JP2022039341A - Coloring composition, color filter, liquid crystal display device, and solid-state imaging device - Google Patents

Abstract

To provide a coloring composition which is less in foreign matter generation, is excellent in a voltage holding rate, and is less in brightness deterioration.SOLUTION: A coloring composition contains a coloring agent (A), a metal salt (B) of a quinophthalone compound having a sulfo group, an alkali-soluble resin (C) and a surface active agent (D), in which the coloring agent (A) contains a phthalocyanine pigment (A1) and a quinophthalone pigment (A2), metal of the metal salt (B) of the quinophthalone compound having the sulfo group is one or more metal selected from the group consisting of copper, silver, zinc, iron and aluminum, and the surface active agent (D) contains a surface active agent (D1) that is a copolymer of a monomer (d1) having one or more of a fluorinated alkyl group and a poly(perfluoroalkylene ether) chain, and other monomer (d2).SELECTED DRAWING: Figure 1

Description

The present invention relates to a coloring composition used for a color filter or the like.

Generally, a color filter has a fine band (striped) shape composed of a red filter layer (R), a green filter layer (G), and a blue filter layer (B) formed on the surface of a transparent substrate such as glass. The filter segments (pixels) of the above are arranged in parallel or crossed each other, or fine filter segments are arranged in a constant vertical and horizontal arrangement. The filter segments are as fine as several microns to several hundreds of microns, and are arranged in a predetermined arrangement for each hue.

In the green filter segment in the color filter, a yellow pigment is used as a color adjusting agent (coloring agent for toning) in addition to the green pigment as a colorant. I. Pigment Yellow 138, C.I. I. Pigment Yellow 139, C.I. I. Pigment Yellow 150, C.I. I. Pigment Yellow 185 and the like are used. Among them, C.I. I. Pigment Yellow 138 is often used. However, the quinophthalone pigment, C.I. I. Pigment Yellow 138 has a problem that foreign matter is generated when heat of 230 ° C. or higher is applied.

Furthermore, C.I., which is widely used as a green pigment. I. Pigment Green 7, C.I. I. Pigment Green 36, C.I. I. Pigment Green 58, C.I. I. Pigment Green 59, C.I. I. Pigment Green 62, C.I. I. Pigment Green 63, Japanese Patent Application Laid-Open No. 2008-13983, Japanese Patent Application Laid-Open No. 2007-320986, Japanese Patent Application Laid-Open No. 2004-070342, etc. The phthalocyanine pigment of Japanese Patent Publication No. 2017-197685 and the green filter segment using the yellow pigment have a problem that the brightness decreases when exposed to a backlight (see, for example, Non-Patent Document 1) and a decrease in the voltage retention rate. There is a problem that it occurs and adversely affects the drive of the liquid crystal display device.

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

Further, as an effort to solve the decrease in brightness, Patent Document 3 discloses a phthalocyanine-based colorant, a yellow colorant, and a colorable resin composition containing a metal compound which is a component different from the colorant. There is.

Japanese Unexamined Patent Publication No. 2002-179979 Japanese Unexamined Patent Publication No. 2011-122125 Japanese Unexamined Patent Publication No. 2017-186546

Journal of Photopolymer Science and Technology, Volume7, Number1 (1994) p. 151-158

However, in the colored compositions of References 1 and 2, the suppression of the generation of foreign substances is not satisfactory, and the decrease in brightness and the decrease in the voltage retention rate are not considered. In addition, the coloring composition of Cited Document 3 was not at a satisfactory level in suppressing the decrease in lightness. In addition, no consideration was given to suppressing the generation of foreign matter and reducing the voltage holding rate.

An object of the present invention is to provide a coloring composition capable of forming a color filter having less foreign matter, excellent voltage retention, and less decrease in brightness.

The coloring composition of the present invention is a coloring composition containing a coloring agent (A), a metal salt (B) of a quinophthalone compound having a sulfo group, 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 the 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) is a copolymer of a monomer (d1) having at least one of a fluorinated alkyl group and a poly (perfluoroalkylene ether) chain and another monomer (d2). Contains a surfactant (D1).

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a coloring composition, a color filter, a liquid crystal display device, and a solid-state image sensor capable of forming a color filter having less foreign matter generation, excellent voltage retention, and less decrease in brightness.

It is a schematic cross-sectional view of the liquid crystal display device.

Hereinafter, embodiments for carrying out the present invention will be described in detail. The present invention is not limited to the following embodiments, and can be variously modified and implemented within the scope of the gist thereof.

In the present specification, the term "(meth) acryloyl", "(meth) acrylic", "(meth) acrylic acid", "(meth) acrylate", or "(meth) acrylamide" is particularly described. Unless there is an acryloyl and / or methacrylic acid, acrylic and / or methacrylic acid, acrylic acid and / or methacrylic acid, acrylate and / or methacrylate, or acrylamide and / or methacrylamide, respectively. It shall be represented. "CI" means a color index (CI). 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 coloring agent (A), a metal salt (B) of a quinophthalone compound having a sulfo group, 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 the 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) is a monomer (d1) having at least one of a fluorinated alkyl group and a poly (perfluoroalkylene ether) chain (hereinafter, also referred to as a monomer (d1)), and others. It contains a surfactant (D1) which is a copolymer with the monomer (d2).

Hereinafter, the components contained in or may be contained in the coloring composition of one embodiment will be described in detail.

[Colorant (A)]
(Futarusinin pigment (A1))
The coloring composition of the present invention contains a phthalocyanine pigment (A1) as a coloring agent (A).

The phthalocyanine pigment (A1) is specifically classified as a Pigment in the Color Index (CI; The Society of Dyers and Colorists). I. Pigment Green 7,10,36,37,58,59,62,63, Japanese Patent Application Laid-Open No. 2008-19383, Japanese Patent Application Laid-Open No. 2007-320986, Japanese Patent Laid-Open No. 2004-70342, etc. The aluminum phthalocyanines, C.I. I. Bigment blue 15, 15: 1, 15: 2, 15: 3, 15: 4, etc. can be mentioned. Among these, C.I. I. The phthalocyanine pigments described in Pigment Green 36,58,59,62,63, JP-A-2016-57635, JP-A-2016-153481, and JP-A-2017-197685 are preferable.

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

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

(Kinophthalone pigment (A2))
The coloring composition of the present invention contains a quinophthalone pigment (A2) as a coloring agent (A).

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

General formula (1)

In the general formula (1), R ₁ to R ₁₃ each independently have a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, and a substituent. Indicates a optionally aryl group. Adjacent groups of R ₁ to R ₄ and / or R ₅ to R ₈ may be combined to form an aromatic ring that may have a substituent.

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

Examples of the halogen atom include fluorine, chlorine, bromine and iodine.

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

Examples of the alkoxyl group that may have a substituent include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutyloxy group, a tert-butyloxy group, a neopentyloxy group, and a few. -In addition to linear or branched alkoxyl groups such as dimethyl-3-pentoxy, n-hexyloxy group, n-octyloxy group, stearyloxy group and 2-ethylhexyloxy group, trichloromethoxy group, trifluoromethoxy group, 2 , 2,2-Trifluoroethoxy group, 2,2,3,3-tetrafluoropropyloxy group, 2,2-ditrifluoromethylpropoxy group, 2-ethoxyethoxy group, 2-butoxyethoxy group, 2-nitropropoxy Examples thereof include an alkoxyl group having a substituent such as a group and a benzyloxy group.

Examples of the aryl group which may have a substituent include an aryl group such as a phenyl group, a naphthyl group and an anthranyl group, as well as a p-methylphenyl group, a p-bromophenyl group, a p-nitrophenyl group and p-. Methoxyphenyl group, 2,4-dichlorophenyl group, pentafluorophenyl group, 2-aminophenyl group, 2-methyl-4-chlorophenyl group, 4-hydroxy-1-naphthyl group, 6-methyl-2-naphthyl group, 4 , 5,8-Trichloro-2-naphthyl group, anthraquinonyl group, 2-aminoanthraquinonyl group and other aryl groups having substituents can be mentioned.

Adjacent groups of R ₁ to R ₄ and / or R ₅ to R ₈ of the general formula (1) together form an aromatic ring which may have a substituent. Examples of the aromatic ring here include a hydrocarbon aromatic ring and a complex aromatic 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 quinoxalin 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, and an indole ring. , Carbazole ring and the like.

The quinophthalone pigment (A2) is C.I. I. Pigment Yellow 138, or any of the quinophthalone pigments represented by the following general formulas (2) to (4) is preferable. Here, in R ₁₄ to R ₂₈ , R ₂₉ to R ₄₃ , and R ₄₄ to R ₆₀ , a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, and the like. The aryl group which may have a substituent is synonymous with the group described by the general formula (1).

一般式（４）

General formula (4)

In the general formulas (2) to (4), R ₁₄ to R ₂₈ , R ₂₉ to R ₄₃ , and R ₄₄ to R ₆₀ may independently have a hydrogen atom, a halogen atom, a hydroxyl group, and a substituent. An alkyl group, an alkoxyl group which may have a substituent, and an aryl group which may have a substituent are shown.

Further, in the quinophthalone pigment (A2) used in the coloring composition of the present invention, R ₁₄ to R ₂₈ , R ₂₉ to R ₄₃ , and R ₄₄ to R ₆₀ of the general formulas (2) to (4) are hydrogen atoms or. It is more preferably a halogen atom.

The quinophthalone pigment (A2) can be used alone or in combination of two or more.

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

[Manufacturing method of quinophthalone pigment (A2) represented by the general 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 the general formula (1) include those shown below, but the present invention is not limited thereto.

(Other pigments (A3))
The coloring composition of the present invention can contain other pigments (A3) other than the phthalocyanine pigment (A1) and the quinophthalone pigment (A2) to the extent that the problem can be solved.

Other pigments (A3) are, for example, C.I. 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, 151,152,153,154,155,156,161,162,164,166,167,168,169,170,171,172,173,174,175,176,177,179,180,181, 182,185,187,188,193,194,198,199,213,214,218,219,220,221, C.I. I. Bigment 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. 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: 1,109,112,113,114,122,123,144,146,147,149,1511 166,168,169,170,172,173,174,175,176,177,178,179,181,184,185,187,188,190,193,194,200,202,206,207,208, 209,210,214,216,220,221,224,230,231,232,233,235,236,237,238,239,242,243,245,247,249,250,251,253,254 255,256,257,258,259,260,262,263,264,265,266,267,268,269,270,271,272,273,274,275,276,277,278,279,280, 281,282,283,284,285,286,287,291,295,296, C.I. I. Pigment Violet 1,1: 1,2,2: 2,3,3: 1,3: 3,5,5: 1,14,15,16,19,23,25,27,29,31,32, 37,39,42,44,47,49,50, C.I. I. Pigment Orange 36, 38, 43, 64, 71, 73 and the like.

(dye)
The colorant (A) can contain a dye.
The dye is, for example, C.I. I. Solvent Green 1,4,5,7,34,35, C.I. I. Acid Green 1,3,5,9,16,50,58,63,65,80,104,105,106,109, C.I. I. Direct Green 25,27,31,32,34,37,63,65,66,67,68,69,72,77,79,82, C.I. I. Modant Green 1,3,4,5,10,15,26,29,33,34,35,41,43,53, C.I. 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, 51,53,55,56,60,63,65,66,67,68,69,72,76,82,83,84,86,87,90,94,105,115,117,122,127, 131,132,136,141,142,143,144,145,146,149,153,159,166,168,169,172,174,175,178,180,183,187,188,189,190, 191,192,199, C.I. 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. 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. 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, 79,81,82,83,85,88,89,90,93,94,98,104,107,114,116,117,124,130,131,133,135,138,141,143,1455 146,147,157,160,162,163,167,172,174,175,176,177,179,181,182,183,184,185,186,187,188,190,191,192,194 195, C.I. 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 and 245, 246, 247, 248, 249, 250, 251 and the like.

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

(Pigment miniaturization)
In the present invention, the pigment is preferably used in a finely divided form. The miniaturization method is not particularly limited, and for example, wet grinding, dry grinding, and dissolution precipitation method can be used. Among these, the salt milling treatment by the kneader method, which is one of the wet grinding methods, is preferable. The average primary particle size determined by the TEM (transmission electron microscope) of the finely divided pigment is preferably 5 to 90 nm. From the viewpoint of dispersibility and contrast ratio, the average primary particle size is more preferably 10 to 70 nm.

Salt milling is a machine that heats a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent using a kneader such as a kneader, a 2-roll mill, a 3-roll mill, a ball mill, an attritor, and a sand mill. After kneading, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt acts as a crushing aid, and the pigment is crushed by utilizing the high hardness of the inorganic salt during salt milling. By optimizing the conditions for the salt milling treatment of the pigment, it is possible to obtain a pigment having a very fine primary particle size, a narrow distribution width, and a sharp particle size distribution.

Examples of the water-soluble inorganic salt include sodium chloride, potassium chloride, sodium sulfate and the like, and sodium chloride (salt) is preferable from the viewpoint of price. The amount of the water-soluble inorganic salt used is preferably 50 to 2,000 parts by mass, more preferably 300 to 1,000 parts by mass with respect to 100 parts by mass of the pigment, from the viewpoints of both treatment efficiency and production efficiency.

The water-soluble organic solvent has a function of wetting the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (mixes) in water and does not substantially dissolve the inorganic salt used. However, since the temperature rises during salt milling and the solvent easily evaporates, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint 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 and the like are 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 with respect to 100 parts by mass of the pigment.

For the salt milling treatment, the resin may be changed if necessary. The type of the resin is not particularly limited, and examples thereof include a natural resin, a modified natural resin, a synthetic resin, and a synthetic resin modified with a natural resin. Among these, it is preferable that it is solid at room temperature, is insoluble in water, and is partially soluble in the above organic solvent. The amount of the resin used is preferably 2 to 200 parts by mass with respect to 100 parts by mass 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, wherein the metal is 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), a colored composition with less foreign matter generation, excellent voltage retention, and less decrease in brightness can be obtained.

