JP7415697B2 - Colored composition, color filter substrate and display device using the same - Google Patents

Description

The present invention relates to a coloring composition, a color filter substrate, and a display device using the same.

Liquid crystal display devices are used in a variety of applications, such as televisions, notebook computers, personal digital assistants, smartphones, and digital cameras, due to their characteristics of being lightweight, thin, and low power consumption. Liquid crystal display devices are required to have three to six optimal colors depending on the application, and use color filter substrates that provide various color performances.

A color filter substrate is generally produced by performing exposure and development when forming colored pixels, and then baking at a temperature of 200° C. or higher. On the other hand, in order to form colored pixels on a film or a light emitting element in color filter type electronic paper, silicon OLED, etc., in order to suppress the deterioration of the film or the light emitting element, the temperature is below 100 degrees Celsius. It is required to be fired.

For green pixels, various combinations of pigments have been studied, but it is common to combine a green coloring material having a metal phthalocyanine skeleton with a yellow coloring material. Green colored compositions containing epoxy compounds are known for the purpose of improving developability, solvent resistance, heat resistance, electrical properties, spectral properties, etc. (for example, Patent Document 1, Patent Document 2, Patent Document (See 3). However, even when these coloring compositions are used, if the residue in unexposed areas during development is insufficiently suppressed or the firing temperature is low, green pixels may be mixed in color as pixels are repeatedly formed. There was a problem.

JP2011-22371A Japanese Patent Application Publication No. 2012-212051 International Publication No. 2015/182285

The present invention provides a coloring composition that suppresses residues during development, has excellent patterning properties, is hard to cause pattern peeling during overcoating even when baked at low temperatures, and is capable of suppressing color mixing of patterns, and such a coloring composition. The present invention aims to provide a color filter substrate and a display device using a colored composition.

The present invention provides the following.
(1) A coloring composition containing a green colorant having a metal phthalocyanine skeleton, a compound represented by general formula (1), a binder resin, a radically polymerizable compound, and a photopolymerization initiator , ) has an epoxy equivalent of 100 g/mol or more and 300 g/mol or less, and the ratio of the number of moles E of epoxy groups contained in the solid content to the number K of moles of carboxyl groups contained in the solid content A colored composition in which 0<E/K<0.27 .

(In the above general formula (1), R ¹ to R ⁸ independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and n represents an integer of 1 to 30.)

(2) The colored composition according to (1), wherein the compound represented by the general formula (1) has an epoxy equivalent of 150 g/mol or more and 200 g/mol or less.
(3) The ratio of the number of moles E of epoxy groups contained in the solid content to the number K of moles of carboxyl groups contained in the solid content is 0<E/K<0.20 (1) or ( The coloring composition described in 2).
(4) The green coloring material having a metal phthalocyanine skeleton is C.I. I. Pigment Green 58 and/or C.I. I. The colored composition according to any one of (1) to (3), containing Pigment Green 59.
(5)C. I. Pigment Yellow 150 and/or C.I. I. The colored composition according to any one of (1) to (4), further comprising Pigment Yellow 185.
(6) The colored composition according to any one of (1) to (5), wherein the radically polymerizable compound contains dipentaerythritol hexaacrylate and pentaerythritol triacrylate.
(7) A color filter substrate having pixels made of a photocured product of the coloring composition according to any one of (1) to (6).
(8) The color filter substrate according to (7), wherein the substrate is a film.
(9) (A) After applying the colored composition according to any one of (1) to (6) on a substrate, (B) forming a pattern by exposure and development, (C) further forming a pattern on the formed pattern. A method for manufacturing a color filter substrate, including a step of exposing.
(10) A display device comprising the color filter substrate according to (7) or (8).

According to the coloring composition of the present invention, the coloring composition suppresses residues during development, has excellent patterning properties, is resistant to pattern peeling during overcoating even when baked at low temperatures, and further suppresses pattern color mixing. can be provided.

The colored composition of the present invention contains a green colorant having a metal phthalocyanine skeleton, a compound represented by general formula (1), a binder resin, a radically polymerizable compound, and a photopolymerization initiator.

(In the above general formula (1), R ¹ to R ⁸ independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and n represents an integer of 1 to 30).

The colored composition of the present invention contains a green coloring material having a metal phthalocyanine skeleton. As a green colorant having a metal phthalocyanine skeleton, C.I. I. Pigment Green 58, C. I. Pigment Green 59 is preferred. Also, C. I. Pigment Green 58, C. I. Pigment Green 59 may be used alone or in combination.

