the acid group-containing monomer (H1) is used to form a pattern by a photolithography method, development residues can be suppressed.

Examples of the acid group-containing monomer (H1) include esters of free hydroxyl group-containing poly(meth)acrylates of polyhydric alcohols and (meth)acrylic acid with dicarboxylic acids; esters of polycarboxylic acids with monohydroxyalkyl (meth)acrylates, etc. Specific examples include free carboxyl group-containing monoesters of monohydroxy oligoacrylates or monohydroxy oligomethacrylates such as trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate with dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, and phthalic acid; and free carboxyl group-containing oligoesters of tricarboxylic acids such as propane-1,2,3-tricarboxylic acid (tricarballylic acid), butane-1,2,4-tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, and benzene-1,3,5-tricarboxylic acid with monohydroxy monoacrylates or monohydroxy monomethacrylates such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl methacrylate.

Commercially available products of the acid group-containing monomer (H1) include Viscoat #2500P manufactured by Osaka Organic Industries, and Aronix M-5300, M-5400, M-5700, M-510, M-520, and M-521 manufactured by Toagosei Co., Ltd.

(Urethane bond-containing monomer (H2))
Examples of the urethane bond-containing monomer (H2) include polyfunctional urethane acrylates obtained by reacting a (meth)acrylate having a hydroxyl group with a polyfunctional isocyanate, and polyfunctional urethane acrylates obtained by reacting an alcohol with a polyfunctional isocyanate and further reacting the alcohol with a (meth)acrylate having a hydroxyl group.

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

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

Commercially available products of the urethane bond-containing monomer (H2) include AH-600, AT-600, UA-306H, UA-306T, UA-306I, UA-510H, UF-8001G, and DAUA-167 manufactured by Kyoeisha Chemical Co., Ltd., UA-160TM and 1100H manufactured by Shin-Nakamura Chemical Co., Ltd., and UV-4108F and UV-4117F manufactured by Osaka Organic Chemical Industry Co., Ltd.

(Other monomers)
Examples of other monomers include methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, β-carboxyethyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, trimethylolpropane PO-modified tri(meth)acrylate, trimethylolpropane EO-modified tri(meth)acrylate, isocyanuric acid EO-modified di(meth)acrylate, isocyanuric acid EO-modified tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, Examples of the acrylic acid esters and methacrylic acid esters include pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,6-hexanediol diglycidyl ether di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tricyclodecanyl (meth)acrylate, (meth)acrylic acid esters of methylolated melamine, epoxy (meth)acrylates, and urethane acrylates; (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-vinyl formamide, and acrylonitrile.

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

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

The content of the polymerizable compound (H) is preferably 1 to 60 mass%, and more preferably 2 to 50 mass%, based on 100 mass% of the nonvolatile content of the coloring composition.

[Photopolymerization initiator (I)]
The coloring composition of the present invention may contain a photopolymerization initiator (I). By containing the photopolymerization initiator (I), the coloring composition can be cured by ultraviolet irradiation and a filter segment can be formed by a photolithography method.

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

Commercially available photopolymerization initiators (I) include acetophenone compounds such as "Omnirad 907" (2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one), "Omnirad 369E" (2-(dimethylamino)-1-[4-(4-morpholino)phenyl]-2-(phenylmethyl)-1-butanone), and "Omnirad 379EG" (2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone) (all manufactured by IGM Resins), and phosphine compounds such as "Omnirad 819" (bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide) and "Omnirad TPO" (diphenyl-2,4,6-trimethylbenzoylphosphine oxide) (all manufactured by IGM Resins), and oxime compounds such as 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)] (IRGACURE OXE-01), ethanol, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) (IRGACURE OXE 02), and IRGACURE OXE 04 (all manufactured by BASF Japan), N-1919, NCI-730, NCI-831, and NCI-930 (all manufactured by ADEKA), TRONLY TR-PBG-304, and TRONLY TR-PBG-305, TRONLY TR-PBG-309, TRONLY TR-PBG-3054 (all manufactured by Changzhou Strong New Materials Co., Ltd.), etc. In addition, oxime ester photopolymerization initiators described in JP-A-2007-210991, JP-A-2009-179619, JP-A-2010-037223, JP-A-2010-215575, JP-A-2011-020998, etc. can also be used.

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

The content of the photopolymerization initiator (I) is preferably 2 to 50 parts by mass, and more preferably 2 to 30 parts by mass, per 100 parts by mass of the colorant (A) from the viewpoints of photocurability and developability.

[Sensitizer (J)]
The colored composition of the present invention may contain a sensitizer (J).

Sensitizers (J) include, for example, chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzil and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, polymethine dyes such as oxonol derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, and tetrapyrazinoporphyrazine. Derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organic ruthenium complexes, or Michler's ketone derivatives, α-acyloxy esters, acyl oxides, methylphenyl glyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl anthraquinone, 4,4'-diethylisophthalophenone, 3,3' or 4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 4,4'-bis(diethylamino)benzophenone, etc.

Among these, thioxanthone derivatives, Michler's ketone derivatives, and carbazole derivatives are preferred. Specific compounds that are preferred are 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, and 3,6-dibenzoyl-N-ethylcarbazole.

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

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

[Thermosetting compound (K)]
The colored composition of the present invention may contain a thermosetting compound (K). This allows the thermosetting compound (K) to react in the heating step after the formation of the coating film, increasing the crosslink density and improving the heat resistance.

The thermosetting compound (K) may be a low molecular weight compound or a high molecular weight compound such as a resin. Examples of the thermosetting compound (K) include epoxy compounds, oxetane compounds, benzoguanamine compounds, rosin-modified maleic acid compounds, rosin-modified fumaric acid compounds, melamine compounds, urea compounds, and phenol compounds. Among these, epoxy compounds and oxetane compounds are preferred.

(Epoxy compound (K1))
Examples of the epoxy compound (K1) include polycondensates of bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkyl aldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.), polycondensates of phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, etc.), and polycondensates of phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, etc.). , divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.), polycondensates of phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.), polycondensates of phenols and aromatic dimethanols (benzenedimethanol, α,α,α',α'-benzenedimethanol, biphenyldimethanol, α,α,α',α'-biphenyldimethanol, 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, alicyclic epoxy resins, heterocyclic epoxy resins, aliphatic epoxy resins, glycidylamine-based epoxy resins, and glycidyl ester-based epoxy resins.

Commercially available products include, for example, Epicoat 807, 815, 825, 827, 828, 190P, and 191P (all trade names: manufactured by Yuka Shell Epoxy Co., Ltd.), Epicoat 1004 and 1256 (all trade names: manufactured by Japan Epoxy Resins Co., Ltd.), TECHMORE VG3101L (trade name: manufactured by Mitsui Chemicals, Inc.), EPPN-501H and 502H (trade names: manufactured by Nippon Kayaku Co., Ltd.), JER 1032H60 (trade name: manufactured by Japan Epoxy Resins Co., Ltd.), and JER Examples include 157S65, 157S70 (trade names; manufactured by Japan Epoxy Resins Co., Ltd.), EPPN-201 (trade name; manufactured by Nippon Kayaku Co., Ltd.), JER152, 154 (all trade names; manufactured by Japan Epoxy Resins Co., Ltd.), EOCN-102S, 103S, 104S, 1020 (all trade names; manufactured by Nippon Kayaku Co., Ltd.), Celloxide 2021, EHPE-3150 (all 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 (all trade names; manufactured by Nagase ChemteX Corporation), TEPIC-L, H, S (manufactured by Nissan Chemical Industries, Ltd.), etc.

From the viewpoint of the heat resistance of the coating, the content of the epoxy compound (K1) is preferably 0.5 to 300 parts by mass, and more preferably 1.0 to 50 parts by mass, per 100 parts by mass of the colorant (A).

(Oxetane Compound (K2))
The oxetane compound (K2) is a known compound having an oxetane group. Examples of the oxetane compound include monofunctional oxetane compounds, bifunctional oxetane compounds, and trifunctional or higher oxetane compounds.

Examples of the monofunctional oxetane compound include (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, and 3-ethyl-3-{[3-(triethoxysilyl)propoxy]methyl}oxetane.
Examples of commercially available products include OXE-10 and 30 manufactured by Osaka Organic Chemical Industry Co., Ltd., and OXT-101 and 212 manufactured by Toagosei Co., Ltd.