The quinophthalone compound is a compound having a structure represented by the following chemical formula (2). Specifically, C.I. I. Commercially available dyes such as Acid Yellow 3, 5 and C.I. I. Pigment Yellow 138, C.I. I. Solvent Yellow 33,114,157, C.I. I. Examples include commercially available pigments and dyes such as Disperse Yellow 54, 64, 67.

Chemical formula (2)

The quinophthalone compound having a sulfo group is a compound obtained by sulfonated a compound having a structure represented by the chemical formula (2) by a known method, and specific examples thereof include those shown below. It is not limited to these.

The metal salt (B) of the quinophthalone compound having a sulfo group can be obtained by counter-exchange of −SO ₃ H 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 suppressed more effectively. Further, when the metal is either zinc or aluminum, the voltage retention rate is excellent and the generation of foreign matter can be suppressed more effectively.

It is preferable to use two or more kinds of the metal salt (B) of the 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 preferably a copper salt and an aluminum salt of a quinophthalone compound having a sulfo group, or the copper salt and zinc salt.

The content of the metal salt (B) of the quinophthalone compound having a sulfo group is 1 to 40 with respect to 100 parts by mass of the phthalocyanine pigment (A1) from the viewpoint of suppressing the generation of foreign substances, the voltage retention rate, and the suppression of the decrease in brightness. By mass is preferable, and 5 to 30 parts by mass is more preferable.

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 20 to 80% by mass of 100% by mass of the metal salt (B) of the quinophthalone compound having a sulfo group. 60% by mass is more preferable.

[Dispersed resin (F)]
The coloring composition of the present invention may contain a dispersion resin (F), if necessary.
The dispersed resin (F) has an adsorbing group having a high affinity for the pigment. The adsorbing group is preferably one or more of a cationic group and an anionic group.

Examples of the resin having a cationic group include a primary amino group, a secondary amino group, a tertiary amino group, a quaternary ammonia base, and a group containing a nitrogen atom such as a nitrogen-containing heterocycle as the cationic group. Will be.

Examples of the resin having an anionic group include a carboxyl group, a phosphoric acid group, a sulfonic acid group and the like as anionic groups. Of these, a carboxyl group and a phosphoric acid group are preferable from the viewpoint of adsorptivity to pigments.

The resin type of the dispersed resin (F) is, for example, a urethane resin, a polycarboxylic acid ester such as polyacrylate, an unsaturated polyamide, a polycarboxylic acid, a polycarboxylic acid (partial) amine salt, a polycarboxylic acid ammonium salt, or a polycarboxylic acid. Alkylamine salts, polysiloxanes, long-chain polyaminoamidophosphates, hydroxyl group-containing polycarboxylic acid esters and modified products thereof, amides formed by the reaction of poly (lower alkyleneimine) with polyesters having free carboxyl groups. Water-soluble such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, etc. Examples thereof include sex resins, water-soluble polymer compounds, polyester-based materials, modified polyacrylate-based compounds, ethylene oxide / propylene oxide-added compounds, and phosphoric acid ester-based compounds.

Examples of the structure of the dispersed resin (F) include a random structure, a block structure, a graft structure, a comb-shaped structure, and a star-shaped structure. Among these, a block structure or a comb-shaped structure is preferable from the viewpoint of dispersion stability.

Commercially available products of the dispersed resin (F) include, for example, Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, manufactured by Big Chemie Japan. 166, 167, 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 2163 2164, or Anti-Terra-U203,204, or BYK-P104, P104S, 220S, or Lactimon, Lactimon-WS, or Bykuman, etc. , 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 56000, 76500 Etc., EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300 manufactured by BASF Japan Ltd. , 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc. In JP-A-2008-029901, JP-A-2009-155406, JP-A-2010-185934, JP-A-2011-157416, etc. The resin described is mentioned.

The dispersed resin (F) can be used alone or in combination of two or more.

The content of the dispersion resin (F) is preferably 3 to 200 parts by mass, more preferably 5 to 100 parts by mass with respect to 100 parts by mass of the colorant (A) from the viewpoint of dispersion stability.

[Dispersion aid (G)]
The coloring composition of the present invention may contain a dispersion aid (G), if necessary.

The dispersion aid (G) is not particularly limited, and examples thereof include compounds having an acidic group, a basic group, a neutral group, or the like in the organic dye residue. The dispersion aid (G) is specifically a compound having an acidic substituent such as a sulfo group, a carboxy group or a phosphate group, an amine salt thereof, a sulfonamide group or a tertiary amino group at the terminal. Examples thereof include a compound having a basic substituent and a compound having a neutral substituent such as a phenyl group and a phthalimidealkyl group.
Organic dyes include, for example, diketopyrrolopyrrole pigments, anthracinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiazine indigo pigments, triazine pigments, benzimidazolone pigments, benzoisoindole and the like. Examples thereof include pigments, isoindolin-based pigments, isoindolinone pigments, naphthol pigments, slene pigments, metal complex-based pigments, and azo-based pigments such as azo, disazo, and polyazo.

The dispersion aid (G)) can be used alone or in combination of two or more.

The content of the dispersion aid (G) is preferably 1 to 15 parts by mass, more preferably 2 to 10 parts by mass with respect to 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 alkaline developer, and a resin having a transmittance of 80% or more in the entire wavelength region of 400 to 700 nm when a film having a thickness of 2 μm is formed is preferable. 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 preferable. Further, the alkali-soluble resin (C) can contain a thermosetting group such as an epoxy group or an oxetanyl group.

(Non-photosensitive alkali-soluble resin)
The non-photosensitive alkali-soluble resin is, for example, an acrylic resin having an acidic group, an α-olefin / (anhydrous) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, and the like. Alternatively, isobutylene / (anhydrous) maleic acid copolymer and the like can be mentioned. Among these, an acrylic resin having an acidic group and a styrene / styrene sulfonic acid copolymer are preferable.

(Photosensitive alkali-soluble resin)
The photosensitive alkali-soluble resin has a photosensitive unsaturated group because it has a polymerizable unsaturated group. The photosensitive alkali-soluble resin may be alkali-soluble and may have photosensitivity, and a known resin can be used. Therefore, the resin synthesized by the following methods (i) and (ii) is preferable. When the alkali-soluble photosensitive resin is used, it is three-dimensionally crosslinked by light irradiation to increase the crosslink density, so that the chemical resistance of the coating film is improved.

[Method (i)]
In method (i), for example, first, an epoxy group-containing monomer and a polymer of other monomers are synthesized. Next, a method of adding a monocarboxyl group-containing monomer to the epoxy group of the polymer and reacting the generated hydroxyl group with a polybasic acid anhydride to obtain an alkali-soluble photosensitive resin can be mentioned. The monocarboxyl group-containing monomer is a monomer having one carboxyl group.

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

The monocarboxyl group-containing monomer is, for example, (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, cyano substituted. Examples thereof include monocarboxylic acids such as the body.

Examples of the polybasic acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, maleic anhydride and the like. The polybasic acid anhydride may have a carboxyl group that does not form an acid anhydride.

Other monomers include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and 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, methoxypolypropylene glycol (meth) acrylate, or ethoxypolyethylene glycol (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclo Penthenyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, EO-modified cresol acrylate, n-nonylphenoxypolyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl acrylate, phenol Ethylene oxide (EO) modified (meth) acrylate, EO of paracumylphenol or propylene oxide (PO) modified (meth) acrylate, EO-modified (meth) acrylate of nonylphenol, PO-modified (meth) acrylate of nonylphenol, etc. (meth) ) Acrylate,
Alternatively, (meth) such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, or acryloylmorpholin. Acrylamides styrene or styrenes such as α-methyl styrene, vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether, vinyl acetate, fatty acid vinyls such as vinyl propionate. And so on.

Also, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimideethane 1,6-bismaleimidehexane, 3-maleimidepropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimide. Kumarin, 4,4'-bismaleimidediphenylmethane, bis (3-ethyl-5-methyl-4-maleimidephenyl) methane, N, N'-1,3-phenylenedimaleimide, N, N'-1,4- Phenylened maleimide, N- (1-pyrenyl) maleimide, N- (2,4,6-trichlorophenyl) maleimide, N- (4-aminophenyl) maleimide, N- (4-nitrophenyl) maleimide, N-benzyl Maleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimidebenzoate, N-succinimidyl-3-maleimidepropionate, N-succinimidyl-4-maleimidebutyrate, N-succinimidyl-6-maleimide Examples thereof include N-substituted maleimides such as hexanoate, N- [4- (2-benzoimidazolyl) phenyl] maleimide, and 9-maleimide acrydin.

Further, 2- (meth) acryloyloxyethyl acid phosphate, a phosphoric acid ester group such as a compound obtained by reacting a hydroxyl group of a hydroxyl group-containing monomer described later with a phosphoric acid esterifying agent such as phosphorus pentoxide or polyphosphoric acid, for example. Examples include contained monomers

[Method (ii)]
The method (ii) synthesizes, for example, a polymer of a hydroxyl group-containing monomer, a carboxyl group-containing monomer, and other monomers. Next, a method of reacting the hydroxyl group of the polymer with the isocyanate group of the isocyanate group-containing monomer to synthesize an alkali-soluble photosensitive resin can be mentioned.

The hydroxyl group-containing monomer is, for example, 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, glycerol mono (meth). Examples thereof include hydroxyalkyl methacrylates such as acrylates and cyclohexanedimethanol mono (meth) acrylates. Further, a polyether mono (meth) acrylate obtained by superpolymerizing hydroxyalkyl (meth) acrylate with ethylene oxide, propylene oxide, and / or butylene oxide, poly γ-valerolactone, poly ε-caprolactone, and / or poly. Polyester mono (meth) acrylate to which 12-hydroxystearic acid or the like is added can also be mentioned. Among these, 2-hydroxyethyl methacrylate and glycerol mono (meth) acrylate are preferable, and glycerol mono (meth) acrylate is more preferable.

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

As the carboxyl group-containing monomer and other monomers, the monomers already described can be used.

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

The weight average molecular weight (Mw) of the alkali-soluble resin (C) is 2,000 to 40,000, preferably 3,000 to 3,000, and more preferably 4,000 to 20,000 from the viewpoint of developability. preferable. Further, the value of Mw / Mn is preferably 10 or less. Adhesion to the substrate and alkali development solubility are improved by an appropriate weight average molecular weight (Mw).

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. Adhesion to the substrate and alkali development solubility are improved by an appropriate acid value.

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

[Surfactant (D)]
(Surfactant (D1))
The coloring composition of the present invention contains a monomer (d1) having at least one of a fluorinated alkyl group and a poly (perfluoroalkylene ether) chain as a surfactant (D), and other ethylenically unsaturated groups. It contains a surfactant (D1) which is a copolymer with the monomer (d2).
By using the surfactant (D1) and the metal salt (B) of the quinophthalone compound having a sulfo group in combination, the generation of foreign substances can be greatly suppressed.

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

Examples of the method for producing the surfactant (D1) include a method of solution polymerization using a polymerization initiator. The solvent used for solution polymerization is preferably ketones, esters, amides, sulfoxides, ethers, and hydrocarbons. Specifically, 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, xylene and the like. These can be appropriately selected in consideration of boiling point, compatibility and polymerizable property. Examples of the polymerization initiator include peroxides such as benzoyl peroxide and azo compounds such as azobisisobutyronitrile. Further, if necessary, chain transfer agents such as lauryl mercaptan, 2-mercaptoethanol, thioglycerol, ethylthioglyco-lic acid, and octylthioglyco-lic acid can be used.

Examples of the monomer (d1) having a fluorinated alkyl group constituting the surfactant (D1) include a monomer represented by the following general formula (5).

General formula (5)

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

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

N in the above equations (Z-1) to (Z-4) is, for example, an integer of 1 to 6, preferably an integer of 4 to 6. In the above equation (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 equation (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, and p is an integer of 0 to 5. Moreover, the total product of m, p and 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 m, p and n. The sum of the products of and l is 2 to 23.

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

The monomer (d1) having a poly (perfluoroalkylene ether) chain constituting the surfactant (D1) has a structure in which divalent fluorocarbon groups having 1 to 3 carbon atoms and oxygen atoms are alternately linked. Examples thereof include monomers having. The divalent fluorocarbon group having 1 to 3 carbon atoms may be one kind or a mixture of a plurality of kinds, and specifically, the linking group represented by the following formula (Y) is used. Can be mentioned.

In the above formula (Y), A is the following formulas (Y-1) to (Y-5), and all A in the formula (Y) may have the same structure, or a plurality of A may have the same structure. The structure may be randomly or in blocks. Further, n is an integer of 1 or more representing a repeating unit.

Among these, from the viewpoint of suppressing the generation of foreign matter, the one in which the perfluoromethylene structure represented by the above formula (Y-1) and the perfluoroethylene structure represented by the above formula (Y-2) coexist is particularly the one. preferable. 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 a monomer capable of copolymerizing with a monomer (d1) having at least one of a fluorinated alkyl group and a poly (perfluoroalkylene ether) chain. It may be a quantity (for example, various monomers described in the photosensitive alkali-soluble resin) and is not limited. Of these, a polycyclic alicyclic structure-containing monomer is preferable from the viewpoint of suppressing the generation of foreign substances.

Examples of the polycyclic alicyclic structure-containing monomer include an adamantyl group-containing monomer and a dicyclopentanyl group-containing monomer. Among these, the adamantyl group-containing monomer is preferable in terms of suppressing the generation of foreign substances.

The monomer having an adamantyl group is a compound having an adamantane structure represented by the following general formula (6) and a (meth) acryloyl group. The (meth) acryloyl group may be attached to any carbon atom in the adamantane structure. Further, the hydrogen atom bonded to the carbon atom constituting the adamantane structure may be partially or wholly substituted with a hydroxyl group, an alkyl group or the like.