The content of the green colorant having a metal phthalocyanine skeleton (if two or more types are used together, the total amount, hereinafter the same in this specification) is preferably 20% by mass or more in the solid content from the viewpoint of pixel coloring. , more preferably 30% by mass or more. In addition, from the viewpoint of patterning properties, it is preferably 40% by mass or less based on the solid content.

The colored composition of the present invention may contain a green coloring material other than the green coloring material having a metal phthalocyanine skeleton. Examples of green coloring materials other than green coloring materials having a metal phthalocyanine skeleton include organic pigments, inorganic pigments, and dyes, such as C.I. I. Pigment Green (hereinafter referred to as "PG") PG1, PG2, PG4, PG8, PG10, PG13, PG14, PG15, PG17, PG18, PG19, PG26, PG38, PG39, PG45, PG48, PG50, PG51, PG54, PG55 (and above) , all numbers are color index No.). Two or more types of these may be contained.

The colored composition of the present invention contains a compound represented by the following general formula (1).

In the above general formula (1), R ¹ to R ⁸ independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and n represents an integer of 1 to 30.

The epoxy equivalent of the compound represented by the general formula (1) is preferably 300 g/mol or less, more preferably 200 g/mol or less, from the viewpoint of color mixture and residue suppression. Further, the epoxy equivalent of the compound represented by the general formula (1) is preferably 100 g/mol or more, more preferably 150 g/mol or more from the viewpoint of patterning properties.

The content of the compound represented by the general formula (1) is preferably 0.2% by mass or more, more preferably 0.4% by mass or more in the solid content, from the viewpoint of suppressing color mixture. Further, from the viewpoint of suppressing residue, the content is preferably 1.4% by mass or less, more preferably 1% by mass or less. Moreover, the compound represented by the general formula (1) can be used alone or in combination of two or more kinds.

The colored composition of the present invention contains a binder resin. By containing the binder resin, it is possible to suppress unevenness in film thickness during film formation and to suppress pattern deformation due to flow during firing.

Examples of the binder resin include acrylic resin, epoxy resin, polyimide resin, urethane resin, urea resin, polyvinyl alcohol resin, melamine resin, polyamide resin, polyamideimide resin, polyester resin, and polyolefin resin. Two or more types of these may be contained. From the viewpoint of stability, acrylic resin is preferably used.

As the acrylic resin, a copolymer of an unsaturated carboxylic acid and an ethylenically unsaturated compound is preferred.

Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetic acid, and acid anhydrides thereof. Two or more types of these may be used.

Examples of ethylenically unsaturated compounds include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, ( sec-butyl meth)acrylate, iso-butyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, benzyl (meth)acrylate, etc. unsaturated carboxylic acid alkyl esters, aromatic vinyl compounds such as styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, α-methylstyrene, unsaturated carboxylic acid aminoalkyl esters such as aminoethyl acrylate, glycidyl Unsaturated carboxylic acid glycidyl esters such as acrylate and glycidyl methacrylate, carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate, vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, and α-chloroacrylonitrile, 1,3-butadiene, and isoprene. Examples include aliphatic conjugated dienes such as, polystyrene having a (meth)acryloyl group at the end, macromonomers such as polymethyl acrylate, polymethyl methacrylate, polybutyl acrylate, polybutyl methacrylate, and polysilicone. Two or more types of these may be used.

The acrylic resin preferably has an ethylenically unsaturated group in its side chain, which can improve sensitivity. Examples of the ethylenically unsaturated group include a vinyl group, an allyl group, an acrylic group, and a methacryl group. Examples of the acrylic resin having an ethylenically unsaturated group in its side chain include "Cyclomer" (registered trademark) P (Daicel Chemical Industries, Ltd.), alkali-soluble cardo resin, and the like.

The weight average molecular weight of the binder resin is preferably 3,000 or more, more preferably 9,000 or more from the viewpoint of the strength of the cured film. On the other hand, from the viewpoint of stability of the coloring composition, the weight average molecular weight of the binder resin is preferably 200,000 or less, more preferably 100,000 or less. Here, the weight average molecular weight of the binder resin refers to a standard polystyrene equivalent value measured by gel permeation chromatography.