Examples of the bifunctional oxetane compound include 4,4'-bis[(3-ethyl-3-oxetanyl)methoxymethyl]biphenyl), 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]benzene, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, di[1-ethyl(3-oxetanyl)]methyl ether, di[1-ethyl(3-oxetanyl)]methyl ether 3-ethyl-3-hydroxymethyl oxetane, 3- Ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(2-phenoxymethyl)oxetane, 3,7-bis(3-oxetanyl)-5-oxa-nonane, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3-bis[(3-ethyl-3-oxetanylmethoxy)methyl]propane, ethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, dicyclopentenyl bis(3-ethyl- 3-oxetanylmethyl) ether, triethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, 1,4-bis(3-ethyl-3-oxetanylmethoxy)butane, 1,6-bis(3-ethyl-3-oxetanylmethoxy)hexane, polyethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, ethylene oxide (EO) modified bis(3-ethyl-3-oxetanylmethyl) ether, Examples of bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether include 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, and EO-modified bisphenol F(3-ethyl-3-oxetanylmethyl) ether.
Commercially available products include OXBP and OXTP manufactured by Ube Industries, and OXT-121 and 221 manufactured by Toagosei Co., Ltd.

Examples of trifunctional or higher oxetane compounds include pentaerythritol tris(3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexa(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, and caprolactone-modified dipentaerythritol. Examples include erythritol hexa(3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropane tetrakis(3-ethyl-3-oxetanylmethyl) ether, resins containing oxetane groups (such as the oxetane-modified phenol novolac resin described in Japanese Patent No. 3783462), and polymers obtained by radical polymerization of (meth)acrylic monomers such as the aforementioned OXE-30.

The content of the oxetane compound (K2) is preferably 0.5 to 50 mass%, and more preferably 1 to 40 mass%, based on 100 mass% of the nonvolatile content of the coloring composition.

A melamine compound is a compound having a melamine ring structure. The melamine compound is preferably a methylol type or ether type compound, and more preferably a melamine compound having an average of 5.0 or more methylol groups and/or ether groups per melamine ring. Having an appropriate number of methylol groups or ether groups makes it easier to obtain just the right amount of heat resistance.

Commercially available products include, for example, Nikalac 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, and MX-410 (manufactured by Sanwa Chemical Co., Ltd.), and Cymel 232, 235, 236, 238, 285, 300, 301, 303, 350, and 370 (manufactured by Nippon Cytec Industries Co., Ltd.).

Among these, Nikarak MW-30HM, MW-390, MW-100LM, MX-750LM, MW-30M, MW-30, MW-22, MS-21, MS-11, MW-24X, MX-45 (manufactured by Sanwa Chemical Co., Ltd.) and Cymel 232, 235, 236, 238, 300, 301, 303, 350 (manufactured by Nippon Cytec Industries Co., Ltd.), which have an average of 5.0 or more methylol groups and/or ether groups per melamine ring, are preferred in terms of increasing the crosslink density.

The thermosetting compound (K) may be used alone or in combination of two or more types.

The coloring composition of the present invention can be used in combination with a curing agent (curing accelerator) to aid in the curing of the thermosetting compound. Examples of the curing agent include amine compounds, acid anhydrides, active esters, carboxylic acid compounds, and sulfonic acid compounds. Examples of the curing agent include amine compounds (e.g., dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (e.g., triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (e.g., dimethylamine, etc.), imidazole derivatives, bicyclic amidine compounds and their salts (e.g., imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-methyl ... -phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, etc.), phosphorus compounds (e.g., triphenylphosphine, etc.), S-triazine derivatives (e.g., 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine-isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine-isocyanuric acid adduct, etc.).

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

The content of the curing agent is preferably 0.01 to 15 parts by mass per 100 parts by mass of the thermosetting compound (K).

[Thiol-based chain transfer agent (L)]
The coloring composition of the present invention can contain a thiol-based chain transfer agent (L). When the thiol-based chain transfer agent (L) is used in combination with the photopolymerization initiator (I), a thiyl radical that is not easily inhibited by oxygen during radical polymerization after irradiation with light is generated, improving the photosensitivity of the coloring composition.

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

Examples of polyfunctional thiols include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthioglycolate, Examples of the thiopropionate include thritol tetrakisthiopropionate, trimercaptopropionic acid tris(2-hydroxyethyl)isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine, and preferably ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthiopropionate, and the like.

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

The content of the thiol chain transfer agent (L) is preferably 0.1 to 10% by mass, and more preferably 0.5 to 5% by mass, based on 100% by mass of the nonvolatile content of the coloring composition. When an appropriate amount is contained, the photosensitivity is improved and wrinkles are less likely to occur on the coating surface.

[Polymerization inhibitor (M)]
The colored composition of the present invention may contain a polymerization inhibitor (M).
Examples of the polymerization inhibitor (M) include alkyl catechol compounds such as catechol, resorcinol, 1,4-hydroquinone, 2-methyl catechol, 3-methyl catechol, 4-methyl catechol, 2-ethyl catechol, 3-ethyl catechol, 4-ethyl catechol, 2-propyl catechol, 3-propyl catechol, 4-propyl catechol, 2-n-butyl catechol, 3-n-butyl catechol, 4-n-butyl catechol, 2-t-butyl catechol, 3-t-butyl catechol, 4-t-butyl catechol, and 3,5-di-t-butyl catechol; 2-methyl resorcinol, 4-methyl resorcinol, 2-ethyl resorcinol, 4-ethyl resorcinol, 2-propyl resorcinol, 4-propyl resorcinol, and 2-n-butyl catechol; Examples of the alkyl resorcinol compounds include ethylresorcinol, 4-n-butylresorcinol, 2-t-butylresorcinol, and 4-t-butylresorcinol; alkylhydroquinone compounds such as methylhydroquinone, ethylhydroquinone, propylhydroquinone, t-butylhydroquinone, and 2,5-di-t-butylhydroquinone; phosphine compounds such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, and tribenzylphosphine; phosphine oxide compounds such as trioctylphosphine oxide and triphenylphosphine oxide; phosphite compounds such as triphenylphosphite and trisnonylphenylphosphite; pyrogallol; and phloroglucine.

The content of the polymerization inhibitor (M) is preferably 0.01 to 0.4 mass % based on 100 mass % of the nonvolatile content of the coloring composition.

[Ultraviolet absorber (N)]
The coloring composition of the present invention may contain an ultraviolet absorber (N). The ultraviolet absorber (N) is an organic compound having an ultraviolet absorbing function, and examples of the ultraviolet absorber (N) include benzotriazole-based organic compounds, triazine-based organic compounds, benzophenone-based organic compounds, salicylic acid ester-based organic compounds, cyanoacrylate-based organic compounds, and salicylate-based organic compounds.

Benzotriazole compounds include, for example, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, 2-[2-hydroxy-3,5-bis(α, α-Dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, 5% 2-methoxy-1-methylethyl acetate and 95% benzenepropanoic acid, 3-(2H-benzotriazol-2-yl)-(1,1-dimethylethyl)-4-hydroxy, C7-9 branched and linear alkyl ester mixture, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, methyl 3-(3-(2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxyphenyl)propionate/polyethylene glycol 300 reaction products, 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 These include octyl-4-methylphenol, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole, octyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate, and 2-ethylhexyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate.

Commercially available products include TINUVIN P, PS, 234, 326, 329, 384-2, 900, 928, 99-2, and 1130 manufactured by BASF Japan, ADK STAB LA-29, LA-31RG, LA-32, and LA-36 manufactured by ADEKA, KEMISORB 71, 73, 74, 79, and 279 manufactured by Chemipro Chemicals, and RUVA-93 manufactured by Otsuka Chemical.

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

Commercially available products include KEMISORB 102 manufactured by Chemipro Chemicals, TINUVIN 400, 405, 460, 477, 479, and 1577ED manufactured by BASF Japan, Adeka STAB LA-46 and LA-F70 manufactured by ADEKA, and CYASORB UV-1164 manufactured by Sun Chemical.

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

Commercially available products include KEMISORB 10, 11, 11S, 12, and 111 manufactured by Chemipro Chemicals, SEESORB 101 and 107 manufactured by Shipro Chemicals, Adeka STAB 1413 manufactured by ADEKA, and UV-12 manufactured by Sun Chemical.

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

The content of the ultraviolet absorber (N) is preferably 5 to 70% by mass, based on 100% by mass of the photopolymerization initiator and ultraviolet absorber combined.