General formula (6)

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

Commercially available products of the surfactant (D1) are AGC Seimi Chemical's Surflon S-242, S-243, S-420, S-611, S-651, S-386, DIC's Megafuck 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- Examples thereof include K, DS-21, FC-4430 and FC-4432 manufactured by Sumitomo 3M, EF-PP31N09, EF-PP33G1, EF-PP32C1 manufactured by Mitsubishi Materials Electronics Chemicals, and Futergent 602A manufactured by Neos.

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

The content of the surfactant (D1) is preferably 0.01 to 2 parts by mass, more preferably 0.1 to 1 part by mass with respect to 100 parts by mass of the colorant (A) from the viewpoint of suppressing the generation of foreign substances. preferable.

(Other surfactant (D2))
The surfactant (D) can contain other surfactants (D2) other than the surfactant (D1). Examples of the other surfactant (D2) include a silicone-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant and the like.

Examples of the silicone-based surfactant include a linear polymer composed of a siloxane bond and a modified siloxane polymer having an organic group introduced into a side chain or a terminal. Commercially available products are BYK-300, 306, 310, 313,315N, 320,322,323,330,331,333,342,345,346,347,348,349,370,377,378,3455 manufactured by Big Chemie. , UV3510, 3570, FZ-7002, 2110, 2122, 2123, 2191, 5609, manufactured by Toray Industries, Inc., X-22-4952, X-22-4272, X-22-6266, KF manufactured by Shin-Etsu Chemical Co., Ltd. Examples thereof include -351A, KF-354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-4515, KF-6004, KP-341 and the like.

Nonionic surfactants include, for example, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyethylene myristel ether, and polyoxyethylene octyl. Dodecyl ether, polyoxyalkylene alkyl ether, polyoxyphenylenedistyrene phenyl ether, polyoxyethylene tribenzylphenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyalkylene alkenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Alkyl ether phosphate ester, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, sorbitan tristearate, sorbitan monoolate, sorbitan triolate, sorbitan sesquiolate, polyoxyethylene sorbitan mono Laurate, Polyoxyethylene sorbitan monopalmitate, Polyoxyethylene sorbitan monostearate, Polyoxyethylene sorbitan tristearate, Polyoxyethylene sorbitan monoolate, Polyoxyethylene sorbitan triisostearate, Polyoxytetraoleate Ethylene sorbit, glycerol monostearate, glycerol monooleate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol monostearate, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkylamine, alkyl Examples thereof include alkanolamide and alkylimidazolin. Commercially available products are Kao Emargen 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, LS-106, LS-110, LS-114, MS-110, A-60, A-90, B- 66, PP-290, Polymer 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, TW-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, Emmanon 1112, 3199V, 3299V, 3299RV, 4110, CH-25, CH-40, CH-60 (K), Polymer 102, 105, 105A, 302, 320, Aminone PK-02S, L-02, Homogenol L-95, ADEKA Adecapluronic® L-23, 31, 44, 61, 62,64,71,72,101,121, TR-701,702,704,913R, Kyoeisha Chemical Co., Ltd. (meth) acrylic acid-based (co) polymer Polyflow No. 75, No. 90, No. 95 and the like can be mentioned.

Examples of the cationic surfactant include alkylquaternary ammonium salts such as alkylamine salts, lauryltrimethylammonium chlorides, stearyltrimethylammonium chlorides, and cetyltrimethylammonium chlorides, and ethylene oxide adducts thereof. Examples of commercially available products include Kao Corporation's acetamine 24, coatamine 24P, 60W, 86P conch piercing and the like.

Anionic surfactants include, for example, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalene sulfonate, sodium alkyldiphenyl ether disulfonate, monoethanol lauryl sulfate. Examples thereof include amine, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate and the like. Examples of commercially available products include Husqent 100, 150 manufactured by Neos, Adeka Hope YES-25 manufactured by ADEKA, Adecacol TS-230E, PS-440E, EC-8600 and the like.

Examples of the amphoteric tenside include alkyl betaines such as lauric acid amidopropyl betaine, lauryl betaine, cocamidopropyl betaine, stearyl betaine and alkyldimethylaminoacetic acid betaine, and alkylamine oxides such as lauryldimethylamine oxide. Examples of commercially available products include Anhitor 20AB, 20BS, 24B, 55AB, 86B, 20Y-B, 20N manufactured by Kao Corporation.

[Triarylsulfonium compound (E)]
The coloring composition of the present invention preferably contains the triarylsulfonium compound (E). By using the metal salt (B) of the quinophthalone compound having a sulfo group and the triarylsulfonium compound (E) in combination, it is possible to form a film having a better voltage retention rate and more suppressing the decrease in brightness.

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

General formula (7)

In the general formula (7), R ₁ to R ₃ independently have a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an alkyl group which may have a substituent, and an alkoxyl which may have a substituent. The aryl group which may have a group and a substituent is shown. X ^- represents a monovalent counter anion.

R ₁ to R ₃ and X ^- in the general formula (7) will be described.

In the general formula (7), R ₁ to R ₃ independently have a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an alkyl group which may have a substituent, and an alkoxyl which may have a substituent. The aryl group which may have a group and a substituent is shown.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine.

The alkyl group which may have a substituent is, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a neopentyl group, an n-hexyl group, an n-octyl group, and the like. Linear alkyl groups such as stearyl group and 2-ethylhexyl group, or branched alkyl groups, cyclic alkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group and cyclohexyl group, as well as trichloromethyl group and trifluoromethyl group. , 2,2,2-Trifluoroethyl group, 2,2-dibromoethyl group, 2,2,3,3-tetrafluoropropyl group, 2-ethoxyethyl group, 2-butoxyethyl group, 2-nitropropyl group , Benzyl group, 4-methylbenzyl group, 4-tert-butylbenzyl group, 4-methoxybenzyl group, 4-nitrobenzyl group, 2,4-dichlorobenzyl group and other alkyl groups having substituents.

The alkoxyl group which may have a substituent is a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutyloxy group, a tert-butyloxy group, a neopentyloxy group, a 2,3-dimethyl-. A linear alkoxyl group such as 3-pentoxy, n-hexyloxy group, n-octyloxy group, stearyloxy group, 2-ethylhexyloxy group, or a branched alkoxyl group, and cyclopropyloxy group, cyclobutyloxy group, cyclopentyl. In addition to cyclic alkoxyl groups such as oxy group and cyclohexyloxy group, trichloromethoxy group, trifluoromethoxy group, 2,2,2-trifluoroethoxy group, 2,2,3,3-tetrafluoropropyloxy group, 2, Examples thereof include an alkoxyl group having a substituent such as a 2-ditrifluoromethylpropoxy group, a 2-ethoxyethoxy group, a 2-butoxyethoxy group, a 2-nitropropoxy group and a benzyloxy group.

The aryl group which may have a substituent includes an aryl group such as a phenyl group, a naphthyl group and an anthranyl group, as well as a p-methylphenyl group, a p-bromophenyl group, a p-nitrophenyl group and a p-methoxyphenyl group. , 2,4-Dichlorophenyl group, pentafluorophenyl group, 2-aminophenyl group, 2-methyl-4-chlorophenyl group, 4-hydroxy-1-naphthyl group, 6-methyl-2-naphthyl group, 4,5 Examples thereof include an aryl group having a substituent such as a 8-trichloro-2-naphthyl group, an anthraquinonyl group and a 2-aminoanthraquinonyl group.

Among these, from the viewpoint of suppressing the 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- ^, compounds represented by the following general formulas (8) to (13), and the like.

General formula (8 ⁾ MY _a-
In the general 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 preferable.

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 hydrogen atoms are substituted with fluorine atoms. The alkyl group may be linear, branched or cyclic. b represents an integer of 1 to 5.

The compounds represented by the general formula (9) are, for example, (CF ₃ CF ₂ ) ₂ PF ^- ₄ , (CF ₃ CF ₂ ) ₃ PF _3- ^, (CF ₃ CF ₂ CF ₂ ) ₂ PF _4- ^, (((CF 3 CF 2)) CF ₃ ) ₂ CF) ₃ PF _3- ^, (CF ₃ CF ₂ CF ₂ ) ₂ PF ₄ ^-and the like.

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

The compounds represented by the general formula (10) are, for example, (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-, (C ₆ H ₃ F ₂ ) ₄ Ga ^{- and} the like.

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 perfluolalkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and represents an alkyl group and a perfluolol group. The alkyl group may be linear, branched or cyclic, and the aryl group may be unsubstituted or having a substituent.

The compound represented by the general formula (11) is, for example, trifluoromethanesulfonic acid anion, pentafluoroethanesulfonic acid anion, heptafluoropropanesulfonic acid anion, nanofluorbutane sulfonic acid anion, pentafluorophenylsulfonic acid anion, p-toluene. Examples thereof include sulfonic acid anion, benzene sulfonic acid anion, camphor sulfonic acid anion, butane sulfonic acid anion.

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, and an alkyl group and a perfluoroalkyl group. May be linear, branched or cyclic, and the aryl group may be unsubstituted or having a substituent.

The compounds represented by the general formula (12) are, for example, (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 ^- etc.

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, and an alkyl group and a perfluoroalkyl group. May be linear, branched or cyclic, and the aryl group may have a substituent.

The compounds represented by the general formula (13) are, for example, (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 ^- etc.

In addition to the above anions, ^{perhalochloride} ion (Cl0 _4- , BrO _4- ^, etc.), halogenated sulfonic acid ion (FSO _3- ^, ClSO _3- ^, etc.), sulfate ion (CH ₃ SO _4- ^, CF ₃ SO, etc.) _4- ^, HSO _4- ^, etc.), Carbonate ion (HCO _3- ^, CH ₃ CO _3- ^, etc.), Aluminate ion (AlCl _4- ^, AlF _4- ^, etc.), Carboxylic acid ion (CHCOO- ^, CF ₃ COO- ^, etc.), C ₆ H ₅ COO- ^, CH ₃ C ₆ H ₄ COO- ^, C ₆ F ₅ COO- ^, etc.), Arylborate ion (B (C ₆ H ₅ ) _4- ^, etc.), JP2013-092657, p. Examples thereof include the anions described in Japanese Patent Application Laid-Open No. 2013-080245, Japanese Patent Application Laid-Open No. 2013-080240, Japanese Patent Application Laid-Open No. 2013-047211, Japanese Patent Application Laid-Open No. 2013-033161 and the like.

Among these, Cl ⁻ , Br ⁻ , PF ₆ ⁻ , BF ₆ ⁻ , trifluoromethanesulfonate anion, and nonafluorobutane sulfonate anion are preferable as X ⁻ from the viewpoint of suppressing the decrease in brightness.

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

Commercially available products of the triarylsulfonium compound (E) include, for example, WPAG-336, 367, 370, 469, 638 (all manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.), SP-056,066 (manufactured by ADEKA), TS- 91 (manufactured by Sanwa Chemical Industries, Ltd.), T1608, 1609 (all manufactured by Tokyo Chemical Industry Co., Ltd.) and the like can be mentioned.

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

The content of the triarylsulfonium compound (E) is preferably 0.1 to 15 parts by mass and 1 to 12 parts by mass with respect to 100 parts by mass of the phthalocyanine pigment (A1) from the viewpoint of voltage retention and suppression of decrease in brightness. The portion is more preferable, and 2 to 10% by mass is particularly preferable.

[Polymerizable compound (H)]
The coloring composition of the present invention can contain a polymerizable compound (H). The polymerizable compound (H) is a monomer and an oligomer containing a polymerizable unsaturated group. Examples of the polymerizable unsaturated group include a vinyl group, a (meth) allyl group, a (meth) acryloyl group, a (meth) acryloyloxy group and the like. Examples of the polymerizable compound (H) include an acid group-containing monomer (H1), a urethane bond-containing monomer, 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, and a phosphoric acid group. Development residue can be suppressed when pattern formation is performed by a photolithography method using an acid group-containing monomer (H1).

The acid group-containing monomer (H1) is, for example, an esterified product of free hydroxyl group-containing poly (meth) acrylates of polyvalent alcohol and (meth) acrylic acid; and dicarboxylic acids; polyvalent carboxylic acid and monohydroxy. Examples thereof include esterified products with alkyl (meth) acrylates. Specific examples include monohydroxyoligoacrylates such as trimethylolpropanediacrylate, trimethylolpropanedimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate, or monohydroxyoligomethacrylates. , Free carboxyl group-containing monoesteride with dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, phthalic acid; propane-1,2,3-tricarboxylic acid (tricarboxylic acid), butane-1,2,4- Tricarboxylic acids such as tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid, 2-hydroxyethyl acrylate, 2-hydroxy Examples thereof include monohydroxymonoacrylates such as ethyl methacrylate, 2-hydroxypropyl acrylate and 2-hydroxypropyl methacrylate, and oligoesterides containing a free carboxyl group with monohydroxymonomethacrylates.

Commercially available acid group-containing monomers (H1) are Viscoat # 2500P manufactured by Osaka Organic Co., Ltd., Aronix M-5300, M-5400, M-5700, M-510, M-520, M- of Toagosei Co., Ltd. 521 and the like can be mentioned.

(Urethane bond-containing monomer (H2))
The urethane bond-containing monomer (H2) is, for example, a polyfunctional urethane acrylate obtained by reacting a (meth) acrylate having a hydroxyl group with a polyfunctional isocyanate, or reacting an alcohol with a polyfunctional isocyanate and further having a hydroxyl group (meth). ) Polyfunctional urethane acrylate obtained by reacting acrylate and the like can be mentioned.

The (meth) acrylate having a hydroxyl group includes 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, and ditrimethylol propanetri (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 , Gloxydimethacrylate, 2-hydroxy-3-acryloylpropylmethacrylate, a reaction product of an epoxy group-containing compound and a carboxy (meth) acrylate, a hydroxyl group-containing polyol polyacrylate and the like.