The content of the binder resin is preferably 10% by mass or more in the solid content, more preferably 20% by mass or more, and even more preferably 30% by mass or more, from the viewpoint of suppressing film thickness unevenness during film formation. On the other hand, from the viewpoint of patterning properties, the content of the binder resin is preferably 60% by mass or less, more preferably 50% by mass or less, based on the solid content.

The colored composition of the present invention contains a radically polymerizable compound. The radically polymerizable compound is preferably a compound having an unsaturated hydrocarbon group. Examples of the unsaturated hydrocarbon group include a (meth)acryloyl group, a vinyl group, and a maleimide group. You may have two or more types of these.

Examples of radically polymerizable compounds include dipentaerythritol penta(meth)acrylate, tetratrimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and penta(meth)acryloyloxy. Ethylene oxide modified products or propylene oxide modified products such as dipentaerythritol monosuccinate, dipentaerythritol hexa(meth)acrylate, styrene derivatives, polyfunctional maleimide compounds, poly(meth)acrylate carbamates, 1,6-hexane adipic acid Oligomers such as diol (meth)acrylic acid ester, phthalic anhydride propylene oxide (meth)acrylic acid ester, trimellitic acid diethylene glycol (meth)acrylic acid ester, rosin-modified epoxy di(meth)acrylate, alkyd-modified (meth)acrylate, etc. Bifunctional (meth)acrylates such as propylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, triacryl formal, bisphenoxyethanolfluorene diacrylate, dicyclo Examples include pentanedienyl diacrylate, alkyl-modified products, alkyl ether-modified products, and alkyl ester-modified products thereof. Two or more types of these may be contained.

Among these, from the viewpoint of solubility and patterning properties, compounds having (meth)acryloyl groups are preferred, and polyfunctional compounds having three or more (meth)acryloyl groups are preferred. By using a polyfunctional compound having three or more (meth)acryloyl groups, it is possible to form a film that has excellent heat resistance and is sufficiently cured. Further, from the viewpoint of alkali developability, compounds having a carboxyl group are preferred. More preferred are compounds having three or more (meth)acryloyl groups and carboxyl groups. Such a compound includes penta(meth)acryloyloxydipentaerythritol monosuccinic acid ester.

Among these radically polymerizable compounds, dipentaerythritol hexaacrylate and pentaerythritol triacrylate are preferably used in combination from the viewpoint of suppressing color mixture and patterning properties. When dipentaerythritol hexaacrylate and pentaerythritol triacrylate are used in combination as radically polymerizable compounds, the content of pentaerythritol triacrylate in the radically polymerizable compounds is preferably 20% by mass or more from the viewpoint of suppressing color mixture, More preferably 40% by mass or more. In addition, when dipentaerythritol hexaacrylate and pentaerythritol triacrylate are used in combination as radically polymerizable compounds, the content of dipentaerythritol hexaacrylate in the radically polymerizable compounds is 20% by mass or more from the viewpoint of patterning properties. is preferable, and 40% by mass or more is more preferable.

The content of the radically polymerizable compound in the colored composition of the present invention is preferably 40% by mass or more based on the solid content from the viewpoint of patterning properties. On the other hand, from the viewpoint of suppressing film thickness unevenness during film formation and pattern deformation due to flow during firing, the content of the radically polymerizable compound is preferably 90% by mass or less, and 70% by mass in the solid content. The following is more preferable, and 60% by mass or less is even more preferable. In addition, from the viewpoint of patterning properties, the content of the radically polymerizable compound having three or more (meth)acryloyl groups and carboxyl groups is preferably 50% by mass or more in the radically polymerizable compound, and further preferably 60% by mass or more. preferable.

In the colored composition of the present invention, when the number of moles of epoxy groups contained in the solid content is E and the number of moles of carboxyl groups contained in the solid content is K, the quotient of E and K, E/K, is , 0<E/K<0.27. The solid content herein refers to all components contained in the coloring composition, excluding the organic solvent. The number of moles E of epoxy groups can be calculated from the epoxy equivalent of the compound having an epoxy group and its weight in the coloring composition. Moreover, the number of moles K of carboxyl groups can be calculated from the acid value of the carboxyl group-containing binder resin, radically polymerizable compound, etc. and its weight in the coloring composition. From the viewpoint of preventing color mixture, it is preferable that 0<E/K, more preferably 0.04<E/K. Further, from the viewpoint of suppressing residue, E/K<0.27 is preferable, and E/K<0.20 is more preferable.