[Antioxidant (O)]
The coloring composition of the present invention can contain an antioxidant (O). The antioxidant (O) can prevent the photopolymerization initiator or thermosetting compound contained in the coloring composition from yellowing due to oxidation during the thermal process of heat curing or ITO annealing, and can suppress a decrease in the transmittance of the coating. In particular, when the pigment concentration of the photosensitive composition is high, the content of the photopolymerizable compound is relatively reduced, so that the coating is likely to yellow when the amount of the photopolymerization initiator is increased or a thermosetting compound is blended. Therefore, by including an antioxidant, yellowing due to oxidation during the heating process can be prevented, and a decrease in the transmittance of the coating can be suppressed.

Examples of the antioxidant (O) 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, from the viewpoint of achieving both transmittance and sensitivity of the coating film, hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants are preferred.

Examples of hindered phenol antioxidants include 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1,1,3-tris-(2'-methyl-4'-hydroxy-5'-t-butylphenyl)-butane, 4,4'-butylidene-bis-(2-t-butyl-5-methylphenol), 3-(3,5-di-t-butyl-4-hydroxyphenyl)stearyl propionate, pentaerythritol tetrakis[3-(3,5-di-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) 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)-phenol, etc.

Commercially available products include Adeka STAB AO-20, AO-30, AO-40, AO-50, AO-60, AO-80, and AO-330 manufactured by ADEKA CORPORATION; KEMINOX 101, 179, 76, and 9425 manufactured by ChemiPro Corporation; IRGANOX 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 5057, and 565 manufactured by BASF Japan; and Cyanox CY-1790 and CY-2777 manufactured by Sun Chemical Co., Ltd.

Examples of hindered amine antioxidants include tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butane tetracarboxylate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)1,2,3,4-butane tetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl)carbonate, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 2,2 ,6,6-tetramethyl-4-piperidyl methacrylate, polycondensation product of dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine, poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-s-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidyl)imino]-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imino]], ester of 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol and 3,5,5-trimethylhexanoic acid, N,N'-4,7-tetrakis(tetramethylbutyl)amino, Bis[4,6-bis{N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino}-1,3,5-triazin-2-yl]-4,7-diazadecane-1,10-diamine, decanedioic acid bis(2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidinyl)ester, reaction products of 1,1-dimethylethyl hydroperoxide with octane, bis(1,2,2,6,6-pentamethyl-4-pyridyl)[[3,5-bis(1,1dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate methyl 1,2,2,6,6-pentamethyl-4-pyridylsebake ester, poly[[6-morpholino-s-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidyl)imino]-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imino]], 2,2,6,6-tetramethyl-4-piperidyl-C12-21 and C18 unsaturated fatty acid esters, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,6-hexamethylenediamine, 2-methyl-2-(2,2,6,6-tetramethyl-4-piperidyl)amino-N-(2,2,6,6-tetramethyl-4-piperidyl)propionamide, etc.

Commercially available products include Adeka STAB LA-52, LA-57, LA-63P, LA-68, LA-72, LA-77Y, LA-77G, LA-81, LA-82, LA-87, LA-402F, and LA-502XP manufactured by ADEKA CORPORATION; KAMISTAB 29, 62, 77, and 94 manufactured by Chemipro Chemicals; Tinuvin 249, TINUVIN 111FDL, 123, 144, 292, and 5100 manufactured by BASF Japan; and Cyasorb UV-3346, UV-3529, and UV-3853 manufactured by Sun Chemical Co., Ltd.

Examples of phosphorus-based antioxidants include di(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, 2,2'-methylenebis(4,6-di-t-butylphenyl)2-ethylhexyl phosphite, tris(2,4-di-t-butylphenyl)phosphite, tris(nonylphenyl)phosphite, tetra(C12-C15 alkyl)-4,4'-isopropylidene diphenyl diphosphite, diphenyl mono (2-ethylhexyl)phosphite, diphenyl isodecyl phosphite, tris(isodecyl)phosphite, triphenyl phosphite, tetrakis(2,4-di-t-butylphenyl)-4,4-biphenyl diphosphonate, tris(tridecyl)phosphite, phenyl isooctyl phosphite, phenyl isodecyl phosphite, phenyl di(tridecyl)phosphite, diphenyl isooctyl phosphite, diphenyl tridecyl phosphite, 4,4'-isopropylidene diphenyl alkyl phosphite, trisnonylphenyl phosphite, trisdinonylphenyl phosphite, tris(biphenyl) phosphite, di(2,4-di-t-butylphenyl)pentaerythritol diphosphite, di(nonylphenyl)pentaerythritol diphosphite, phenyl bisphenol A pentaerythritol diphosphite, tetratridecyl 4,4'-butylidenebis(3-methyl-6-t-butylphenol) diphosphite, hexatridecyl 1 , 1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane triphosphite, 3,5-di-t-butyl-4-hydroxybenzyl phosphite diethyl ester, sodium bis(4-t-butylphenyl)phosphite, sodium-2,2-methylene-bis(4,6-di-t-butylphenyl)-phosphite, 1,3-bis(diphenoxyphosphonyloxy)-benzene, ethyl bis(2,4-di-t-butyl-6-methylphenyl) phosphite, etc.

Commercially available products include Adeka STAB PEP-36, PEP-8, HP-10, 2112, 1178, 1500, C, 135A, 3010, and TPP manufactured by ADEKA Corporation, IRGAFOS168 manufactured by BASF Japan, and Hostanox P-EPQ manufactured by Clariant Chemicals.

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

Commercially available products include Adeka STAB AO-412S and AO-503 manufactured by ADEKA Corporation, and KEMINOX PLS manufactured by Chemipro Chemicals Co., Ltd.

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

The content of the antioxidant (O) is preferably 0.5 to 5.0% by mass based on 100% by mass of the nonvolatile content of the coloring composition. When an appropriate amount is contained, the transmittance, spectral characteristics, and sensitivity are improved.

[Storage stabilizer (P)]
The coloring composition of the present invention may contain a storage stabilizer (P). This stabilizes the viscosity of the coloring composition over time. Examples of the storage stabilizer (P) include quaternary ammonium chlorides such as benzyl trimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, organic phosphines such as t-butylpyrocatechol, tetraethylphosphine and tetraphenyl, and phosphites.

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

[Adhesion improver (Q)]
The coloring composition of the present invention may contain an adhesion improver (Q). This improves the adhesion between the coating and the substrate. In addition, it becomes easier to form a narrow pattern by photolithography.

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

The adhesion improver (Q) can be used alone or in combination of two or more types.

The content of the adhesion improver (Q) is preferably 0.01 to 10 parts by mass, and more preferably 0.05 to 5 parts by mass, per 100 parts by mass of the colorant (A).

[Organic solvent (R)]
The colored composition of the present invention may contain an organic solvent (R).

Examples of organic solvents (R) include 1,2,3-trichloropropane, 1-methoxy-2-propanol, ethyl lactate, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N,N-dimethylacetamide, N,N-dimethylformamide, n-butyl Alcohol, n-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary-butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol Examples of the diglycerol monomethyl ether include diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methylcyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters. Among these, from the viewpoint of pigment dispersibility and alkali-soluble resin solubility, glycol acetates such as ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate, alcohols such as benzyl alcohol and diacetone alcohol, and ketones such as cyclohexanone are preferred.

The organic solvent (R) can be used alone or in combination of two or more types.

<Method of producing colored composition>
The colored composition of the present invention is, for example, a dispersion produced by adding a colorant (A), a metal salt of a quinophthalone compound having a sulfo group (B), an alkali-soluble resin (C), a triarylsulfonium compound (E), and, if necessary, a dispersing resin (F), an organic solvent (P), etc., and dispersing the mixture. The dispersion may be produced by adding two or more types of colorants simultaneously and dispersing the colorants, or by mixing the colorants that have been separately dispersed.
Thereafter, the surfactant (D), and if necessary, the polymerizable compound (H) and the photopolymerization initiator (I) are added to the dispersion and mixed to produce the dispersion. The timing of mixing each material is arbitrary. The dispersion process can also be performed multiple times.

Examples of dispersing machines used for dispersion processing include a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, or an attritor.

The average dispersed particle size (secondary particle size) of the colorant (A) in the dispersion is preferably 30 to 200 nm, more preferably 40 to 200 nm. A moderate particle size makes it easier to obtain a coloring composition with high dispersion stability.