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

Commercially available products of the urethane bond-containing monomer (H2) are 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, 1100H manufactured by Shin-Nakamura Chemical Industry Co., Ltd., UV-4108F, UV-4117F manufactured by Osaka Organic Chemical Industry Co., Ltd., and the like.

(Other monomers)
Other monomers include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, β-carboxyethyl (meth). ) Acrylate, Polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, Triethylene glycol di (meth) acrylate, Polypropylene glycol di (meth) acrylate, Trimethylol propanthry (meth) acrylate, Phenoxy Tetraethylene 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, isocianul Acid EO modified tri (meth) acrylate, ditrimethylol propanetetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglycidyl ether di (meth) acrylate, bisphenol A Diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodecanyl (meth) acrylate, methylol Various acrylic acid esters such as (meth) acrylic acid ester, epoxy (meth) acrylate, and urethane acrylate of melamine and methacrylic acid ester, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, penta. Examples thereof include erythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, acrylonitrile and the like.

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

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

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

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

The photopolymerization initiator (I) is, for example, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2. -Methylpropane-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2- (dimethylamino) -1-[ 4- (4-Molholino) phenyl] -2- (phenylmethyl) -1-butanone, or 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) ) Phenyl] -1-butanone and other acetophenone compounds;
Benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyl dimethyl ketal;
Benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylicized benzophenone, 4-benzoyl-4'-methyldiphenylsulfide, or 3,3', 4, Benzophenone compounds such as 4'-tetra (t-butylperoxycarbonyl) benzophenone;
Thioxanthone compounds such as thioxanthone, 2-chlorthioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethylthioxanthone;
2,4,6-Trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s -Triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) Methyl) -6-styryl-s-triazine, 2- (naphtho-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy-naphtho-1-yl) -4 , 6-Bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4-trichloromethyl- (4'-methoxystyryl) -6-triazine. System compounds;
1,2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyloxime)], or ester, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole 3-Il]-, 1- (O-acetyloxime) and other oxime ester compounds;
Phosphine compounds such as bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide or diphenyl-2,4,6-trimethylbenzoylphosphine oxide;
Examples thereof include quinone compounds such as 9,10-phenanslenquinone, camphor-quinone, and ethylanthraquinone; borate compounds; carbazole compounds; imidazole compounds; and titanosen compounds.

Commercially available products of the photopolymerization initiator (I) include "Omnirad 907" (2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one) as an acetophenone-based compound. "Omnirad 369E" (2- (dimethylamino) -1- [4- (4-morpholino) phenyl] -2- (phenylmethyl) -1-butanone), "Omnirad 379EG" (2- (dimethylamino) -2 -[(4-Methylphenyl) Methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone) (both manufactured by IGM Resins), as a phosphine-based compound, "Omnirad 819" (bis (2) , 4,6-trimethylbenzoyl) -phenylphosphinoxide), "Omnirad TPO" (diphenyl-2,4,6-trimethylbenzoylphosphinoxide) (both manufactured by IGM Resins), 1,2- as an oxime compound. Octanedione, 1- [4- (Phenylthio) Phenyl-, 2- (O-benzoyloxime)] (IRGACURE OXE-01), Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H- Carbazole 3-yl]-, 1- (O-acetyloxime) (IRGACURE OXE 02), IRGACURE OXE 04 (all manufactured by BASF Japan), N-1919, NCI-730, NCI-831, NCI-930 (all) Also manufactured by ADEKA), TRONLY TR-PBG-304, TRONLY TR-PBG-305, TRONLY TR-PBG-309, TRONLY TR-PBG-3054 (all manufactured by Joshu Strong New Materials Co., Ltd.) and the like. Further, the oxime ester-based photopolymerization described in JP-A-2007-210991, JP-A-2009-179619, JP-A-2010-037223, JP-A-2010-215575, JP-A-2011-02998, etc. Initiators can also be mentioned.

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

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

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

The sensitizer (J) is, for example, a chalcone derivative, unsaturated ketones typified by dibenzalacetone, 1,2-diketone derivative typified by benzyl, camphorquinone, etc., benzoin derivative, fluorene derivative, etc. Polymethine dyes such as naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, acridin derivatives, azine derivatives, thiazine derivatives, oxadins. Derivatives, indolin derivatives, azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triallylmethane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquino Xalilloporphyrazine derivative, naphthalocyanine derivative, subphthalocyanine derivative, pyrylium derivative, thiopyrilium derivative, tetraphyllin derivative, anurene derivative, spiropyran derivative, spiroxazine derivative, thiospiropyrane derivative, metal allene complex, organic ruthenium complex, or Mihira -Ketone derivatives, α-acyloxyesters, acyloxides, methylphenylglycilate, benzyls, 9,10-phenanthrenquinones, kanfa-quinones, ethyl anthracinones, 4,4'-diethylisophthalofenone, Examples thereof include 3,3'or 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, and 4,4'-bis (diethylamino) benzophenone.

Among these, a thioxanthone derivative, a Mihira-ketone derivative, and a carbazole derivative are preferable. Specific compounds include 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4'-bis. (Dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4,4'-bis (ethylmethylamino) benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, 3,6-Dibenzoyl-N-ethylcarbazole and the like are preferable.

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

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

[Thermosetting compound (K)]
The coloring composition of the present invention can contain a thermosetting compound (K). As a result, the thermosetting compound (K) reacts in the heating step after the film is formed, and the crosslink density is increased, so that the heat resistance is improved.

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 an epoxy compound, an oxetane compound, a benzoguanamine compound, a rosin-modified maleic acid compound, a rosin-modified fumaric acid compound, a melamine compound, a urea compound, and a phenol compound. Among these, epoxy compounds and oxetane compounds are preferable.

(Epoxy compound (K1))
The epoxy compound (K1) includes, for example, bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene). , Alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthoaldehyde, glutaaldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.) Polymerization of substances, phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnolbornene, tetrahydroinden, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.) Phenols and polycondensates of phenols and ketones (acetone, methylethylketone, methylisobutylketone, acetophenone, benzophenone, etc.), phenols and aromatic dimethanols (benzenedimethanol, α, α, α' , Α'-benzenedimethanol, biphenyldimethanol, α, α, α', α'-biphenyldimethanol, etc.), phenols and aromatic dichloromethyls (α, α'-dichloroxylene, etc. Polycondensate with (bischloromethylbiphenyl, etc.), polycondensate of bisphenols and various aldehydes, glycidyl ether-based epoxy resin obtained by glycidylizing alcohols, alicyclic epoxy resin, heterocyclic epoxy resin, aliphatic epoxy Examples thereof include resins, glycidylamine-based epoxy resins, and glycidyl ester-based epoxy resins.

Commercially available products include, for example, Epicoat 807,815,825,827,828,190P, 191P (trade name; manufactured by Yuka Shell Epoxy), Epicoat 1004, 1256 (trade name; manufactured by Japan Epoxy Resin). , TECHMORE VG3101L (trade name; manufactured by Mitsui Chemicals, Inc.), EPPN-501H, 502H (trade name; manufactured by Nippon Kayaku Co., Ltd.), JER 1032H60 (trade name; manufactured by Japan Epoxy Resin), JER 157S65, 157S70 (trade name; Japan Epoxy Resin Co., Ltd.), EPPN-201 (trade name; manufactured by Nippon Kayaku Co., Ltd.), JER152, 154 (the above are product names; manufactured by Japan Epoxy Resin Co., Ltd.), EOCN-102S, 103S, 104S, 1020 (the above are products). Name; manufactured by Nippon Kayaku Co., Ltd.), Serokiside 2021, EHPE-3150 (trade name; manufactured by Daicel Chemical Industry Co., Ltd.), Denacol EX-21,212,252,313,314,321,411,421,512,5211 611, 612, 614, 614B, 622, 711,721 (the above are trade names; manufactured by Nagase ChemteX Corporation), TEPIC-L, H, S (manufactured by Nissan Chemical Industry Co., Ltd.) and the like can be mentioned.

The content of the epoxy compound (K1) is preferably 0.5 to 300 parts by mass, more preferably 1.0 to 50 parts by mass with respect to 100 parts by mass of the colorant (A) from the viewpoint of heat resistance of the coating film. ..

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

The monofunctional oxetane compound is, for example, (3-ethyloxetane-3-yl) methyl acrylate, (3-ethyloxetane-3-yl) methylmethacrylate, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-. (2-Ethylhexyloxymethyl) oxetane, 3-ethyl-3- (phenoxymethyl) oxetane, 3-ethyl-3- (2-methacryloxymethyl) oxetane, 3-ethyl-3-{[3- (triethoxy) Cyril) propoxy] methyl} oxetane and the like.
Examples of commercially available products include OXE-10,30 manufactured by Osaka Organic Chemical Industry Co., Ltd., OXT-101,212 manufactured by Toagosei Co., Ltd., and the like.

Bifunctional oxetane compounds include, for example, 4,4'-bis [(3-ethyl-3-oxetanyl) methoxymethyl] biphenyl), 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl] benzene, 1,4-Bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, di [1-ethyl (3-oxetanyl)] methyl ether, di [1-ethyl (3-oxetanyl)] methyl ether 3 -Ethyl-3-hydroxymethyloxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3- (2-phenoxymethyl) oxetane, 3,7-bis (3-oxetanyl)- 5-oxa-nonane, 1,2-bis [(3-ethyl-3-oxetanylmethoxy) methyl] ethane, 1,3-bis [(3-ethyl-3-oxetanylmethoxy) methyl] propane, ethylene glyco-subis (3-Ethyl-3-oxetanylmethyl) ether, dicyclopentenylbis (3-ethyl-3-oxetanylmethyl) ether, triethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tetraethyleneglycolbis (3) -Ethyl-3-oxetanylmethyl) ether, 1,4-bis (3-ethyl-3-oxetanylmethoxy) butane, 1,6-bis (3-ethyl-3-oxetanylmethoxy) hexane, polyethylene glycol bis (3-) Ethyl-3-oxetanylmethyl) ether, ethylene oxide (EO) modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, propylene oxide (PO) modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified hydrogenated bisphenol A-bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol F (3-ethyl-3-oxetanyl) Methyl) ether and the like can be mentioned.
Examples of commercially available products include OXBP and OXTP manufactured by Ube Industries, Ltd., and OXT-121,221 manufactured by Toagosei Co., Ltd.

Examples of the trifunctional or higher functional oxetane compound include pentaerythritol tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, and dipentaerythritol hexa (3-ethyl-3). -Oxetanylmethyl) ether, dipentaerythritol pentax (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexa (3-ethyl-) 3-Oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentaxe (3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropanetetrakis (3-ethyl-3-oxetanylmethyl) ether, resin containing oxetane group (3-ethyl-3-oxetanylmethyl) ether For example, a polymer obtained by radically polymerizing a (meth) acrylic monomer such as the oxetane-modified phenol novolac resin described in Patent No. 3783462 and the above-mentioned OXE-30 can be mentioned.

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

The 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 number of methylol groups and / or ether groups of 5.0 or more per melamine ring. If the number of methylol groups and ether groups is appropriate, it is easy to obtain heat resistance that is not excessive or insufficient.

Commercially available products include, for example, Nikarak MW-30HM, MW-390, MW-100LM, MX-750LM, MW-30M, MW-30, MW-22, MS-21, MS-11, MW-24X, MS- 001, MX-002, MX-730, MX-750, MX-708, MX-706, MX-042, MX-45, MX-500, MX-520, MX-43, MX-417, MX-410 ( Sanwa Chemical Co., Ltd.), Cymel 223, 235, 236,238, 285, 300, 301, 303, 350, 370 (manufactured by Nippon Cytec Industries Co., Ltd.) and the like.

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

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

In the coloring composition of the present invention, a curing agent (curing accelerator) can be used in combination to assist the curing of the thermosetting compound. Examples of the curing agent include amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like. The curing agent is, for example, an amine compound (for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl-N, N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (eg, triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (eg, dimethylamine, etc.), imidazole derivative bicyclic amidin compounds and salts thereof (eg, imidazole, 2). -Methyl imidazole, 2-ethyl imidazole, 2-ethyl-4-methyl imidazole, 2-phenyl imidazole, 4-phenyl imidazole, 1-cyanoethyl-2-phenyl imidazole, 1- (2-cyanoethyl) -2-ethyl-4 -Methylimidazole, etc.), phosphorus compounds (eg, triphenylphosphine, etc.), S-triazine derivatives (eg, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino- Examples thereof include S-triazine, 2-vinyl-4,6-diamino-S-triazine / isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine / isocyanuric acid adduct, etc.).

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

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

[Thiol 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), chiyl radicals that are less susceptible to polymerization inhibition by oxygen are generated during radical polymerization after light irradiation, and the photosensitivity of the coloring composition is improved. ..

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

Polyfunctional thiols include, for example, hexanedithiol, decandithiol, 1,4-butandio-rubistiopropionate, 1,4-butandio-rubistioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate. , Trimethylol Propanetristhioglycolate, Trimethylol Propantristhiopropionate, Trimethylol Propantris (3-mercaptobutyrate), Pentaerythritol Tetrakissthioglycolate, Pentaerythritol Tetrakissthiopropionate, Trimercapto Tris (2-hydroxyethyl) propionate isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2- (N, N-dibutylamino) -4,6-dimercapto- Examples thereof include s-triazine, and preferred examples include ethylene glycol bisthiopropionate, trimethylol propanthithiopropionate, pentaerythritol tetrakisthiopropionate and the like.