The colored composition of the present invention contains a photopolymerization initiator. By containing a photopolymerization initiator, sensitivity during patterning can be improved. Here, the photopolymerization initiator refers to a compound that decomposes and/or reacts with light (including ultraviolet rays or electron beams) to generate radicals. Examples of photopolymerization initiators include oxime ester compounds, benzophenone compounds, acetophenone compounds, oxanthone compounds, anthraquinone compounds, imidazole compounds, benzothiazole compounds, benzoxazole compounds, carbazole compounds, and triazine compounds. compounds, phosphorus compounds, titanocene compounds, and the like.

More specifically, examples of oxime ester compounds include 1,2-octanedione, 1-[4-(phenylthio)phenyl]-,2-(O-benzoyloxime), ethanone, 1-[9-ethyl -6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime), ethanone, 1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylmethoxy) benzoyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime), ethanone,1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3) -dioxolanyl)methoxybenzoyl}-9H-carbazol-3-yl]-,1-(O-acetyloxime), 1,2-octanedione,1-[4-(phenylthio)-2-(O-benzoyloxime) ], "ADEKA ARCURES" (trademark registered) N-1919, NCI-930 (manufactured by ADEKA Corporation), "IRGACURE" (trademark registered) OXE01, OXE02 (manufactured by BASF Corporation), and the like. Examples of benzophenone compounds include benzophenone, N,N'-tetraethyl-4,4'-diaminobenzophenone, and 4-methoxy-4'-dimethylaminobenzophenone. Examples of acetophenone compounds include 2,2-diethoxyacetophenone, benzoin, benzoin methyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, α-hydroxyisobutylphenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[ 4-(Methylthio)phenyl]-2-morpholino-1-propane, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(dimethylamino)-2-[(4- methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, “IRGACURE ” (trademark registration) 369, 379, 907 (manufactured by BASF Corporation). Examples of anthraquinone compounds include t-butylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-2-methylanthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone, and 9,10-phene. Examples include nanthraquinone, 1,2-benzoanthraquinone, 1,4-dimethylanthraquinone, and 2-phenylanthraquinone. Examples of imidazole compounds include 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer. Examples of benzothiazole compounds include 2-mercaptobenzothiazole. Examples of benzoxazole compounds include 2-mercaptobenzoxazole. Examples of triazine compounds include 4-(p-methoxyphenyl)-2,6-di-(trichloromethyl)-s-triazine. Two or more types of these may be contained. Among these, the green colorant having a metal phthalocyanine skeleton of the present invention, Pigment Yellow 138 and C.I. I. 2-Methyl-1-[4-(methylthio)phenyl] -2-morpholinopropan-1-one is preferred, and in addition to 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, a sensitizer described below may be used in combination. is even more preferable. In addition, from the viewpoint of patterning properties and color mixing prevention in the coloring composition of the present invention, as a photopolymerization initiator, an oxime ester compound such as "ADEKA Arkles" (registered trademark) NCI831 (manufactured by ADEKA Corporation) and "Irgacure" are used as photopolymerization initiators. It is more preferable to use an acetophenone compound such as "(registered trademark) 379 (manufactured by BASF Japan Co., Ltd.) in combination, and examples of the acetophenone compound include 2-dimethylamino-2-(4-methylbenzyl)-1-( It is more preferable to use 4-morpholinophenyl)butan-1-one in combination.

From the viewpoint of sensitivity, patternability, and processability, the content of the photopolymerization initiator is preferably 1% by mass or more, more preferably 2% by mass or more, and 5% by mass in the solid content excluding the coloring material of the coloring composition. The above is more preferable. On the other hand, the content of the photopolymerization initiator is preferably 30% by mass or less, more preferably 20% by mass or less in the solid content excluding coloring materials of the coloring composition, from the viewpoints of sensitivity, patternability, processability, and heat resistance. It is preferably 15% by mass or less, and more preferably 15% by mass or less.