The average dispersed particle size (secondary particle size) is measured, for example, using Nikkiso's Microtrac UPA-EX150, which employs dynamic light scattering (FFT power spectrum method), with particle permeability set to absorption mode, particle shape aspheric, and the D50 particle size as the average size. The organic solvent used for dispersion is used as the dilution solvent for measurement, and it is preferable to measure samples treated with ultrasound immediately after sample preparation, as this tends to give results with less variation.

The coloring composition is preferably subjected to centrifugation, filtration with a sintered filter or membrane filter, or other means to remove coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, and more preferably coarse particles of 0.5 μm or more, as well as contaminated dust. The coloring composition of the present invention preferably does not substantially contain particles of 0.5 μm or more, and more preferably does not contain particles of 0.3 μm or less.

<Color filter>
The color filter of the present invention comprises a substrate and a filter segment formed using the colored composition of the present invention.

[Color filter manufacturing method]
The color filter is preferably formed by forming a black matrix on a substrate and then forming filter segments.
Examples of the black matrix include a multilayer film of chromium or 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, etc. Among these, the photolithography method is preferred in terms of being able to produce a color filter with high precision.
In the photolithography method, for example, a photosensitive coloring composition containing a colorant of a certain color tone is applied to a transparent substrate so that the dry film thickness is about 0.2 to 5 μm to form a coating. The obtained coating (hereinafter referred to as the first coating) is exposed (irradiated with light) through a mask having a predetermined pattern. Then, the coating is developed by immersing in a solvent or an alkaline developer or spraying the developer with a spray or the like, and the uncured parts are removed to obtain a desired pattern. This process can be similarly carried out using a photosensitive coloring composition containing a colorant of another color tone to produce a color filter having filter segments of each color. In addition, a second coating (oxygen barrier film) can be formed on the first coating before exposure using polyvinyl alcohol or a water-soluble acrylic resin. This prevents the first coating from coming into contact with oxygen, thereby further improving the exposure sensitivity. In addition, the color filter can be heated to cure the uncured photopolymerizable compound in the filter segment.

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

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

<Liquid Crystal Display Device>
The liquid crystal display device of the present invention comprises the color filter of the present invention.
In the liquid crystal display device, the color filter after the filter segment is formed is bonded to the counter substrate using a sealant, liquid crystal is injected from an injection port provided in the seal portion, and the injection port is sealed. If necessary, a polarizing film or a retardation film is bonded to the outside of the substrate to produce a liquid crystal display device.

The liquid crystal display device of the present invention comprises the color filter of the present invention and a light source. Examples of light sources include cold cathode fluorescent lamps (CCFLs) and white LEDs, but in the present invention, it is preferable to use white LEDs because they broaden the red reproduction range. Figure 1 is a schematic cross-sectional view of a liquid crystal display device 10 equipped with the color filter of the present invention. The device 10 shown in Figure 1 comprises a pair of transparent substrates 11 and 21 arranged at a distance from each other, with liquid crystal LC sealed between them.

The liquid crystal LC is aligned according to the driving mode, such as TN (Twisted Nematic), STN (Super Twisted Nematic), IPS (In-Plane Switching), VA (Vertical Alignment), OCB (Opticaly Compensated Birefringence), etc. 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. A polarizing plate 15 is formed on the outer surface of the transparent substrate 11.

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

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

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

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

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

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

<Solid-state imaging element>
The solid-state imaging device of the present invention includes the color filter of the present invention. The configuration of the solid-state imaging device is not limited as long as it functions as a solid-state imaging device. For example, the following configurations can be mentioned.

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

The present invention will be described in more detail below with reference to examples. However, the present invention is not limited to these examples. Note that "parts" means "parts by mass" and "%" means "% by mass."

Before going into the examples, we will explain each measurement method.

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 alkali-soluble resin and dispersing resin)
The number average molecular weight (Mn) and weight average molecular weight (Mw) of the alkali-soluble resin and the dispersed resin were measured by gel permeation chromatography (GPC) equipped with an RI detector. The apparatus used was HLC-8220GPC (manufactured by Tosoh Corporation), two separation columns were connected in series, and both packings were "TSK-GEL SUPER HZM-N" connected in series. The oven temperature was 40°C, a tetrahydrofuran (THF) solution was used as the eluent, and the measurement was performed at a flow rate of 0.35 ml/min. The sample was dissolved in a solvent consisting of 1 wt% of the above eluent, and 20 microliters were injected. The molecular weight is a polystyrene equivalent value.

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

(Amine value of dispersing resin)
The amine value of the dispersing resin is the total amine value (mg KOH/g) measured in accordance with the method of ASTM D 2074, converted into solid content.

<Production Example of Fine Phthalocyanine Pigment (A1)>
(Fine Phthalocyanine Pigments (A1-1 to A1-3))
According to the examples of JP 2017-111398 A, finely divided phthalocyanine pigments (A1-1 to A1-3) represented by the following chemical formulas 2 to 4 were obtained. The structures are shown below.

(Fine Phthalocyanine Pigment (A1-4)
100 parts of C.I. Pigment Green 58 (DIC Corporation "FASTGEN GREEN A110"), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (Inoue Manufacturing Co., Ltd.) and kneaded for 6 hours at 70 ° C. This kneaded product was added to 3000 parts of warm water, heated to 70 ° C. and stirred for 1 hour to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 24 hours to obtain 97 parts of fine phthalocyanine pigment (A1-4).

(Fine Phthalocyanine Pigment (A1-5))
200 parts of C.I. Pigment Green 36 ("Lionol Green 6YK" manufactured by Toyo Color Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 6 hours at 80° C. Next, this kneaded product was put into 8 liters of warm water, heated to 80° C. and stirred for 2 hours to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85° C. for one day to obtain 190 parts of a finely divided phthalocyanine pigment (A1-5).

(Fine Phthalocyanine Pigment (A1-6))
In a 300 mL flask, 91 parts of sulfuryl chloride, 109 parts of aluminum chloride, 15 parts of sodium chloride, 30 parts of zinc phthalocyanine, and 44 parts of bromine were charged. The mixture was heated to 130°C over 40 hours, taken out in water, and then filtered to obtain a green crude pigment. 20 parts of the obtained green crude pigment, 140 parts of pulverized sodium chloride, 32 parts of diethylene glycol, and 1.8 parts of xylene were charged in a 1 L double-arm kneader and kneaded at 100°C for 6 hours. After kneading, the mixture was taken out in 2 kg of water at 80°C, stirred for 1 hour, filtered, washed with hot water, dried, and pulverized to obtain a fine phthalocyanine pigment (A1-6). The obtained fine phthalocyanine pigment (A1-6) was found to have an average of 11.98 halogen atoms per molecule from fluorescent X-ray analysis, of which the average number of bromine atoms was 9.00 and the average number of chlorine atoms was 2.98, making it a halogenated zinc phthalocyanine pigment.

<Production of fine quinophthalone pigment (A2)>
(Fine Quinophthalone Pigment (A2-1))
100 parts of C.I. Pigment Yellow 138 (BASF Japan "Paliotol Yellow K0960-HD"), 700 parts of sodium chloride, and 180 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (Inoue Seisakusho) and kneaded for 6 hours at 80° C. This mixture was added to 2,000 parts of warm water, heated to 80° C. and stirred for 1 hour to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then dried at 80° C. for 24 hours to obtain 95 parts of fine quinophthalone pigment (A2-1).

(Fine Quinophthalone Pigment (A2-2))
According to Example 1 of JP 2012-226110 A, a fine quinophthalone pigment (A2-2) represented by the following chemical formula (5) was obtained, the structure of which is shown below.

Chemical formula (5)

(Fine Quinophthalone Pigment (A2-3))
According to the method for producing a yellow colorant described in Japanese Patent No. 6432076, a finely divided quinophthalone pigment (A2-3) represented by the following formula (6) was obtained, the structure of which is shown below.

Chemical formula (6)

<Production of Metal Salt of Quinophthalone Compound Having a Sulfo Group (B)>
(Copper Salt of Quinophthalone Compound Having a Sulfo Group (B-1))
30 parts of C.I. Pigment Yellow 138 (BASF Japan "Paliotol Yellow K0960-HD"), which is a quinophthalone compound, was dissolved in 300 parts of 101% sulfuric acid, and the mixture was stirred at 70°C for 8 hours to carry out a sulfonation reaction. The end point of the reaction was determined by measuring the spectroscopic spectrum of the sulfuric acid solution, and the point at which no change in the spectrum was observed was determined. Next, this reaction solution was poured into 3,000 parts of ice water, and the precipitate was filtered off, washed with water, and then dried at 80°C to obtain a quinophthalone compound (b-1) having a sulfo group represented by the following chemical formula (7).