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

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

[Polymerization inhibitor (M)]
The coloring composition of the present invention can contain a polymerization inhibitor (M).
The polymerization inhibitor (M) is, for example, catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol. , 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-butylcatechol, alkylcatechol compounds such as 3,5-di-t-butylcatechol, 2-methylresorcinol, 4-methylresorcinol, 2-ethylresorsinol, 4-ethylresorsinol, 2 -Alkylresolsinol compounds such as propylresorsinol, 4-propylresorsinol, 2-n-butylresorsinol, 4-n-butylresorsinol, 2-t-butylresorsinol, 4-t-butylresorsinol, etc. Alkylhydroquinone compounds such as methylhydroquinone, ethylhydroquinone, propylhydroquinone, t-butylhydroquinone, 2,5-di-t-butylhydroquinone, tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenyl Examples thereof include phosphine compounds such as phosphine and tribenzylphosphine, phosphine oxide compounds such as trioctylphosphine oxide and triphenylphosphine oxide, phosphite compounds such as triphenylphosphite and trisnonylphenylphosphite, pyrogallol and fluoroglucin. ..

The content of the polymerization inhibitor (M) is preferably 0.01 to 0.4% by mass in 100% by mass of the non-volatile content of the coloring composition.

[Ultraviolet absorber (N)]
The coloring composition of the present invention can contain an ultraviolet absorber (N). The ultraviolet absorber (N) is an organic compound having an ultraviolet absorbing function, and is a benzotriazole-based organic compound, a triazine-based organic compound, a benzophenone-based organic compound, a salicylic acid ester-based organic compound, a cyanoacrylate-based organic compound, and salicylate. Examples include system 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-benzotriazole 2-yl)-(1,1- Dimethylethyl) -4-hydroxy, C7-9 side chain and linear alkyl ester mixture, 2- (2H-benzotriazole 2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2- (2H-benzotriazole 2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3,3-tetramethylbutyl) phenol, methyl 3- (3- (2H) -Reaction product of -benzotriazole 2-yl) -5-t-butyl-4-hydroxyphenyl) propionate / polyethylene glycol 300, 2- (2H-benzotriazole 2-yl) -4- (1,1,3) 3-Tetramethylbutyl) Phenol, 2,2'-Methylenebis [6- (2H-benzotriazole2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol], 2- (2H-) Benzotriazole 2-yl) -p-cresol, 2- (5-chloro-2H-benzotriazole 2-yl) -6-t-butyl-4-methylphenol, 2- (3,5-di-t-amyl) -2-Hydroxyphenyl) benzotriazole, 2- [2-hydroxy-5- [2- (methacryloyloxy) ethyl] phenyl] -2H-benzotriazole, octyl-3- [3-tert-butyl-4-hydroxy- 5- (5-Chloro-2H-benzotriazole2-yl) phenyl] propionate, 2-ethylhexyl-3- [3-tert-butyl-4-hydroxy-5- (5-chloro-2H-benzotriazole2-yl) ) Phenol] propionate.

Commercially available products are BASF Japan's TINUVIN P, PS, 234, 326, 329, 384-2, 900, 928, 99-2, 1130, ADEKA's ADEKA STAB LA-29, LA-31RG, LA-32, LA. -36, KEMISORB71, 73, 74, 79, 279 manufactured by Chemipro Kasei Co., Ltd., RUVA-93 manufactured by Otsuka Chemical Co., Ltd., and the like.

The triazine compounds include, for example, 2,4-bis (2,4-dimethylphenyl) -6- (2-hydroxy-4-n-octyloxyphenyl) -1,3,5-triazine, 2- [4. 6-bis (2,4-dimethylphenyl) -1,3,5-triazine-2-yl] -5- [3- (dodecyloxy) -2-hydroxypropoxy] phenol, 2- (2,4-dihydroxy) Phenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine and (2-ethylhexyl) -glycidate ester reaction product, 2,4-bis "2-hydroxy-4 -Butoxyphenyl "-6- (2,4-dibutoxyphenyl) -1,3,5-triazine, 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5-( Hexyloxy) phenol, 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5- [2- (2-ethylhexanoyloxy) ethoxy] phenol, 2,4,6- Examples thereof include tris (2-hydroxy-4-hexyloxy-3-methylphenyl) -1,3,5-triazine.

Examples of commercially available products include KEMIPROB 102 manufactured by Chemipro Kasei Co., Ltd., TINUVIN 400, 405, 460, 477, 479, 1577ED manufactured by BASF Japan, ADEKA Adecaster LA-46, LA-F70 manufactured by ADEKA, and CYASORB UV-1164 manufactured by Sun Chemical Co., Ltd. Be done.

Examples of the benzophenone compound include 2,4-di-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone 5-sulfonic acid-3 water temperature, 2 -Hydroxy-4-n-octoxybenzophenone, 2,2'-di-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4-dodecyloxy- 2-Hydroxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2'dihydroxy-4,4'-dimethoxybenzophenone, 2,2', 4,4'-tetrahydroxybenzopheno , 2-Hydroxy-4-methoxy-2'-carboxybenzophenone and the like.

Examples of commercially available products include KEMIPROB 10, 11, 11S, 12, 111 manufactured by Chemipro Kasei Co., Ltd., SEESORB 101, 107 manufactured by Sipro Kasei Co., Ltd., ADEKA STAB 1413 manufactured by ADEKA Co., Ltd., UV-12 manufactured by Sun Chemical Co., Ltd. and the like.

Examples of the salicylic acid ester compound include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butyl phenyl salicylate.

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

[Antioxidant (O)]
The coloring composition of the present invention may contain an antioxidant (O). As the antioxidant (O), the photopolymerization initiator and the thermosetting compound contained in the coloring composition prevent yellowing due to oxidation by the thermosetting and the thermal process at the time of ITO annealing, and the transmittance of the film is lowered. Can be suppressed. In particular, when the pigment concentration of the photosensitive composition is high, the content of the photopolymerizable compound decreases relatively, so if the amount of the photopolymerization initiator is increased or the thermosetting compound is blended, the film will turn yellow. easy. Therefore, by including an antioxidant, it is possible to prevent yellowing due to oxidation during the heating step and suppress a decrease in the transmittance of the coating film.

Examples of the antioxidant (O) include hydride-based phenol-based, hydride-based amine-based, phosphorus-based, sulfur-based, and hydroxylamine-based compounds. In the present specification, the antioxidant is preferably a compound containing no halogen atom.

Among these, from the viewpoint of achieving both the transmittance and the sensitivity of the coating film, a hydride-based phenol-based antioxidant, a hydride-based amine-based antioxidant, a phosphorus-based antioxidant, and a sulfur-based antioxidant are preferable.

Hindered phenolic antioxidants include, for example, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 ( 1H, 3H, 5H) -trion, 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) -propionate, N, N-hexamethylene Bis (3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), i-octyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 4,6- Bis (dodecylthiomethyl) -o-cresol, 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 And so on.

Commercially available products are ADEKA's ADEKA STUB AO-20, AO-30, AO-40, AO-50, AO-60, AO-80, AO-330, Chemipro's KEMINOX 101, 179, 76, 9425, BASF Japan. Examples thereof include IRGANOX 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 5057, 565, and Sianox CY-1790 and CY-2777 manufactured by Sun Chemical.

Examples of the hindered amine antioxidants include tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate and tetrakis (2,2,6). , 6-Tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (2,2,6) , 6-Tetramethyl-4-piperidyl) sebacate, bis (1-undecanoxy-2,2,6,6-tetramethylpiperidine-4-yl) carbonate, 1,2,2,6,6-pentamethyl-4-yl Weights of piperidyl methacrylate, 2,2,6,6-tetramethyl-4-piperidylmethacrylate, dimethyl succinate and 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine Condensate, poly [[6-[(1,1,3,3-tetramethylbutyl) amino] -s-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4) -Piperidyl) imino] -hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl) imino]], 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinethanol Ester of 3,5,5-trimethylhexanoic acid, N, N'-4,7-tetrakis [4,6-bis {N-butyl-N- (1,2,2,6,6-pentamethyl-4-) Piperidine) amino} -1,3,5-triazine-2-yl] -4,7-diazadecan-1,10-diamine, bisdecanediate (2,2,6,6-tetramethyl-1- (octyl) Oxy) -4-piperidinyl) ester, reaction product of 1,1-dimethylethylhydroperoxide and octane, bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (3,5-bis (3,5-bis) 1,1 dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate methyl 1,2,2,6,6-pentamethyl-4-piperidylsevakate, poly [[6-morpholino-s-triazine-2 , 4-Diyl]-[(2,2,6,6-tetramethyl-4-piperidyl) imino] -hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl) imino]], 2,2,6,6-tetramethyl-4-piperidyl-C12-21 and C18 unsaturated fatty acid ester, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -1, 6 -Hexamethylenediamine, 2-methyl-2- (2,2,6,6-tetramethyl-4-piperidyl) amino-N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide, etc. Can be mentioned.

Commercially available products are ADEKA's ADEKA STAB LA-52, LA-57, LA-63P, LA-68, LA-72, LA-77Y, LA-77G, LA-81, LA-82, LA-87, LA- 402F, LA-502XP, KAMISTAB29, 62, 77, 94 manufactured by Chemipro Kasei Co., Ltd., Tinuvin249 manufactured by BASF Japan, TINUVIN111FDL, 123, 144, 292, 5100, Siasorb UV-3346, UV-3349 manufactured by Sun Chemical Co., Ltd., UV -3853 and the like can be mentioned.

Phylline antioxidants include, for example, 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' -Isopropyridene diphenyl diphosphite, diphenylmono (2-ethylhexyl) phosphite, diphenylisodecylphosphite, tris (isodecyl) phosphite, triphenylphosphite, tetrakis (2,4-di-t-butylphenyl)- 4,4-Biphenyldiphoshonito, Tris (tridecyl) phosphite, phenylisooctylphosphite, phenylisodecylphosphite, phenyldi (tridecyl) phosphite, diphenylisooctylphosphite, diphenyltridecylphosphite, 4,4 '-Isopropyridene diphenol alkyl phosphite, trisnonylphenyl phosphite, trisdinonylphenyl phosphite, tris (biphenyl) phosphite, di (2,4-di-t-butylphenyl) pentaerythritol diphosphite, di (Nonylphenyl) Pentaerythritol diphosphite, Phenylbisphenol A Pentaerythritol diphosphite, tetratridecyl 4,4'-butylidenebis (3-methyl-6-t-butylphenol) diphosphite, hexatridecyl 1,1,3- Tris (2-methyl-4-hydroxy-5-t-butylphenyl) butanetriphosphite, 3,5-di-t-butyl-4-hydroxybenzylphosphite diethyl ester, sodiumbis (4-t-butylphenyl) phos Fight, Sodium-2,2-Methylene-bis (4,6-di-t-butylphenyl) -phosphite, 1,3-bis (diphenoxyphosphonyloxy) -benzene, ethylbis phosphite (2,4) -Dit-butyl-6-methylphenyl) and the like.

Examples of commercially available products include ADEKA's ADEKA STAB PEP-36, PEP-8, HP-10, 2112, 1178, 1500, C, 135A, 3010, TPP, BASF Japan's IRGAFOS168, and Clariant Chemicals' HostanoxP-EPQ. Be done.

Sulfur-based antioxidants include, for example, 2,2-bis {[3- (dodecylthio) -1-oxopropoxy] methyl} propane-1,3-diylbis [3- (dodecylthio) propionate], 3,3'-. Ditridecyl thiobispropionate, 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis [(octylthio) methyl] -o- Cresol, 2,4-bis [(laurylthio) methyl] -o-cresol and the like can be mentioned.

Examples of commercially available products include ADEKA Stab AO-412S and AO-503 manufactured by ADEKA, and KEMINOXPLS manufactured by Chemipro Kasei Co., Ltd.

The antioxidant (O) can be used alone or in combination of two or more.

The content of the antioxidant (O) is preferably 0.5 to 5.0% by mass based on 100% by mass of the non-volatile 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 can contain a storage stabilizer (P). This stabilizes the viscosity of the coloring composition over time. The storage stabilizer (P) includes, for example, quaternary ammonium chloride such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and phosphorous acid and their methyl ethers, t-butylpyrocatechol, tetraethylphosphin and tetraphenyl. Examples thereof include organic phosphine and phosphite.

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

[Adhesion improver (Q)]
The coloring composition of the present invention can contain an adhesion improver (Q). This improves the adhesion between the coating and the base material. In addition, the photolithography method facilitates the formation of narrow patterns.

Examples of the adhesion improver (Q) include a silane coupling agent and the like. Examples of the silane coupling agent include vinylsilanes such as vinyltrimethoxysilane and vinyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-methacryloxypropylmethyldiethoxysilane. (Meta) acrylic silanes such as 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane , 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane and other epoxysilanes, N-2- (aminoethyl) -3-aminopropyl Methyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-) Aminosilanes such as dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, 3-mercaptopropyl Melcaptos such as methyldimethoxysilane and 3-mercaptopropyltrimethoxysilane, styryls such as p-styryltrimethoxysilane, ureids such as 3-ureidopropyltriethoxysilane, bis (triethoxysilylpropyl) tetrasulfide and the like. Examples thereof include silane coupling agents such as sulfides and isocyanates such as 3-isocyanuspropyltriethoxysilane.

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

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

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

The organic solvent (R) is, for example, 1,2,3-trichloropropane, 1-methoxy-2-propanol, ethyl lactate, 1,3-butandiole, 1,3-butylene glycol, 1,3-butylene glycol. Diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexene-1-one, 3,3,5-trimethylcyclohexyl Sanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butandiol, 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, Isophoron, Ethylene Glycol Diethyl Ether, Ethylene Glycol Dibutyl Ether, Ethylene Glycol Monoisopropyl Ether, Ethylene Glycol Monoethyl Ether, Ethylene Glycol Monoethyl Ether Acetate, Ethylene Glycol Monoter Shari-Butyl Ether, Ethylene Glycol Monobutyl Ether, Ethylene Glycol Mono Butyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl 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 ace Tate, Dipropylene Glycol Monoethyl Ether, Dipropylene Glycol Monobutyl Ether, Dipropylene Glycol Monopropyl Ether, Dipropylene Glycol Monomethyl Ether, 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 Examples thereof include alcohol, methylisobutylketone, methylcyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic acid ester and the like. Among these, from the viewpoint of dispersibility of pigments and solubility of alkali-soluble resins, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate and the like Alcohols such as glycol acetates, benzyl alcohols and diacetone alcohols and ketones such as cyclohexanone are preferable.