The colored composition of the present invention preferably contains a yellow coloring material from the viewpoint of patterning properties. Examples of the yellow coloring material include organic pigments, inorganic pigments, dyes, etc. For example, C.I. I. Pigment Yellow (hereinafter referred to as "PY") 12, PY13, PY17, PY20, PY24, PY83, PY86, PY93, PY95, PY109, PY110, PY117, PY125, PY129, PY137, PY139, PY147, PY148, PY150, PY153, PY1 54 , PY166, PY168 (all numbers are color index numbers). Two or more types of these may be contained. From the viewpoint of color purity, light transmittance, and contrast, PY129, PY139, PY150, and PY185 are preferred, and PY150 and PY185 are more preferred. Further, in order to suppress a decrease in transmittance of other pixels, it is particularly preferable to use PY150 as the yellow coloring material. Further, from the viewpoint of suppressing color mixture, it is preferable to use PY150 as the yellow coloring material. Yellow coloring materials can be used alone or in combination of two or more. When the colored composition of the present invention contains a yellow colorant, its content is usually about 5% to 30% by weight, preferably about 5% to 20% by weight based on the solid content.

The colored composition of the present invention may contain coloring materials other than the above-mentioned green coloring material and yellow coloring material. Examples of the coloring material include organic pigments, inorganic pigments, dyes, etc., and two or more types of these may be contained. Among these, organic pigments and dyes are preferred from the viewpoint of further improving transmittance.

As the red coloring material, for example, C.I. I. Pigment Red (hereinafter referred to as "PR") 9, PR48, PR97, PR122, PR123, PR144, PR149, PR166, PR168, PR177, PR179, PR180, PR192, PR209, PR215, PR216, PR217, PR220, PR223, PR22 4, PR226 , PR227, PR228, PR240, PR254, etc.

As the orange coloring material, for example, C.I. I. Pigment Orange (hereinafter referred to as "PO") 13, PO31, PO36, PO38, PO40, PO42, PO43, PO51, PO55, PO59, PO61, PO64, PO65, PO71, and the like.

As the blue coloring material, for example, C.I. I. Pigment Blue (hereinafter referred to as "PB") 15, PB15:3, PB15:4, PB15:6, PB21, PB22, PB60, PB64, and the like.

As the purple coloring material, for example, C.I. I. Pigment violet (hereinafter referred to as "PV") 19, PV23, PV29, PV30, PV32, PV37, PV40, PV50, etc. (all numbers are color index numbers).

Examples of the dye include oil-soluble dyes, acid dyes, direct dyes, basic dyes, and acid mordant dyes. Further, the above dye may be made into a lake, or a salt-forming compound of the dye and a nitrogen-containing compound may be used.

Examples of red, green, blue, purple, or yellow dyes include direct dyes, acid dyes, and basic dyes. Specific examples of these dyes include azo dyes, benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, xanthene dyes, cyanine dyes, squarylium dyes, croconium dyes, merocyanine dyes, stilbene dyes, Examples include diarylmethane dyes, triarylmethane dyes, fluoran dyes, spiropyran dyes, phthalocyanine dyes, indigo dyes, fulgide dyes, nickel complex dyes, and azulene dyes. The dye may be dissolved in the coloring composition or dispersed as particles.

In order to increase resistance to heat, light, acid, alkali or organic solvents, the basic dye is preferably a salt-forming compound consisting of an organic acid such as an organic sulfonic acid or an organic carboxylic acid or perchloric acid, and Tobias' acid etc. A salt-forming compound consisting of naphthalenesulfonic acid or perchloric acid is more preferred. Similarly, in order to increase resistance to heat, light, acids, alkalis, organic solvents, etc., salt-forming compounds comprising quaternary ammonium salts, primary to tertiary amines, or sulfonamides are preferred as acidic dyes and direct dyes.

The coloring composition of the present invention further contains a dispersant, a chain transfer agent, a sensitizer, an organic solvent, a polymerization inhibitor, an adhesion improver, a surfactant, an organic acid, an organic amino compound, a curing agent, etc. Good too.

The coloring material contained in the colored composition of the present invention can be identified by laser Raman spectroscopy (Ar + laser (457.9 nm)) or mass spectrometry using a MALDI mass spectrometer or a time-of-flight secondary ion mass spectrometer. I can do it.

In addition, the content of the coloring material in the coloring composition can be quantified by mass spectrometry using a MALDI mass spectrometer or a time-of-flight secondary ion mass spectrometer, and the mass of the coloring material obtained and the amount of other components From the content, the proportion (mass %) in the solid content in the coloring composition can be determined. In addition, if the blending ratio of the raw materials of the coloring composition is known, the proportion (mass%) in the solid content of the coloring composition can be calculated from the blending amount of the coloring material and the blending amount of other components. I can do it.