Chemical formula (7)

Next, 10 g of quinophthalone compound (b-1) having a sulfo group was added to 500 parts of water and redispersed by stirring at 25°C for 2 hours. 4.8 parts of copper (II) sulfate pentahydrate was then gradually added to this solution and reacted at 60°C for 2 hours. The reaction product was filtered, washed with water, and dried at 80°C to obtain copper salt (B-1) of quinophthalone compound having a sulfo group represented by the following chemical formula (8).

Chemical formula (8)

(Silver Salt of Quinophthalone Compound Having a Sulfo Group (B-2))
A silver salt (B-2) of a quinophthalone compound having a sulfo group represented by the following chemical formula (9) was obtained in the same manner as in the production of the copper salt (B-1) of a quinophthalone compound having a sulfo group, except that 6.6 parts of silver nitrate (I) was used instead of the copper sulfate (II) pentahydrate used in the production of the copper salt (B-1) of a quinophthalone compound having a sulfo group.

Chemical formula (9)

(Zinc Salt of Quinophthalone Compound Having a Sulfo Group (B-3))
A zinc salt (B-3) of a quinophthalone compound having a sulfo group represented by the following chemical formula (10) was obtained in the same manner as in the production of the copper salt (B-1) of a quinophthalone compound having a sulfo group, except that 4.3 parts of zinc acetate dihydrate was used instead of the copper (II) sulfate pentahydrate used in the production of the copper salt (B-1) of a quinophthalone compound having a sulfo group.

Chemical Formula (10)

(Iron salt of quinophthalone compound having a sulfo group (B-4))
An iron salt (B-4) of a quinophthalone compound having a sulfo group represented by the following chemical formula (11) was obtained in the same manner as in the production of the copper salt (B-1) of a quinophthalone compound having a sulfo group, except that 5.2 parts of iron (III) chloride hexahydrate was used instead of the copper sulfate (II) pentahydrate used in the production of the copper salt (B-1) of a quinophthalone compound having a sulfo group.

Chemical formula (11)

(Aluminum Salt of Quinophthalone Compound Having a Sulfo Group (B-5))
According to the synthesis method described in Japanese Patent No. 4,585,781, an aluminum salt (B-5) of a quinophthalone compound having a sulfo group represented by the following chemical formula (12) was obtained.

Chemical Formula (12)

(Copper salt of quinophthalone compound having a sulfo group (B-6))
A quinophthalone compound (b-2) having a sulfo group represented by the following chemical formula (13) was obtained by the same production method as that for the quinophthalone compound (QL-c-1) described in the examples of JP2015-172732A.

Chemical formula (13)

Next, 10 g of quinophthalone compound (b-2) having a sulfo group was added to 500 parts of water and redispersed by stirring at 25°C for 2 hours. Next, 5.5 parts of copper (II) sulfate pentahydrate was gradually added to this solution and reacted at 60°C for 2 hours. The reaction product was filtered, washed with water, and dried at 80°C to obtain copper salt of quinophthalone compound having a sulfo group (B-6) represented by the following chemical formula (14).

Chemical formula (14)

(Aluminum salt of quinophthalone compound having a sulfo group (B-7))
An aluminum salt (B-7) of a quinophthalone compound having a sulfo group represented by the following chemical formula (15) was obtained in the same manner as in the production of the copper salt (B-6) of a quinophthalone compound having a sulfo group, except that 5 parts of aluminum sulfate were used instead of 5.5 parts of copper (II) sulfate pentahydrate.

Chemical formula (15)

<Production of alkali-soluble resin (C)>
(Alkali-soluble resin (C-1) solution)
A separable 4-neck flask was fitted with a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube and a stirrer, and 196 parts of cyclohexanone was charged into the reaction vessel. The temperature was raised to 80°C, and the inside of the reaction vessel was replaced with nitrogen. From the dropping tube, a mixture of 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.), and 1.1 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropping, the reaction was continued for another 3 hours to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled and dried by heating at 180°C for 20 minutes to measure the non-volatile content, and propylene glycol monomethyl ether acetate (hereinafter also referred to as PGMAc) was added to the previously synthesized resin solution so that the non-volatile content was 20%, to prepare an alkali-soluble resin (C-1) solution. The weight average molecular weight (Mw) was 26,000.

(Alkali-soluble resin (C-2) solution)
A separable 4-neck flask was fitted with a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube and a stirrer, and 207 parts of cyclohexanone was charged into the reaction vessel, which was then heated to 80°C and substituted with nitrogen in the reaction vessel. From the dropping tube, a mixture of 20 parts of methacrylic acid, 20 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate and 1.33 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropping, the reaction was continued for another 3 hours to obtain a copolymer resin solution. Next, the total amount of the copolymer solution obtained was stirred while stopping the nitrogen gas and injecting dry air for 1 hour, and then cooled to room temperature, and a mixture of 6.5 parts of 2-methacryloyloxyethyl isocyanate (Karenz MOI manufactured by Showa Denko K.K.), 0.08 parts of dibutyltin laurate, and 26 parts of cyclohexanone was added dropwise at 70 ° C. over 3 hours. After completion of the dropwise addition, the reaction was continued for another 1 hour to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, and cyclohexanone was added to the resin solution previously synthesized so that the non-volatile content was 20% to prepare an alkali-soluble resin (C-2) solution. The weight average molecular weight (Mw) was 18,000.

(Alkali-soluble resin (C-3) solution)
A separable 4-neck flask equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube and a stirrer was charged with 370 parts of cyclohexanone, and the temperature was raised to 80°C. After replacing the atmosphere in the flask with nitrogen, a mixture of 18 parts of paracumylphenol 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 was dropped over 2 hours from the dropping tube. After the dropping, the mixture was further reacted at 100°C for 3 hours, and then a solution of 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was 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) were added to the container with 0.5 parts of trisdimethylaminophenol and 0.1 parts of hydroquinone, and the reaction was continued for 6 hours at 120 ° C., and the reaction was terminated when the non-volatile acid value reached 0.5, to obtain an acrylic resin solution. Furthermore, 19.5 parts of tetrahydrophthalic anhydride (100% of the generated hydroxyl groups) and 0.5 parts of triethylamine were added and reacted at 120 ° C. for 3.5 hours to obtain an acrylic resin solution. After cooling to room temperature, about 2 g of the resin solution was sampled and dried at 180 ° C. for 20 minutes to measure the non-volatile content, and PGMAc was added to the resin solution synthesized earlier so that the non-volatile content was 20% by mass to prepare an alkali-soluble resin (C-3) solution. The weight average molecular weight (Mw) was 19,000.

(Alkali-soluble resin (C-4) solution)
A separable flask equipped with a cooling tube was prepared as a reaction vessel. Meanwhile, a thoroughly stirred mixture of 40 parts of dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, 40 parts of methacrylic acid, 120 parts of methyl methacrylate, 4 parts of t-butylperoxy 2-ethylhexanoate ("Perbutyl O" manufactured by Nippon Oil & Fats), and 40 parts of PGMAc was prepared as a monomer dropping vessel. A thoroughly stirred mixture of 8 parts of n-dodecanethiol and 32 parts of PGMAc was prepared as a chain transfer agent dropping vessel.
395 parts of PGMAc was charged into the reaction vessel, and after replacing with nitrogen, the temperature of the reaction vessel was raised to 90 ° C. by heating in an oil bath while stirring. After the temperature of the reaction vessel was stabilized at 90 ° C., dropping was started from the monomer dropping tank and the chain transfer agent dropping tank. Dropping was carried out over 135 minutes while maintaining the temperature at 90 ° C. 60 minutes after the end of dropping, the temperature was raised to 110 ° C. After maintaining 110 ° C. for 3 hours, a gas introduction tube was attached to the separable flask, and bubbling of a mixed gas of oxygen / nitrogen = 5 / 95 (volume ratio) was started. Next, 70 parts of glycidyl methacrylate, 0.4 parts of 2,2'-methylenebis (4-methyl-6-t-butylphenol), and 0.8 parts of triethylamine were charged into the reaction vessel, and the reaction was carried out at 110 ° C. for 12 hours. Then, 150 parts of PGMAc was added and cooled to room temperature, and about 2 g of the resin solution was sampled and dried by heating at 180°C for 20 minutes to measure the non-volatile content, and PGMAc was added to the previously synthesized resin solution so that the non-volatile content was 20 mass%, to obtain an alkali-soluble resin (C-4) solution. The weight average molecular weight of the resin was 18,000, and the acid value per non-volatile content was 2 mgKOH/g.