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

<Manufacturing method of coloring composition>
The coloring composition of the present invention is, for example, a colorant (A), a metal salt (B) of a quinophthalone compound having a sulfo group, an alkali-soluble resin (C), a triarylsulfonium compound (E), and if necessary. A dispersion is produced by adding a dispersion resin (F), an organic solvent (P), and the like to carry out a dispersion treatment. The dispersion may be subjected to the dispersion treatment by adding two or more kinds of colorants at the same time, or may be mixed separately subjected to the dispersion treatment.
Then, it can be produced by mixing the surfactant (D), the polymerizable compound (H), and the photopolymerization initiator (I), if necessary, with the dispersion. The timing of blending each material is arbitrary. Further, the dispersion step can be performed a plurality of times.

Examples of the disperser for performing the dispersion treatment include a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annual bead mill, and 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. When the particle size is appropriate, it is easy to obtain a colored composition having high dispersion stability.

As a method for measuring the average dispersed particle size (secondary particle size), for example, Nikkiso's Microtrack UPA-EX150, which employs a dynamic light scattering method (FFT power-spector method), is used to absorb particle permeability. The particle shape is non-spherical, and the D50 particle diameter is the average diameter. As the diluting solvent for measurement, the organic solvent used for dispersion is used, and it is preferable to measure the sample treated by ultrasonic waves immediately after sample preparation because it is easy to obtain results with little variation.

The coloring composition was mixed with coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably 0.5 μm or more, by means such as centrifugation, filtration with a sintering filter or a membrane filter. It is preferable to remove dust. The coloring composition of the present invention preferably contains substantially no 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 includes a substrate and a filter segment formed by using the coloring composition of the present invention.

[Manufacturing method of color filter]
The color filter preferably forms a black matrix on the substrate and then forms a filter segment.
Examples of the black matrix include a multilayer film of chromium and chromium / chromium oxide, an inorganic film such as titanium nitride, and a resin film in which a light-shielding agent is dispersed.

The formation of the filter segment can be produced by, for example, a printing method, an electrodeposition method, a transfer method, an inkjet method, a photolithography method, or the like. Among these, the photolithography method is preferable in terms of being able to produce a highly accurate color filter.
In the photolithography method, for example, a photosensitive coloring composition containing a colorant having a certain color tone is applied onto a transparent substrate so that the dry film thickness is about 0.2 to 5 μm to form a film. The obtained film (hereinafter referred to as the first film) is exposed (light irradiation) through a mask having a predetermined pattern. Then, the developer is immersed in a solvent or an alkaline developer, or the developer is sprayed with a spray or the like for development, and the uncured portion is removed to obtain a desired pattern. By performing this step in the same manner using a photosensitive coloring composition having a colorant having another color tone, a color filter having filter segments of each color can be produced. Further, a second film (oxygen blocking film) can be further formed on the first film before exposure by using polyvinyl alcohol or a water-soluble acrylic resin. As a result, the first film does not come into contact with oxygen, so that the exposure sensitivity is further improved. In addition, the color filter can be heated to cure the uncured photopolymerizable compound in the filter segment.

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

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

<Liquid crystal display device>
The liquid crystal display device of the present invention includes the color filter of the present invention.
In the liquid crystal display device, the color filter is attached to the facing substrate by using a sealing agent for the color filter after the filter segment is formed, and the liquid crystal is injected from the injection port provided in the seal portion, and then the injection port is sealed. Further, a liquid crystal display device can be manufactured by laminating a polarizing film or a retardation film on the outside of a substrate as needed.

The liquid crystal display device of the present invention includes the color filter of the present invention and a light source. Examples of the light source include a cold cathode fluorescent lamp (CCFL) and a white LED, but in the present invention, it is preferable to use a white LED because the red reproduction region is widened. FIG. 1 is a schematic cross-sectional view of a liquid crystal display device 10 provided with the color filter of the present invention. The device 10 shown in FIG. 1 includes a pair of transparent substrates 11 and 21 arranged so as to be separated from each other, and a liquid crystal LC is enclosed between them.

The liquid crystal LC is driven by TN (Twisted Nematic), STN (Super Twisted Nematic), IPS (In-Plane switching), VA (Vertical Alignment), OCB (Optical Aligned Mode), 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 on the TFT (thin film transistor) array 12. An alignment layer 14 is provided on the transparent electrode layer 13. Further, 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 constituting the color filter 22 are separated by a black matrix (not shown).

A transparent protective film (not shown) is formed over the color filter 22 as needed, and a transparent electrode layer 23 made of, for example, ITO is formed on the transparent protective film (not shown), and the alignment layer 24 covers the transparent electrode layer 23. Is provided.

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

White LED light sources include those in which a fluorescent filter is formed on the surface of a blue LED and those in which a phosphor is contained in a resin package of a blue LED, and the wavelength at which the emission intensity becomes maximum in the range of 430 nm to 485 nm ( It has λ3), has a wavelength (λ4) that maximizes the emission intensity in the range of 530 nm to 580 nm, has a wavelength (λ5) that maximizes the emission intensity in the range of 600 nm to 650 nm, and has a wavelength. The ratio (I4 / I3) of the emission intensity I3 at the wavelength λ3 and the emission intensity I4 at the wavelength λ4 is 0.2 or more and 0.4 or less, and the ratio of the emission intensity I3 at the wavelength λ3 and the emission intensity I5 at the wavelength λ5 (I5 / I3). ) Is 0.1 or more and 1.3 or less, and has a white LED light source (LED1) having a spectral characteristic and a wavelength (λ1) having the maximum emission intensity in the range of 430 nm to 485 nm, and is in the range of 530 nm to 580 nm. Spectral characteristics having a peak wavelength (λ2) of the second emission intensity within, and the ratio (I2 / I1) of the emission intensity I1 at the wavelength λ1 and the emission intensity I2 at the wavelength λ2 is 0.2 or more and 0.7 or less. A white LED light source (LED2) having a wavelength of 2 is preferable.

Examples of the LED1 include NSSW306D-HG-V1 (manufactured by Nichia Corporation), NSSW304D-HG-V1 (manufactured by Nichia Corporation), and the like.

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

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

A transfer electrode made of a plurality of photodiodes, polycarbonate, etc. constituting a light receiving area of a solid-state image sensor (CCD sensor, CMOS sensor, organic CMOS sensor, etc.) is provided on a substrate, and the photodiode and the transfer electrode are on the transfer electrode. It has a light-shielding film made of tungsten or the like in which only the light-receiving part of the photodiode is open, and has a device protective film made of silicon nitride or the like formed on the light-shielding film so as to cover the entire surface of the light-shielding film and the light-receiving part of the photodiode. It is a configuration having the color filter of the present invention on the device protective film.
Further, a configuration having a condensing means (for example, a microlens or the like; the same applies hereinafter) on the device protective layer under the color filter (near the substrate), a configuration having a condensing means on the color filter, and the like. May be.
The organic CMOS sensor is composed of a thin-film panchromatic photosensitive organic photoelectric conversion film and a CMOS signal readout substrate as a photoelectric conversion layer, and the organic material plays a role of capturing light and converting it into an electric signal. It is a two-layer hybrid structure in which the inorganic material plays the role of extracting the signal to the outside, and in principle, the aperture ratio can be set to 100% with respect to the incident light. Since the organic photoelectric conversion film is a structure-free continuous film and can be laid on a CMOS signal reading substrate, it does not require an expensive microfabrication process and is suitable for miniaturization of filter segments.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the present invention is not limited to these. In addition, "part" is "mass part", and "%" is "mass%".

Prior to the embodiment, each measurement method will be described.

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 dispersed 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. Using HLC-8220GPC (manufactured by Tosoh Co., Ltd.) as an apparatus, two separation columns are connected in series, and "TSK-GEL SUPER HZM-N" is connected in two for both fillers, and the oven temperature is 40 ° C. , Tetrahydrofuran (THF) solution was used as an eluent, and the measurement was performed at a flow rate of 0.35 ml / min. The sample was dissolved in a solvent consisting of 1 wt% of the above eluent and injected with 20 microliters. The molecular weight is a polystyrene-equivalent value.

(Acid value of alkali-soluble resin and dispersed resin)
80 ml of acetone and 10 ml of water are added to 0.5 to 1 g of an alkali-soluble resin and a dispersed resin solution, and the mixture is stirred to uniformly dissolve the solution. -555 ”manufactured by Hiranuma Sangyo Co., Ltd.) was used for titration, and the acid value (mgKOH / g) was measured. Then, the acid value per non-volatile component of the resin was calculated from the acid value of the resin solution and the non-volatile content concentration of the resin solution.

(Amine value of dispersed resin)
The amine value of the dispersed resin is a value obtained by converting the measured total amine value (mgKOH / g) into a solid content according to the method of ASTM D 2074.

<Production example of miniaturized phthalocyanine pigment (A1)>
(Miniaturized phthalocyanine pigment (A1-1 to 3))
According to the examples of JP-A-2017-11138, refined phthalocyanine pigments (A1-1 to 3) represented by the following chemical formulas 2 to 4 were obtained. The structure is shown below.

(Miniaturized phthalocyanine pigment (A1-4)
C. I. 100 parts of Pigment Green 58 (“FASTGEN GREEN A110” manufactured by DIC Corporation), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 6 hours. This kneaded product was put into 3000 parts of warm water, stirred for 1 hour while heating at 70 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight and 97. A finely divided phthalocyanine pigment (A1-4) was obtained.

(Miniaturized phthalocyanine pigment (A1-5))
C. I. 200 parts of Pigment Green 36 (“Rionol Green 6YK” manufactured by Toyo Color Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, this kneaded product was put into 8 liters of warm water, stirred for 2 hours while heating at 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. for 24 hours. , 190 parts of a finely divided phthalocyanine pigment (A1-5) was obtained.

(Miniaturized phthalocyanine pigment (A1-6))
A 300 mL flask was charged with 91 parts of sulfuryl chloride, 109 parts of aluminum chloride, 15 parts of sodium chloride, 30 parts of zinc phthalocyanine, and 44 parts of bromine. The temperature was raised to 130 ° C. over 40 hours, taken out into water, and then filtered to obtain a green crude pigment. 20 parts of the obtained green crude pigment, 140 parts of crushed sodium chloride, 32 parts of diethylene glycol, and 1.8 parts of xylene were charged in a 1 L double-armed kneader and kneaded at 100 ° C. for 6 hours. After kneading, the mixture was taken out into 2 kg of water at 80 ° C., stirred for 1 hour, filtered, washed with hot water, dried and pulverized to obtain a finely divided phthalocyanine pigment (A1-6). The obtained finely divided phthalocyanine pigment (A1-6) has an average of 11.98 halogen atoms in one molecule from fluorescent X-ray analysis, of which an average of 9.00 bromine atoms and a chlorine atom number. Was an average of 2.98 halogenated zinc phthalocyanine pigments.

<Manufacturing of miniaturized quinophthalone pigment (A2)>
(Miniaturized quinophthalone pigment (A2-1))
C. I. 100 parts of Pigment Yellow 138 (BASF Japan's "Paliotor Yellow K0960-HD"), 700 parts of sodium chloride, and 180 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. .. This mixture was poured into 2,000 parts of warm water, stirred for 1 hour while heating at 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove salt and solvent, and then dried at 80 ° C. for 24 hours and 95 parts. The finely divided quinophthalone pigment (A2-1) was obtained.

(Miniaturized quinophthalone pigment (A2-2))
According to Example 1 of JP2012-226110A, a miniaturized quinophthalone pigment (A2-2) represented by the following chemical formula (5) was obtained. The structure is shown below.

Chemical formula (5)

(Miniaturized quinophthalone pigment (A2-3))
According to the production of the yellow colorant described in Japanese Patent No. 6432076, a miniaturized quinophthalone pigment (A2-3) represented by the following formula (6) was obtained. The structure is shown below.

Chemical formula (6)

<Production of metal salt (B) of quinophthalone compound having a sulfo group>
(Copper salt of quinophthalone compound having a sulfo group (B-1))
C. quinophthalone compound. I. 30 parts of Pigment Yellow 138 (“Paliotoll Yellow K0960-HD” manufactured by BASF Japan, Inc.) was dissolved in 300 parts of 101% sulfuric acid, and the mixture was stirred at 70 ° C. for 8 hours to carry out a sulfonate reaction. The end point of the reaction was the point where the spectral spectrum of the sulfuric acid solution was measured and no change in the spectrum was observed. Next, this reaction solution was poured into 3000 parts of ice water, the precipitate was filtered off, washed with water, dried at 80 ° C., and the quinophthalone compound (b-1) having a sulfo group represented by the following chemical formula (7) was obtained. Obtained.

Chemical formula (7)

Next, 10 g of the quinophthalone compound (b-1) having a sulfo group was added to 500 parts of water, and the mixture was stirred at 25 ° C. for 2 hours and redispersed. Then, 4.8 parts of copper (II) sulfate pentahydrate was gradually added to this solution, and the mixture was reacted at 60 ° C. for 2 hours. The reaction product was separated by filtration, washed with water, and dried at 80 ° C. to obtain a copper salt (B-1) of a 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))
In the same manner, except that 6.6 parts of silver nitrate (I) was used in place of the copper (II) sulfate pentahydrate used in the production of the copper salt (B-1) of the quinophthalone compound having a sulfo group. , A silver salt (B-2) of a quinophthalone compound having a sulfo group represented by the following chemical formula (9) was obtained.