The colored composition of the present invention may contain a dispersant such as a pigment derivative together with a coloring material. Examples of the dispersant include low molecular dispersants such as pigment intermediates and derivatives, and polymer dispersants. Examples of the pigment derivative include alkylamine modified pigment skeletons, carboxylic acid derivatives, sulfonic acid derivatives, etc., which contribute to appropriate wetting and stabilization of the pigment. Preference is given to sulfonic acid derivatives of the pigment skeleton, which have a significant effect on stabilizing fine pigments.

Examples of the polymeric dispersant include polyester, polyalkylamine, polyallylamine, polyimine, polyamide, polyurethane, polyacrylate, polyimide, polyamideimide, and copolymers thereof. Two or more types of these may be contained. Among these polymeric dispersants, those having an amine value of 5 to 200 mgKOH/g and an acid value of 1 to 100 mgKOH/g in terms of solid content are preferred. Among these, polymeric dispersants having a basic group are preferred and can improve the storage stability of pigment dispersions and coloring compositions. Examples of commercially available polymeric dispersants having a basic group include "Solsperse" (registered trademark) (manufactured by Avecia), "EFKA" (registered trademark) (manufactured by Efka), and "Ajisper" (registered trademark). ) (manufactured by Ajinomoto Fine Techno Co., Ltd.) and "BYK" (registered trademark) (manufactured by BYK Chemie Co., Ltd.). Two or more types of these may be contained. Among them, "Solspers" (registered trademark) 24000 (manufactured by Avecia), "EFKA" (registered trademark) 4300, 4330 (manufactured by Efka), 4340 (manufactured by Efka), "Ajisper" (registered trademark) PB821, PB822 (Ajinomoto) "BYK" (registered trademark) 161 to 163, 2000, 2001, 6919, and 21116 (manufactured by BYK Chemie) are preferred.

When the coloring composition of the present invention contains a polymeric dispersant, the total content of the polymeric dispersant and binder resin is 10% by mass or more based on the solid content from the viewpoint of suppressing film thickness unevenness during film formation. It is preferably 20% by mass or more, more preferably 30% by mass or more. On the other hand, from the viewpoint of patterning properties, the total content of the polymer dispersant and the binder resin is preferably 60% by mass or less, more preferably 50% by mass or less, based on the solid content excluding the coloring material of the coloring composition.

The colored composition of the present invention may contain a chain transfer agent in addition to a photopolymerization initiator, thereby making it possible to further improve sensitivity. Examples of chain transfer agents include thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N-(2-mercaptopropionyl)glycine, and 2-mercaptonicotinic acid. , 3-[N-(2-mercaptoethyl)carbamoyl]propionic acid, 3-[N-(2-mercaptoethyl)amino]propionic acid, N-(3-mercaptopropionyl)alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, dodecyl (4-methylthio) phenyl ether, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto-2-propanol, 3-mercapto -2-butanol, mercaptophenol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercapto-3-pyridinol, 2-mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropane tris (3-mercaptopropionate), 1, 3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione), pentaerythritol tetrakis(3-mercaptopropionate), 1,4-bis(3-mercaptobutyryloxy)butane, “Karenz” (registered trademark) MT PE-1 (manufactured by Showa Denko K.K.), “Karenz” (registered trademark) MT NR-1 (manufactured by Showa Denko K.K.) Mercapto compounds such as "Karens" (registered trademark) MT BD-1 (manufactured by Showa Denko Co., Ltd.), disulfide compounds obtained by oxidizing the mercapto compounds, iodoacetic acid, iodopropionic acid, 2 Examples include iodized alkyl compounds such as -iodoethanol, 2-iodoethanesulfonic acid, and 3-iodopropanesulfonic acid. Two or more types of these may be contained.

The colored composition of the present invention may further contain a sensitizer to further improve sensitivity. Examples of the sensitizer include thioxanthone sensitizers, aromatic or aliphatic tertiary amines, and the like. Examples of thioxanthone-based sensitizers include thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthene-9-one, "KAYACURE" (registered trademark) DETX-S (manufactured by Nippon Kayaku Co., Ltd.), and the like. Can be mentioned. Two or more types of these may be contained.