(Alkali-soluble resin (C-5) solution)
A flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen inlet tube was charged with 333 parts of PGMAc, and the atmosphere in the flask was changed from air to nitrogen. After that, the temperature was raised to 100°C, and a solution obtained by adding 3.6 parts of azobisisobutyronitrile to a mixture consisting of 70.5 parts (0.40 mol) of benzyl methacrylate, 71.1 parts (0.50 mol) of glycidyl methacrylate, 22.0 parts (0.10 mol) of tricyclodecane-skeleton monomethacrylate (FA-513M manufactured by Hitachi Chemical Co., Ltd.), and 164 parts of PGMAc was dropped into the flask from the dropping funnel over 2 hours, and stirring was continued for another 5 hours at 100°C. Next, the atmosphere in the flask was changed from nitrogen to air, and 43.0 parts of methacrylic acid [0.5 moles, (100 mol% relative to the glycidyl group of the glycidyl methacrylate used in this reaction)], 0.9 parts of trisdimethylaminomethylphenol and 0.145 parts of hydroquinone were charged into the flask, and the reaction was continued for 6 hours at 110 ° C., and the reaction was terminated when the non-volatile acid value became 1 mgKOH / g. Next, 60.9 parts (0.40 moles) of tetrahydrophthalic anhydride and 0.8 parts of triethylamine were added, and the reaction was carried out at 120 ° C. for 3.5 hours to obtain a photosensitive transparent resin solution with an acid value of 80 mgKOH / g. After cooling to room temperature, about 2 parts of the photosensitive transparent resin solution was sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, and PGMAc was added to the photosensitive transparent resin solution synthesized earlier so that the non-volatile content was 20% by mass to prepare an alkali-soluble resin (C-5) solution. The weight average molecular weight (Mw) was 12,000.

(Alkali-soluble resin (C-6) solution)
A flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen inlet tube was charged with 182 parts of PGMAc, and the atmosphere in the flask was changed from air to nitrogen. The temperature was then raised to 100°C, after which a solution of 70.5 parts (0.40 mol) of benzyl methacrylate, 43.0 parts (0.5 mol) of methacrylic acid, 22.0 parts (0.10 mol) of tricyclodecane-skeleton monomethacrylate (FA-513M manufactured by Hitachi Chemical Co., Ltd.) and 136 parts of PGMAc was added dropwise to the flask from the dropping funnel over 2 hours, and the mixture was stirred at 100°C for 5 hours. Next, the atmosphere in the flask was changed from nitrogen to air, and 35.5 parts of glycidyl methacrylate [0.25 moles, (50 moles relative to the carboxyl group of the methacrylic acid used in this reaction)], 0.9 parts of trisdimethylaminomethylphenol and 0.145 parts of hydroquinone were charged into the flask, and the reaction was continued for 6 hours at 110 ° C. to obtain a photosensitive transparent resin solution having an acid value of 79 mg KOH / g. After cooling to room temperature, about 2 parts of the photosensitive transparent resin solution was sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, and PGMAc was added to the photosensitive transparent resin solution synthesized earlier so that the non-volatile content was 20 mass% to prepare an alkali-soluble resin (C-6) solution. The mass average molecular weight (Mw) was 13,000.

<Production of Surfactant (D1)>
(Surfactant (D1-1) solution)
In a nitrogen-substituted flask, 65 parts by mass of methyl ethyl ketone as a solvent and 25.6 parts by mass of dicyclopentanyl methacrylate as other monomers (d2) were charged, and the temperature was raised to 60°C while stirring under a nitrogen stream. Next, 3.1 parts by mass of 2,2'-bipyridyl and 1.1 parts by mass of cuprous chloride were charged, and the flask was stirred for 30 minutes while maintaining the temperature at 60°C. Then, 2.0 parts by mass of 2-bromoisoethyl acetate was added, and the mixture was reacted for 2 hours at 40°C under a nitrogen stream. Next, 10.5 parts by mass of 2-(nonafluorobutyl)ethyl methacrylate was added as a monomer (d1) having a fluorinated alkyl group, and the mixture was reacted for 8 hours at 60°C to obtain a reaction product. 30 parts by mass of activated alumina was added to the obtained reaction product and stirred. After filtering through activated alumina, the solvent was removed by distillation under reduced pressure, and PGMAc was added so that the nonvolatile content was 2% by mass, and a surfactant (D1-1) solution was obtained.

(Surfactant (D1-2 to D1-7) Solutions)
Solutions of surfactants (D1-2 to D1-7) were obtained in the same manner as above, except that the monomer (d1) having a fluorinated alkyl group used in the production of surfactant (D1-1) and the other monomer (d2) were replaced with compounds shown in Table 1.

(Surfactant (D1-8) solution)
A glass flask equipped with a stirring device, a thermometer, a cooling tube, and a dropping device was charged with 63 parts by mass of methyl isobutyl ketone as a solvent, and the temperature was raised to 105 ° C. while stirring under a nitrogen stream. Next, 21.5 parts by mass of the compound described in Table 1 as a monomer (d1) having a poly (perfluoroalkylene ether) chain, 41.3 parts by mass of the compound described in Table 1 as other monomers (d2), 9.4 parts by mass of t-butylperoxy-2-ethylhexanoate as a radical polymerization initiator, and 135.4 parts by mass of an initiator solution obtained by mixing 126 parts by mass of methyl isobutyl ketone as a solvent were set in separate dropping devices, and were dropped over 2 hours at the same time while maintaining the flask at 105 ° C. After completion of the dropping, the mixture was stirred at 105 ° C. for 10 hours, and then the solvent was removed by distillation under reduced pressure. Next, 74.7 parts by mass of methyl ethyl ketone as a solvent, 0.1 parts by mass of p-methoxyphenol as a polymerization inhibitor, and 0.06 parts by mass of dibutyltin dilaurate as a urethanization catalyst were charged, and 44.8 parts by mass of 2-acryloyloxyethyl isocyanate was added dropwise over 1 hour while stirring at 60° C. After completion of the dropwise addition, the mixture was stirred at 60° C. for 1 hour, then heated to 80° C. and stirred for 10 hours to react. PGMAc was added so that the nonvolatile content was 2% by mass, and a surfactant (D1-8) solution was obtained.

Compounds d1 and d2 in Table 1 are shown below.

(In formula (d1-3), A is a perfluoromethylene group and a perfluoroethylene group, and there are an average of 7 perfluoromethylene groups and an average of 8 perfluoroethylene groups per molecule, and the average number of fluorine atoms is 46.)

（ｄ２－３）

(d2-3)

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

(Dispersion resin (F-2) solution)
Into a reaction vessel equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer, 3 parts of trimellitic anhydride, 1 part of 3-mercapto-1,2-propanediol, 50 parts of PGMAc, and 0.1 parts of dimethylbenzylamine were added. After replacing the atmosphere with nitrogen gas, the inside of the reaction vessel was heated to 120°C and reacted for 4 hours, and then reacted at 80°C for 2 hours. Further, 30 parts of tertiary butyl acrylate, ETERNACOLL OXMA (methacrylic acid (3- A reaction vessel was charged with 20 parts of ethyloxetan-3-ylmethyl ether (manufactured by Ube Industries), 5 parts of methacrylic acid, 40 parts of ethyl acrylate, and 10 parts of PGMAc, and the inside of the reaction vessel was kept at 80° C. while 2,2′-azobisisobutyric acid was added. Fifteen portions of 0.2 parts of ethyl acetate were added every 30 minutes. A non-volatile measurement was taken one hour after the final addition and found that 95% of the monomers had reacted. PGMAc was added to dilute the solution so that the nonvolatile content was 30% by nonvolatile content measurement, and a dispersion resin (F-2) solution having an acid value of 51 mgKOH/g and a weight average molecular weight (Mw) of 24,000 per nonvolatile content was obtained.