Chemical formula (9)

(Zinc salt of quinophthalone compound having a sulfo group (B-3))
Similar except that 4.3 parts of zinc acetate dihydrate was used in place of the copper (II) sulfate pentahydrate used in the production of the copper salt (B-1) of the quinophthalone compound having a sulfo group. By the method, a zinc salt (B-3) of a quinophthalone compound having a sulfo group represented by the following chemical formula (10) was obtained.

Chemical formula (10)

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

Chemical formula (11)

(Aluminum salt of quinophthalone compound having a sulfo group (B-5))
An aluminum salt (B-5) of a quinophthalone compound having a sulfo group represented by the following chemical formula (12) was obtained according to the synthesis method described in Japanese Patent No. 4585781.

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) can be obtained by the same production method as that of the quinophthalone compound (QL-c-1) described in Examples of JP-A-2015-172732. Obtained.

Chemical formula (13)

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

Chemical formula (14)

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

Chemical formula (15)

<Manufacturing of alkali-soluble resin (C)>
(Alkali-soluble resin (C-1) solution)
196 parts of cyclohexanone was placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirrer in a separable 4-neck flask, the temperature was raised to 80 ° C., and the inside of the reaction vessel was replaced with nitrogen. , 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, paracumylphenol ethylene oxide-modified acrylate (“Aronix M110” manufactured by Toa Synthetic Co., Ltd.) 20. A mixture of 7 parts 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 a solution of acrylic resin. After cooling to room temperature, about 2 parts of the resin solution is sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content. Propylene glycol monomethyl ether so that the non-volatile content is 20% in the previously synthesized resin solution. Acetate (hereinafter, also referred to as PGMAc) was added to prepare an alkali-soluble resin (C-1) solution. The weight average molecular weight (Mw) was 26,000.

(Alkali-soluble resin (C-2) solution)
207 parts of cyclohexanone was placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirrer in a separable 4-neck flask, the temperature was raised to 80 ° C., and the inside of the reaction vessel was replaced with nitrogen. , 20 parts of methacrylic acid, 20 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toa Synthetic Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 2,2'-from the dropping tube. A mixture of 1.33 parts of 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, for the entire amount of the obtained copolymer solution, nitrogen gas was stopped, dry air was injected for 1 hour, and the mixture was stirred, cooled to room temperature, and then 2-methacryloyloxyethyl isocyanate (Showa Denko's Karenz). A mixture of 6.5 parts of MOI), 0.08 part of dibutyltin laurate and 26 parts of cyclohexanone was added dropwise at 70 ° C. over 3 hours. After completion of the dropping, the reaction was continued for another 1 hour to obtain a solution of acrylic resin. After cooling to room temperature, about 2 parts of the resin solution is sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, and cyclohexanone is added to the previously synthesized resin solution so that the non-volatile content is 20%. Addition was made to prepare an alkali-soluble resin (C-2) solution. The weight average molecular weight (Mw) was 18,000.

(Alkali-soluble resin (C-3) solution)
370 parts of cyclohexanone was placed in a separable 4-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirrer, the temperature was raised to 80 ° C., the inside of the flask was replaced with nitrogen, and then the dropping tube was used. , Paracumylphenol Ethylene Oxide Modified Acrylate (Aronix M110 manufactured by Toa Synthetic Co., Ltd.) 18 parts, benzyl methacrylate 10 parts, glycidyl methacrylate 18.2 parts, methyl methacrylate 25 parts, and 2,2'-azobisisobutyronitrile 2 .0 parts of the mixture was added dropwise over 2 hours. After the dropping, the reaction was further carried out at 100 ° C. for 3 hours, 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 100 ° C. for 1 hour. Next, the inside of the container was replaced with air, and 0.5 part of trisdimethylaminophenol and 0.1 part of hydroquinone were added to 9.3 parts of air crilic acid (100% of glycidyl group) into the above container, and the temperature was 120 ° C. The reaction was continued for 6 hours, and when the non-volatile acid value reached 0.5, the reaction was terminated to obtain a solution of acrylic resin. Further, 19.5 parts of tetrahydrophthalic anhydride (100% of the generated hydroxyl group) and 0.5 part of triethylamine were subsequently 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 is sampled, heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content, and PGM Ac is added to the previously synthesized resin solution so that the non-volatile content is 20% by mass. Prepared 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 with a cooling tube was prepared as a reaction tank, while 40 parts of dimethyl-2,2'-[oxybis (methylene)] bis-2-propenoate, 40 parts of methacrylic acid, and methacrylic acid were prepared as a monomer dropping tank. Prepare a well-stirred mixture of 120 parts of methyl, 4 parts of t-butylperoxy2-ethylhexanoate (“Perbutyl O” manufactured by Nippon Oil & Fats), and 40 parts of PGMAc. Eight parts and 32 parts of PGMAc were well mixed and mixed.
After charging 395 parts of PGMAc in the reaction vessel and substituting with nitrogen, the temperature of the reaction vessel was raised to 90 ° C. by heating with an oil bath while stirring. After the temperature of the reaction tank became stable at 90 ° C., dropping was started from the monomer dropping tank and the chain transfer agent dropping tank. The dropping was carried out over 135 minutes while keeping the temperature at 90 ° C. 60 minutes after the dropping was completed, the temperature was raised to 110 ° C. in the reaction vessel. After maintaining 110 ° C. for 3 hours, a gas introduction tube was attached to the separable flask, and bubbling of the oxygen / nitrogen = 5/95 (volume ratio) mixed gas was started. Next, 70 parts of glycidyl methacrylate, 0.4 parts of 2,2'-methylenebis (4-methyl-6-t-butylphenol), and 0.8 part of triethylamine were charged in the reaction vessel, and the reaction was carried out at 110 ° C. for 12 hours. I let you. After that, 150 parts of PGMAc is added and cooled to room temperature, about 2 g of the resin solution is sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, and the non-volatile content becomes 20% by mass in the previously synthesized resin solution. As described above, PGMAc was added 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 component was 2 mgKOH / g.

(Alkali-soluble resin (C-5) solution)
Introduce 333 parts of PGMAc into a flask equipped with a stirrer, thermometer, reflux condenser, dropping rotor and nitrogen introduction tube, change the atmosphere inside the flask from air to nitrogen, raise the temperature to 100 ° C, and then benzyl methacrylate. 70.5 parts (0.40 mol), 71.1 parts (0.50 mol) of glycidyl methacrylate, monomethacrylate of tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) 22.0 parts (0.10 mol) A solution prepared by adding 3.6 parts of azobisisobutyronitrile to a mixture consisting of 164 parts of PGMAc was added dropwise to the flask over 2 hours from the dropping rotor, and stirring was continued at 100 ° C. for 5 hours. Next, the atmosphere in the flask was changed from nitrogen to air, and 43.0 parts of methacrylic acid [0.5 mol, (100 mol% with respect to the glycidyl group of glycidyl methacrylate used in this reaction)], trisdimethylaminomethylphenol 0. 9. 9 parts and 0.145 parts of hydroquinone were put into a flask, and the reaction was continued at 110 ° C. for 6 hours, and the reaction was terminated when the non-volatile acid value reached 1 mgKOH / g. Next, 60.9 parts (0.40 mol) of tetrahydrophthalic anhydride and 0.8 part of triethylamine were added and reacted at 120 ° C. for 3.5 hours to obtain a photosensitive transparent resin solution having 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. PGMAc was added so as to prepare an alkali-soluble resin (C-5) solution. The mass average molecular weight (Mw) was 12,000.

(Alkali-soluble resin (C-6) solution)
Introduce 182 parts of PGMAc into a flask equipped with a stirrer, thermometer, reflux condenser, dropping rotor and nitrogen introduction tube, change the atmosphere inside the flask from air to nitrogen, raise the temperature to 100 ° C, and then benzyl methacrylate. 70.5 parts (0.40 mol), 43.0 parts of methacrylic acid (0.5 mol), monomethacrylate of tricyclodecane skeleton (FA-513M manufactured by Hitachi Kasei Co., Ltd.) 22.0 parts (0.10 mol) A solution prepared by adding 3.6 parts of azobisisobutyronitrile to a mixture consisting of 136 parts of PGMac was added dropwise to the flask over 2 hours from the dropping rotor, and stirring was continued 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 mol, (50 mol% with respect to the carboxyl group of methacrylic acid used in this reaction)], trisdimethylaminomethylphenol 0. 9. 9 parts and 0.145 parts of hydroquinone were put into a flask, and the reaction was continued at 110 ° C. for 6 hours to obtain a photosensitive transparent resin solution having an acid value of 79 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. PGMAc was added so as to prepare an alkali-soluble resin (C-6) solution. The mass average molecular weight (Mw) was 13,000.

<Manufacturing of surfactant (D1)>
(Surfactant (D1-1) solution)
65 parts by mass of methyl ethyl ketone as a solvent and 25.6 parts by mass of dicyclopentanyl methacrylate as another monomer (d2) were charged in a nitrogen-substituted flask, and the temperature was raised to 60 ° C. with 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 inside of the flask was stirred for 30 minutes while keeping the temperature at 60 ° C. Then, 2.0 parts by mass of ethyl 2-bromoisoacetate was added, and the mixture was reacted at 40 ° C. for 2 hours 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 at 60 ° C. for 8 hours to obtain a reaction product. To the obtained reaction product, 30 parts by mass of activated alumina was added and stirred. After filtering the activated alumina, the solvent was removed by vacuum distillation, and PGMAc was added so that the non-volatile content was 2% by mass to obtain a surfactant (D1-1) solution.

(Surfactant (D1-2-7) solution)
The same method except that the monomer (d1) having a fluorinated alkyl group used in the production of the surfactant (D1-1) and the other monomer (d2) used the compounds shown in Table 1 was used. A surfactant (D1-2-7) solution was obtained in.

(Surfactant (D1-8) solution)
63 parts by mass of methyl isobutyl ketone was charged as a solvent into a glass flask equipped with a stirrer, a thermometer, a cooling tube, and a dropping device, and the temperature was raised to 105 ° C. while stirring under a nitrogen stream. Next, 21.5 parts by mass of the compound shown in Table 1 as the monomer (d1) having a poly (perfluoroalkylene ether) chain, and the compound 41.3 shown in Table 1 as the other monomer (d2). 135.4 parts by mass of the initiator solution, which is a mixture of 9.4 parts by mass of t-butylperoxy-2-ethylhexanote as a radical polymerization initiator and 126 parts by mass of methylisobutylketone as a solvent, is placed in a separate dropping device. The mixture was set and dropped simultaneously over 2 hours while keeping the inside of 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 vacuum distillation. Next, 74.7 parts by mass of methyl ethyl ketone as a solvent, 0.1 part 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 2-acryloyloxy was charged with stirring at 60 ° C. 44.8 parts by mass of ethyl isocyanate was added dropwise over 1 hour. After completion of the dropping, the mixture was stirred at 60 ° C. for 1 hour, then heated to 80 ° C. and stirred for 10 hours for reaction. PGMAc was added so that the non-volatile content was 2% by mass to obtain a surfactant (D1-8) solution.

The compounds d1 and d2 in Table 1 are shown below.

(In the formula (d1-3), A is a perfluoromethylene group and a perfluoroethylene group, and each molecule has an average of 7 perfluoromethylene groups and an average of 8 perfluoroethylene groups, and is a fluorine atom. The average number is 46.)

（ｄ２－３）

(D2-3)

<Manufacturing of dispersed resin (F)>
(Dispersed resin (F-1) solution)
A reaction vessel equipped with a gas introduction tube, a temperature, 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 replaced with nitrogen gas. The inside of the reaction vessel was heated and stirred at 50 ° C., and 12 parts of 3-mercapto-1,2-propanediol was added. The temperature was raised to 90 ° C., and the reaction was carried out for 7 hours while adding a solution in which 0.1 part of 2,2'-azobisisobutyronitrile was added to 90 parts of PGMAc. It was confirmed that 95% of the reaction occurred by measuring the non-volatile content. 19 parts of pyromellitic acid anhydride, 50 parts of PGMAc, 50 parts of cyclohexanone, and 0.4 part of 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst were added and reacted at 100 ° C. for 7 hours. .. After confirming that 98% or more of the acid anhydride was half-esterified by measuring the acid value, the reaction was terminated, and PGMAc was added and diluted so that the non-volatile content was 30% by measuring the non-volatile content, and the acid value was 70 mgKOH / g. , A dispersion resin (F-1) solution having a weight average molecular weight of 8,500 was obtained.

(Dispersed resin (F-2) solution)
In a reaction vessel equipped with a gas introduction 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 part of dimethylbenzylamine were added. I prepared it. After replacement with nitrogen gas, the inside of the reaction vessel was heated to 120 ° C. and reacted at 120 ° C. for 4 hours, and then reacted at 80 ° C. for 2 hours. Further, 30 parts of tertiary butyl acrylate, 20 parts of ETERNACOLL OXMA (methyl methacrylate (3-ethyloxetane-3-yl), manufactured by Ube Industries, Ltd.), 5 parts of methacrylic acid, 40 parts of ethyl acrylate, and 10 parts of PGMAc are charged, and a reaction vessel is charged. While keeping the inside at 80 ° C., 0.2 part of 2,2'-azobisisobutyronitrile was added in 15 portions every 30 minutes. The non-volatile content was measured 1 hour after the final addition, and it was confirmed that 95% of the monomers reacted. PGMAc was added and diluted so as to have a non-volatile content of 30% in the non-volatile content measurement to obtain a dispersed resin (F-2) solution having an acid value of 51 mgKOH / g per non-volatile content and a weight average molecular weight (Mw) of 24,000.