The colored composition of the present invention may further contain an organic solvent. Examples of the organic solvent include diethylene glycol monobutyl ether acetate, benzyl acetate, ethyl benzoate, methyl benzoate, diethyl malonate, 2-ethylhexyl acetate, 2-butoxyethyl acetate, ethylene glycol monobutyl ether acetate, diethyl oxalate, ethyl acetoacetate, Cyclohexyl acetate, 3-methoxy-butyl acetate, methyl acetoacetate, ethyl-3-ethoxypropionate, 2-ethylbutyl acetate, isopentyl propionate, propylene glycol monomethyl ether propionate, pentyl acetate, propylene glycol monomethyl ether Acetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, monoethyl ether, methyl carbitol, ethyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol tertiary Butyl ether, dipropylene glycol monomethyl ether, ethyl acetate, butyl acetate, isopentylbutanol acetate, 3-methyl-2-butanol, 3-methyl-3-methoxybutanol, cyclopentanone, cyclohexanone, xylene, ethylbenzene, solvent naphtha, etc. Can be mentioned. Two or more types of these may be contained.

The colored composition of the present invention may further contain a polymerization inhibitor to improve stability. Polymerization inhibitors generally have the effect of inhibiting or stopping polymerization caused by radicals generated by heat, light, radical initiators, etc., and are generally used to prevent gelation of thermosetting resins and to prevent polymerization during polymer production. Used for polymerization termination, etc. Examples of the polymerization inhibitor include hydroquinone, tert-butylhydroquinone, 2,5-bis(1,1,3,3-tetramethylbutyl)hydroquinone, 2,5-bis(1,1-dimethylbutyl)hydroquinone, Examples include catechol and tert-butylcatechol. Two or more types of these may be contained. From the viewpoint of balance between stability and photosensitive properties, the content of the polymerization inhibitor is preferably 0.0001% by mass or more, more preferably 0.005% by mass or more in the solid content. Further, from the viewpoint of balance between stability and photosensitive properties, the content of the polymerization inhibitor is preferably 1% by mass or less, more preferably 0.5% by mass or less in the solid content.

The colored composition of the present invention may further contain an adhesion improver, and can improve the adhesion of the coating film of the colored composition to the substrate. Examples of adhesion improvers include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, and N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane. ethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl Examples include silane coupling agents such as trimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane. Two or more types of these may be contained.

The colored composition of the present invention may further contain a surfactant, and can improve the applicability of the colored composition and the uniformity of the coating surface. Examples of surfactants include anionic surfactants such as ammonium lauryl sulfate and polyoxyethylene alkyl ether sulfate triethanolamine, cationic surfactants such as stearylamine acetate and lauryl trimethylammonium chloride, lauryl dimethylamine oxide, and lauryl sulfate. Amphoteric surfactants such as carboxymethyl hydroxyethylimidazolium betaine, nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, sorbitan monostearate, fluorine surfactants, silicone surfactants, etc. can be mentioned. Two or more types of these may be contained. The content of the surfactant in the coloring composition is preferably 0.001 to 10% by mass from the viewpoint of in-plane uniformity of the coating film.

Identification of the components of the coloring composition of the present invention and confirmation of the blending amount of each component can be performed by the following method. The colored composition is subjected to HPLC measurement and GPC measurement using various eluent compositions to confirm the number of components blended in the colored composition. The solvent is removed using a rotary evaporator, precision distillation, etc., taking care not to denature each component. Thereafter, each component is (isolated) and purified by methods such as preparative HPLC, preparative GPC, and column chromatography using various eluents. Regarding the (isolation) purification of each component, it is also possible to (isolate) and purify each component by methods such as preparative HPLC, preparative GPC, and column chromatography using various eluents without removing the solvent. can. In addition, each component can be identified by methods such as GC-MASS, ¹ HNMR, ¹³ CNMR, various two-dimensional NMR such as HMBC and HMQC, IR measurement, confirmation of parent peaks by mass spectrometry, and fragment analysis. can. Furthermore, from the epoxy compound and carboxyl group-containing compound contained in each component, the number of moles E of epoxy groups contained in the solid content and the number K of moles of carboxyl groups contained in the solid content can be determined, and E/ K can be calculated. Moreover, the epoxy equivalent of an epoxy compound can be measured by measuring the epoxy equivalent of an isolated component.

Next, the color filter substrate of the present invention will be explained. The color filter substrate of the present invention has pixels made of the coloring composition of the present invention on the substrate. It may also include other pixels such as red and blue. Furthermore, it may have a black matrix, a photo spacer, an overcoat layer, an alignment film, a polarizing plate, a retardation plate, an antireflection film, a transparent electrode, a diffusion plate, and the like.