(Dispersion resin (F-3) solution)
A reaction apparatus equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer was charged with 30 parts of methyl methacrylate, 30 parts of n-butyl methacrylate, 20 parts of hydroxyethyl methacrylate, and 13.2 parts of tetramethylethylenediamine, and nitrogen was introduced. The mixture was stirred at 50° C. for 1 hour while stirring, and the atmosphere in the system was replaced with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate, 5.6 parts of cuprous chloride, and 133 parts of PGMAc were charged, and the temperature was raised to 110° C. under a nitrogen stream. After 4 hours of polymerization, the polymerization solution was sampled and the non-volatile content was measured. It was confirmed that the polymerization conversion rate was 98% or more based on the non-volatile content. did.
Next, 61 parts of PGMAc and 20 parts of 1,2,2,6,6-pentamethylpiperidyl methacrylate (Hitachi Chemical Co., Ltd., Fancryl FA-711MM) as a second block (A block) monomer were added to the reaction vessel. The reaction was continued by stirring while maintaining the temperature at 110° C. under a nitrogen atmosphere. Two hours after the addition of 1,2,2,6,6-pentamethylpiperidyl methacrylate, the polymerization solution was sampled and the non-volatile content was measured. It was confirmed that the polymerization conversion rate of the second block (A block) was 98% or more calculated from the nonvolatile content, and the reaction solution was cooled to room temperature to terminate the polymerization. %, to obtain a dispersion resin (F-3) solution having a piperidyl skeleton with an amine value of 57 mgKOH/g per nonvolatile content and a number average molecular weight of 4,500 (Mn).

(Dispersion resin (F-4) solution)
Into a 500 mL round-bottomed, four-necked separable flask equipped with a condenser, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer, 250 parts by mass of tetrahydrofuran (THF) and 5.81 parts by mass of dimethylketene methyltrimethylsilyl acetal as an initiator were added. 0.5 parts by mass of a 1 mol/L acetonitrile solution of tetrabutylammonium m-chlorobenzoate as a catalyst was added using a syringe, and the mixture was thoroughly purged with nitrogen. Solvent-philic blocking monomers: 2-hydroxyethyl methacrylate, 19.7 parts by mass; 2-ethylhexyl methacrylate, 7.5 parts by mass; n-butyl methacrylate, 12.9 parts by mass; and benzyl methacrylate, 10.7 parts by mass. 30.9 parts by weight of methyl methacrylate and 30.9 parts by weight of ethyl acetate were added dropwise over 60 minutes using an addition funnel. The reaction flask was cooled in an ice bath to keep the temperature below 40°C. After 1 hour, 18.3 parts by mass of dimethylaminopropyl methacrylamide, a monomer for a colorant-adsorbing functional block, was added dropwise over 20 minutes. After reacting for 1 hour, 1 part by mass of methanol was added to stop the reaction. The resulting THF solution of the block copolymer was reprecipitated in hexane, filtered, and purified by vacuum drying.
Next, 15.0 parts by mass of the obtained block copolymer was dissolved in 35 parts by mass of PGMAc in a 100 mL round-bottom flask, and 1.1 parts by mass of phenylphosphinic acid (dimethylaminopropyl methacrylamide), which is a salt-forming component, was added. C. for 20 hours, and then PGMAc was added thereto to obtain a dispersion resin (F-4) solution having a non-volatile content of 30%.

<Preparation of Dispersion>
(Dispersion 1)
The following raw materials were mixed and stirred to be uniform, and then dispersed for 3 hours in an Eiger mill (Eiger Japan "Mini Model M-250 MKII") using zirconia beads having a diameter of 0.5 mm, and then filtered through a filter having a pore size of 1.0 μm to prepare Dispersion 1. The organic solvent (R-1) was PGMAc.
Finely divided phthalocyanine pigment (A1-1): 10.0 parts Dispersion resin (F-2) solution: 10.0 parts Dispersion resin (F-3) solution: 7.0 parts Alkali-soluble resin (C-1) solution: 10.0 parts Organic solvent (R-1): 63.0 parts

(Dispersions 2 to 27)
Dispersions 2 to 27 were prepared in the same manner as Dispersion 1, except that the raw materials and amounts shown in Table 2 were changed.

The ingredients listed in Table 2 are as follows:

[Triarylsulfonium compound (E)]
(E-1): T1609 (Tokyo Chemical Industry Co., Ltd.: triphenylsulfonium bromide)
(E-2): SP-066 (manufactured by ADEKA Corporation: triphenylsulfonium trifluoromethanesulfonate (E-3): WPAG-336 (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.: diphenyl-4-methylphenylsulfonium trifluoromethanesulfonate (E-4): TS-01 (manufactured by Sanwa Chemical Co., Ltd.: tris(4-methylphenyl)sulfonium trifluoromethanesulfonate (E-5): WPAG-370 (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.: diphenyl(4-methoxyphenyl)sulfonium trifluoromethanesulfonate (E-6): SP-056 (manufactured by ADEKA Corporation: triphenylsulfonium nonafluorobutanesulfonate (E-7): TS-91 (manufactured by Sanwa Chemical Co., Ltd.: tris(4-methylphenyl)sulfonium hexafluorophosphate

<Production of Colored Composition>
[Example 1]
(Coloring composition 1)
The following raw materials were mixed and stirred to be homogeneous, and then filtered through a filter having a pore size of 1.0 μm to obtain a colored composition 1.
Dispersion 2: 30.0 parts Dispersion 7: 6.25 parts Dispersion 18: 18.75 parts Alkali-soluble resin (C): 5.0 parts Surfactant (D1-1): 1.5 parts Polymerizable compound (H): 2.0 parts Photopolymerization initiator (I): 1.0 parts Sensitizer (J): 0.2 parts Epoxy compound (K1): 1.0 parts Thiol chain transfer agent (L): 0.1 parts Polymerization inhibitor (M): 0.1 parts Ultraviolet absorber (N): 0.1 parts Antioxidant (O): 0.1 parts Storage stabilizer (P): 0.1 parts Organic solvent (R): 33.8 parts

[Examples 2 to 41, Comparative Examples 1 to 4]
(Colored compositions 2 to 45)
Colored compositions 2 to 45 were prepared in the same manner as in the colored composition 1 of Example 1, except that the raw materials and amounts were changed as shown in Table 3. In addition, Examples 1 to 7 and 14 in this specification are reference examples.

The details of each of the raw materials listed in Tables 3-1 to 3-1 are as follows:

[Alkali-soluble resin (C) solution]
The alkali-soluble resin (C-2) to (C-6) solutions were mixed in equal amounts to prepare an alkali-soluble resin (C) solution.

[Surfactant (D)]
(D2-1): 2 parts of BYK-330 (manufactured by BYK-Chemie) are dissolved in 98 parts of PGMAc.

[Polymerizable compound (H)]
(H-1): Aronix M309 (manufactured by Toagosei Co., Ltd.)
(H-2): Aronix M402 (manufactured by Toagosei Co., Ltd.)
(H-3): Aronix M520 (manufactured by Toagosei Co., Ltd.)
(H-4): KAYARAD DPCA-30 (manufactured by Nippon Kayaku Co., Ltd.)
The above (H-1) to (H-4) were mixed in equal amounts to obtain a polymerizable compound (H).

[Photopolymerization initiator (I)]
(I-1): Irgacure 907 (manufactured by BASF Japan)
(I-2): Irgacure 379 (manufactured by BASF Japan)
(I-3): Irgacure OXE01 (manufactured by BASF Japan)
(I-4): Irgacure OXE02 (manufactured by BASF Japan)
(I-5): Irgacure OXE04 (manufactured by BASF Japan)
The above (I-1) to (I-5) were mixed in equal amounts to prepare a photopolymerization initiator (I).

[Sensitizer (J)]
(J-1): Kayacure DETX-S (manufactured by Nippon Kayaku Co., Ltd.)
(J-2): 4,4 CHEMARK DEABP (manufactured by Chemark Chemical Co.)
The above (J-1) and (J-2) were mixed in equal amounts to prepare sensitizer (I).

[Epoxy compound (K1)]
(K1-1): EHPE-3150 (manufactured by Daicel Corporation)
(K1-2): Denacol EX611 (manufactured by Nagase ChemteX Corporation)
(K1-3): Triglycidyl isocyanurate. The above (K1-1) to (K1-3) were mixed in equal amounts to obtain the epoxy compound (K1).