(Dispersed resin (F-3) solution)
A reactor equipped with a gas introduction 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 poured. While stirring at 50 ° C. for 1 hour, the inside of the system was replaced with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate, 5.6 parts of cuprous chloride, and 133 parts of PGMAc were charged, and the temperature was raised to 110 ° C. under a nitrogen stream to start the polymerization of the first block (B block). After polymerization for 4 hours, the polymerization solution was sampled and the non-volatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more in terms of the non-volatile content.
Next, 61 parts of PGMAc and 20 parts of 1,2,2,6,6-pentamethylpiperidylmethacrylate (manufactured by Hitachi Kasei Kogyo Co., Ltd., Funkryl FA-711MM) as a second block (A block) monomer were added to this reactor. The mixture was charged and stirred while maintaining the atmosphere of 110 ° C. and nitrogen, and the reaction was continued. Two hours after the addition of 1,2,2,6,6-pentamethylpiperidylmethacrylate, the polymerization solution was sampled to measure the non-volatile content, and the polymerization conversion rate of the second block (A block) was 98 when converted from the non-volatile content. % Or more, and the reaction solution was cooled to room temperature to terminate the polymerization. A dispersion resin (F-3) having a piperidine skeleton having an amine value of 57 mgKOH / g and a number average molecular weight of 4,500 (Mn), diluted by adding PGMAc so as to have a non-volatile content of 30% in the non-volatile content measurement. A solution was obtained.

(Dispersed resin (F-4) solution)
In a 500 mL round bottom 4-port separable flask equipped with a condenser, an addition funnel, an inlet for nitrogen, a mechanical stirrer, and a digital thermometer, 250 parts by mass of tetrahydrofuran (THF) and the initiator dimethylketenemethyltrimethylsilylacetal 5.81 A mass portion was added via the addition funnel and sufficient nitrogen substitution was performed. 0.5 part by mass of 1 mol / L acetonitrile solution of tetrabutylammonium m-chlorobenzoate as a catalyst is injected using a syringe, and 19.7 parts by mass of 2-hydroxyethyl methacrylate, which is a solvent-friendly blocking monomer, is injected. , 7.5 parts by mass of 2-ethylhexyl methacrylate, 12.9 parts by mass of n-butyl methacrylate, 10.7 parts by mass of benzyl methacrylate, 30.9 parts by mass of methyl methacrylate for 60 minutes using an addition funnel. Dropped over. The temperature was kept below 40 ° C. by cooling the reaction flask in an ice bath. After 1 hour, 18.3 parts by mass of dimethylaminopropylmethacrylamide, which is a monomer for blocking the colorant adsorption function, was added dropwise over 20 minutes. After reacting for 1 hour, 1 part by mass of methanol was added to stop the reaction. The obtained block copolymer THF solution was reprecipitated in hexane, and purified by filtration and vacuum drying.
Subsequently, 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 (dimethylaminopropylmethacrylamide), which is a salt-forming component, was dissolved. On the other hand, 0.5 mol equal amount) was added, and the mixture was stirred at a reaction temperature of 30 ° C. for 20 hours, and PGMAc was added for adjustment to obtain a dispersed resin (F-4) solution having a non-volatile content of 30%.

<Manufacturing of dispersion>
(Dispersion 1)
The following raw materials are stirred and mixed so as to be uniform, and then dispersed for 3 hours with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan Co., Ltd.) using a zirconia bead having a diameter of 0.5 mm, and then the pore diameter. The dispersion 1 was prepared by filtering with a 1.0 μm filter. The organic solvent (R-1) is PGMAc.
Miniaturized phthalocyanine pigment (A1-1): 10.0 parts Dispersed resin (F-2) solution: 10.0 parts Dispersed resin (F-3) solution: 7.0 parts Alkali-soluble resin (C-1) solution: 10.0 parts Organic solvent (R-1): 63.0 parts

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

The raw materials listed in Table 2 are as follows.

[Triarylsulfonium compound (E)]
(E-1): T1609 (manufactured by Tokyo Chemical Industry Co., Ltd .: triphenylsulfonium bromide)
(E-2): SP-066 (made by ADEKA: triphenylsulfonium trifluoromethanesulfonate (E-3): WPAG-336 (manufactured by Fuji Film Wako Junyaku Co., Ltd .: diphenyl-4-methylphenylsulfonium trifluoromethanesulfonate) (E-4): TS-01 (Sanwa Chemical Co., Ltd .: Tris (4-methylphenyl) Sulfonium Trifluoromethanesulfonate (E-5): WPAG-370 (Fuji Film Wako Junyaku Co., Ltd .: Diphenyl (4-methoxy) Phenyl) Sulfonium Trifluoromethane Sulfonate (E-6): SP-056 (ADEKA: Triphenyl Sulfonium Nonaflate Butane Sulfonium (E-7): TS-91 (Sanwa Chemical Co., Ltd .: Tris (4-Methylphenyl) ) Sulfonium Hexafluorophosphate

<Manufacturing of coloring composition>
[Example 1]
(Coloring Composition 1)
The following raw materials were stirred and mixed so as to be uniform, 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 Alkaline-soluble resin (C): 5.0 parts Polymerizer (D1-1): 1.5 parts Polymerizable Compound (H): 2.0 parts Photopolymerization initiator (I): 1.0 part Sensitizer (J): 0.2 parts Epoxy compound (K1): 1.0 part Thiol-based chain transfer agent (L) : 0.1 part Polymerizable inhibitor (M): 0.1 part Ultraviolet absorber (N): 0.1 part Antioxidant (O): 0.1 part Storage stabilizer (P): 0.1 part Organic solvent (R): 33.8 parts

[Examples 2 to 41, Comparative Examples 1 to 4]
(Coloring Compositions 2-45)
Colored compositions 2 to 45 were prepared in the same manner as in Colored Composition 1 of Example 1 except that the raw materials and amounts shown in Table 3 were changed.

The raw materials listed in Tables 3-1 to 3-1 are as follows.

[Alkali-soluble resin (C) solution]
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 Big 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.)
As described above, (H-1) to (H-4) were mixed in the same amount to obtain the polymerizable compound (H).

[Photopolymerization Initiator (I)]
(I-1): Irgacure 907 (manufactured by BASF Japan Ltd.)
(I-2): Irgacure 379 (manufactured by BASF Japan Ltd.)
(I-3): Irgacure OXE01 (manufactured by BASF Japan Ltd.)
(I-4): Irgacure OXE02 (manufactured by BASF Japan Ltd.)
(I-5): Irgacure OXE04 (manufactured by BASF Japan Ltd.)
As described above, the same amounts of (I-1) to (I-5) were mixed to obtain 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)
As described above, (J-1) and (J-2) were mixed in the same amount to prepare the sensitizer (I).

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

[Thiol chain transfer agent (L)]
(L-1): Trimethylol etanthris (3-mercaptobutyrate)
(L-2): Trimethylol propanthris (3-mercaptobutyrate)
(L-3): Pentaerythritol tetrakis (3-mercaptopropionate)
(L-4): Trimethylol propanthris (3-mercaptopropionate)
(L-5): Tris [(3-mercaptopropionyloxy) -ethyl] -isocyanurate or more, (L-1) to (L-5) are mixed in equal amounts, and a thiol chain transfer agent (L) is used. ).

[Polymerization inhibitor (M)]
(M-1): 4-Methylcatechol (M-2): Methylhydroquinone (M-3): t-butylhydroquinone or more, (M-1) to (M-3) are mixed in the same amount. Then, it was used as a polymerization inhibitor (M).

[Ultraviolet absorber (N)]
(N-1): TINUVIN400 (manufactured by BASF Japan Ltd.)
(N-2): TINUVIN900 (manufactured by BASF Japan Ltd.)
As described above, (N-1) and (N-2) were mixed in the same amount to obtain an ultraviolet absorber (N).

[Antioxidant (O)]
(O-1): Pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (O-2): 3,3'-dioctadecylthiodipropanoate (O-3): Tris [2,4-di- (t) -butylphenyl] phosphine (O-4): bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate (O-5): p-octyl salicylate Phenyl and above, (O-1) to (O-5) were mixed in the same amount to prepare an antioxidant (N).

[Storage stabilizer (P)]
(P-1): 2,6-bis (1,1-dimethylethyl) -4-methylphenol (P-2): Triphenylphosphine or more, (P-1), (P-2) in equal amounts, respectively To obtain a storage stabilizer (P).

[Organic solvent (R)]
(R-1): Propylene glycol monomethyl ether acetate 30 parts (R-2): Cyclohexanone 30 parts (R-3): Ethyl 3-ethoxypropionate 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) are mixed in the above mass parts, respectively, and an organic solvent is used. It was designated as (R).

<Evaluation of coloring composition>
Each test was performed by the following method. The evaluation results are shown in Table 3.

[Foreign matter evaluation]
The obtained coloring composition was applied onto a glass substrate using a spin coater so that the chromaticity value of the coating film after the heat treatment was y = 0.60 with a C light source. Next, it was dried at 70 ° C. for 20 minutes, exposed to ultraviolet rays at an integrated light intensity of 50 mJ / cm ² using a predetermined mask and an ultrahigh pressure mercury lamp, spray-developed with a sodium carbonate aqueous solution at 23 ° C., and then washed with ion-exchanged water. , Air-dried to form pattern pixels.
Then, heat treatment was performed at 230 ° C. for 40 minutes in an oven, and the number of foreign substances on the glass substrate between the pattern pixels was measured. For the evaluation, surface observation was performed using a metallurgical microscope "BX60" (manufactured by Olympus System Corporation). The magnification was set to 500 times, and the number of foreign substances observable in any five fields of view by transmission was measured by integration. 3 or more is practical.
5: The number of foreign substances is less than 5
4: The number of foreign substances is 5 or more and less than 10 3: The number of foreign substances is 10 or more and less than 20 2: The number of foreign substances is 20 or more and less than 50 1: The number of foreign substances is 50 or more

[Brightness evaluation]
The obtained coloring 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 at 70 ° C. for 20 minutes. Next, ultraviolet exposure was performed with an integrated light amount of ultraviolet rays of 50 mJ / cm ² using an ultra-high pressure mercury lamp, spray-developed with an aqueous sodium carbonate solution at 23 ° C, washed with ion-exchanged water, air-dried, and heat-treated at 230 ° C for 40 minutes in an oven. To form a colored composition layer on a glass substrate.
Next, an overcoat agent was applied onto the coloring composition layer using a spin coater, and the organic solvent was removed by a vacuum drier. Then, after firing on a hot plate at 90 ° C. for 2 minutes, heat treatment was performed at 230 ° C. for 60 minutes to obtain a substrate for lightness evaluation.
The initial brightness of the obtained lightness evaluation substrate in the XYZ color system was measured by LVmicroZ (manufactured by Lambda Vision). Then, after irradiating with ultraviolet rays for 200 hours using LED lighting, the brightness was measured again. The rate of change in brightness was calculated from the following formula. 3 or more is practical.
Brightness change rate = | 200 hours later brightness-initial brightness | / initial brightness x 100
Less than 5: 3% 4: 3% or more and less than 5% 3: 5% or more and less than 10% 2: 10% or more, less than 15% 1: 15% or more

[Voltage retention rate evaluation]
The obtained coloring composition was applied onto a glass substrate having an ITO transparent electrode having an effective electrode size of 10 mm × 10 mm using a spin coater so that the coating film after drying and heat treatment was 2.0 μm, and the electrode portion was formed. After wiping off the coating film of No. 1 with a solvent, the film was exposed to ultraviolet rays at an integrated light amount of 50 mJ / cm ² and developed with an alkaline developer at 23 ° C. to obtain a coating film substrate. Then, after heating at 230 ° C. for 20 minutes and allowing to cool, two sample-coated substrates for measurement were prepared.
The two sample-coated glass substrates were placed facing each other so that the ITO transparent electrode surfaces faced each other, and a small cell was prepared using a sealant so that the cell gap was 9 μm. A liquid crystal liquid is injected into this small cell between the cell gaps, a voltage is applied at a voltage of 5 V for 60 μsec at 50 ° C., and the cell voltage [V1] after 16.67 msec after the voltage is released is set to VHR manufactured by Toyo Corporation. Measured at -1S. The measured cell voltage was averaged, and the obtained cell voltage was used to obtain the initial VHR (%) from the following formula.
VHR (voltage retention rate) (%) = ([V1] / 5) × 100
The above initial VHR measured cell sample is irradiated with LED lighting of 150,000 nits for 3 hours, VHR (%) is measured again, and ΔVHR (voltage retention rate change rate) is obtained from the following formula. evaluated. 3 or more was set as a practical level.
ΔVHR = | Initial VHR-VHR after exposure |
Less than 5: 2% 4: 2% or more and less than 5% 3: 5% or more and less than 10% 2: 10% or more, less than 15% 1: 15% or more

10 Liquid crystal display 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 Orientation layer 25 Polarizing plate 30 Backlight unit 31 White LED light source LC Liquid crystal

Claims (7)

A coloring composition comprising a colorant (A), a metal salt (B) of a quinophthalone compound having a sulfo group, 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 the 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) is a copolymer of a monomer (d1) having at least one of a fluorinated alkyl group and a poly (perfluoroalkylene ether) chain and another monomer (d2). A coloring composition comprising a surfactant (D1). The coloring composition according to claim 1, wherein the other monomer (d2) is a polycyclic alicyclic structure-containing monomer. The coloring composition according to claim 1 or 2, wherein the quinophthalone pigment (A2) contains a quinophthalone pigment represented by the following general formula (1).
General formula (1)

(In the general formula (1), R ₁ to R ₁₃ independently have a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, and a substituent. Indicates an aryl group that may have. R ₁ to R ₄ and / or adjacent groups of R ₅ to R ₈ together form an aromatic ring that may have a substituent. May be good.) The coloring composition according to any one of claims 1 to 3, further comprising the triarylsulfonium compound (E). A color filter comprising a substrate and a filter segment formed by using the coloring composition according to any one of claims 1 to 4. A liquid crystal display device comprising the color filter according to claim 5. A solid-state image sensor comprising the color filter according to claim 5.

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