[Thiol-based chain transfer agent (L)]
(L-1): Trimethylolethane tris(3-mercaptobutyrate)
(L-2): Trimethylolpropane tris(3-mercaptobutyrate)
(L-3): Pentaerythritol tetrakis(3-mercaptopropionate)
(L-4): Trimethylolpropane tris(3-mercaptopropionate)
(L-5): Tris[(3-mercaptopropionyloxy)-ethyl]-isocyanurate. The above (L-1) to (L-5) were mixed in equal amounts to prepare a thiol-based chain transfer agent (L).

[Polymerization inhibitor (M)]
(M-1): 4-methylcatechol (M-2): methylhydroquinone (M-3): t-butylhydroquinone The above (M-1) to (M-3) were mixed in equal amounts to prepare a polymerization inhibitor (M).

[Ultraviolet absorber (N)]
(N-1): TINUVIN 400 (manufactured by BASF Japan)
(N-2): TINUVIN900 (manufactured by BASF Japan)
The above (N-1) and (N-2) were mixed in equal amounts to prepare an ultraviolet absorber (N).

[Antioxidant (O)]
(O-1): pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate (O-2): dioctadecyl 3,3'-thiodipropanoate (O-3): tris[2,4-di-(t)-butylphenyl]phosphine (O-4): bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate (O-5): p-octylphenyl salicylate. The above (O-1) to (O-5) were mixed in equal amounts to give antioxidant (N).

[Storage stabilizer (P)]
(P-1): 2,6-bis(1,1-dimethylethyl)-4-methylphenol (P-2): triphenylphosphine The above (P-1) and (P-2) were mixed in equal amounts to prepare a storage stabilizer (P).

[Organic solvent (R)]
(R-1): Propylene glycol monomethyl ether acetate 30 parts (R-2): Cyclohexanone 30 parts (R-3): 3-ethoxyethyl propionate 10 parts (R-4): Propylene glycol monomethyl ether 10 parts (R-5): Cyclohexanol acetate 10 parts (R-6): Dipropylene glycol methyl ether acetate 10 parts or more. (R-1) to (R-6) were mixed in the above parts by mass to obtain organic solvent (R).

<Evaluation of Colored Composition>
The tests were carried out according to the following methods. The evaluation results are shown in Table 3.

[Foreign matter evaluation]
The obtained colored composition was applied onto a glass substrate using a spin coater so that the chromaticity value of the coating film after heat treatment was y = 0.60 with a C light source. Next, it was dried at 70 ° C for 20 minutes, exposed to ultraviolet light at an integrated light amount of 50 mJ / cm ² using a specified mask and an ultra-high pressure mercury lamp, spray-developed with an aqueous sodium carbonate solution at 23 ° C, washed with ion-exchanged water, and air-dried to form pattern pixels.
After that, the glass substrate was heat-treated at 230°C for 40 minutes in an oven, and the number of foreign particles on the glass substrate between the pattern pixels was counted. The surface was observed using a metal microscope "BX60" (manufactured by Olympus Systems Co., Ltd.) for evaluation. The magnification was set to 500 times, and the number of foreign particles observable in any five fields of view in transmission was counted by integrating them. A number of 3 or more was considered practical.
5: The number of foreign objects is less than 5
4: The number of foreign objects is 5 or more but less than 10. 3: The number of foreign objects is 10 or more but less than 20. 2: The number of foreign objects is 20 or more but less than 50. 1: The number of foreign objects is 50 or more.

[Lightness evaluation]
The obtained colored composition was applied onto a glass substrate using a spin coater so that the chromaticity value of the coating film after heat treatment was y = 0.60 with a C light source, and dried for 20 minutes at 70 ° C. Next, ultraviolet exposure was performed using an ultra-high pressure mercury lamp with an integrated ultraviolet light amount of 50 mJ / cm ² , and spray development was performed with an aqueous sodium carbonate solution at 23 ° C., followed by washing with ion-exchanged water, air drying, and heat treatment for 40 minutes at 230 ° C. in an oven to form a colored composition layer on the glass substrate.
Next, an overcoat agent was applied onto the colored composition layer using a spin coater, and the organic solvent was removed using a vacuum dryer. After that, the resultant was baked on a hot plate at 90° C. for 2 minutes, and then heat-treated at 230° C. for 60 minutes to obtain a substrate for evaluating brightness.
The initial brightness of the obtained brightness evaluation substrate in the XYZ color system was measured using LVmicroZ (manufactured by Lambda Vision). After that, the substrate was irradiated with ultraviolet light for 200 hours using LED lighting, and the brightness was measured again. The brightness change rate was calculated using the following formula. A value of 3 or more is practical.
Brightness change rate = |Brightness after 200 hours - initial brightness|/initial brightness x 100
5: Less than 3% 4: 3% or more, less than 5% 3: 5% or more, less than 10% 2: 10% or more, less than 15% 1: 15% or more

[Evaluation of voltage holding ratio]
The obtained colored composition was applied to a glass substrate having an ITO transparent electrode with an effective electrode size of 10 mm x 10 mm using a spin coater so that the coating film after drying and heat treatment would be 2.0 μm, the coating film on the electrode part was wiped off with a solvent, and then exposed to ultraviolet light at an integrated light quantity of 50 mJ/cm ² and developed with an alkaline developer at 23° C. to obtain a coating substrate. Next, the substrate was heated at 230° C. for 20 minutes and allowed to cool, and then two sample coated substrates for measurement were prepared.
Two glass substrates coated with the above sample were placed facing each other with the ITO transparent electrode surfaces facing each other, and a small cell was prepared using a sealant so that the cell gap was 9 μm. A liquid crystal liquid was injected into the cell gap of this small cell, and a voltage of 5 V was applied for 60 μs at 50° C., and the cell voltage [V1] 16.67 ms after the voltage was released was measured using a VHR-1S manufactured by Toyo Corporation. The measured cell voltages were averaged, and the initial VHR (%) was calculated using the obtained cell voltage according to the following formula.
VHR (voltage holding rate) (%) = ([V1]/5) x 100
The cell sample after the initial VHR measurement was irradiated with LED lighting at 150,000 nits for 3 hours and then the VHR (%) after irradiation was measured again, and ΔVHR (rate of change in voltage holding ratio) was calculated using the following formula and evaluated according to the following criteria. A value of 3 or higher was determined as a practical level.
ΔVHR = | Initial VHR - Post-exposure VHR |
5: Less than 2% 4: 2% or more, less than 5% 3: 5% or more, less than 10% 2: 10% or more, less than 15% 1: 15% or more

REFERENCE SIGNS LIST 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 (8)

A coloring composition comprising a colorant (A), a metal salt of a quinophthalone compound having a sulfo group (B), an alkali-soluble resin (C), and a surfactant (D),
The colorant (A) contains a phthalocyanine pigment (A1) and a quinophthalone pigment (A2),
the metal salt (B) of a quinophthalone compound having a sulfo group includes at least one selected from the group consisting of a copper salt of a quinophthalone compound having a sulfo group, a silver salt of a quinophthalone compound having a sulfo group, a zinc salt of a quinophthalone compound having a sulfo group, an iron salt of a quinophthalone compound having a sulfo group, and an aluminum salt of a quinophthalone compound having a sulfo group;
The coloring composition includes a surfactant (D1), the surfactant (D) being a copolymer of a monomer (d1) having one or more of a fluorinated alkyl group and a poly(perfluoroalkylene ether) chain and another monomer (d2). The content of the copper salt of the quinophthalone compound having a sulfo group is 20 to 80 mass% in 100 mass% of the metal salt of the quinophthalone compound having a sulfo group (B). The colored composition according to claim 1 or 2 , wherein the other monomer (d2) is a polycyclic alicyclic structure-containing monomer. The colored composition according to any one of claims 1 to 3 , wherein the quinophthalone pigment (A2) contains a quinophthalone pigment represented by the following general formula (1):
General formula (1)

(In general formula (1), R ₁ to R ₁₃ each independently represent a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, or an aryl group which may have a substituent. Adjacent groups among _{R 1} to R ₄ and/or R ₅ to R ₈ may join together to form an aromatic ring which may have a substituent.) The colored composition according to any one of claims 1 to 4 , further comprising a triarylsulfonium compound (E). A color filter comprising a substrate and a filter segment formed using the coloring composition according to any one of claims 1 to 5 . A liquid crystal display device comprising the color filter according to claim 6 . A solid-state imaging device comprising the color filter according to claim 6 .