Examples of substrates include inorganic glass plates such as soda glass, alkali-free glass, borosilicate glass, quartz glass, aluminoborosilicate glass, aluminosilicate glass, alkali aluminosilicate glass, and soda lime glass coated with silica. Examples include silicon wafers, organic plastic films and sheets, etc. Two or more types of these may be laminated. Note that when the display device including the color filter substrate of the present invention is a reflective display device or a display device having a light emitting element such as a silicon OLED, the substrate may be opaque.

The organic plastic film or sheet may be a self-supporting film or may be a film formed by coating on a substrate such as a glass substrate. In the case of such a coating film, it is possible to peel it off by appropriately adjusting the adhesion between the substrate and the film using a laser or the like. Examples of organic plastic materials include polyesters such as polypropylene, polyethylene, polystyrene, and polyethylene terephthalate (PET), polyphenylene sulfide (PPS), polyimide, polyamide, polyamideimide, polyether sulfone, and polytetrafluoroethylene (PTFE). Examples include fluorine-containing polymers, polyether ether ketone, polyphenylene ether, polyarylate, polysulfone, and the like.

From the viewpoint of the strength of the substrate, the substrate preferably has a film thickness of 5 μm or more, more preferably 10 μm or more. On the other hand, from the viewpoint of flexibility, the substrate is preferably a film with a thickness of 100 μm or less.

Examples of pixels include colored pixels such as red and blue, and transparent pixels. Examples of the material constituting the pixel include the colored composition of the present invention and a colored photosensitive composition containing a binder resin such as an acrylic resin or a polyimide resin and a radically polymerizable compound. From the viewpoint of improving color purity, the film thickness of the pixel is preferably 0.5 μm or more, more preferably 1.0 μm or more, and even more preferably 1.4 μm or more. On the other hand, from the viewpoint of improving the flatness, pattern processability, and reliability of the color filter substrate, the thickness is preferably 3.0 μm or less, and more preferably 2.8 μm or less.

The black matrix prevents deterioration of contrast and color purity due to light leakage between pixels, and is preferably arranged between pixels or in the frame area. Examples of the material constituting the black matrix include a photosensitive composition containing a binder resin such as an acrylic resin or a polyimide resin and a radically polymerizable compound, and a non-photosensitive resin composition colored black. The thickness of the black matrix is preferably 0.5 μm or more, more preferably 1.0 μm or more from the viewpoint of light-shielding properties. On the other hand, from the viewpoint of workability, the thickness is preferably 2.0 μm or less, more preferably 1.5 μm or less.

Photo spacers create a certain gap between opposing substrates, and the gap can be filled with a liquid crystal compound, etc., so the process of arranging the spacer can be omitted when manufacturing liquid crystal display devices. can. It is preferable that the color filter substrate be fixed at a specific location on the color filter substrate so as to be in contact with the counter substrate when the liquid crystal display device is manufactured. Examples of the material constituting the photo spacer include a photosensitive composition containing a binder resin such as an acrylic resin or a polyimide resin and a radically polymerizable compound. Examples of the shape of the photo spacer include a cylindrical shape, a prismatic shape, a truncated cone shape, a truncated pyramid shape, and the like. The diameter of the photo spacer is not particularly specified, but is preferably 2 to 20 μm, more preferably 3 to 10 μm. Further, the height of the photo spacer is preferably 1 to 10 μm.

The overcoat layer suppresses the transmission of impurities from the pixels of the color filter substrate, and flattens the steps caused by the pixels of the color filter substrate. Examples of the material constituting the overcoat layer include epoxy resin, acrylic epoxy resin, acrylic resin, siloxane resin, polyimide resin, and photosensitive or non-photosensitive materials commercially available as planarizing materials. From the viewpoint of processability, the thickness of the overcoat layer is preferably 0.5 μm or more, more preferably 1.0 μm or more. On the other hand, from the viewpoint of flatness of the color filter substrate, the thickness is preferably 5.0 μm or less, more preferably 3.0 μm or less.

Examples of the material constituting the transparent electrode include metals such as aluminum, chromium, tantalum, titanium, neodymium, or molybdenum, indium-tin-oxide (ITO), and indium-zinc-oxide (InZnO).

An example of a method for manufacturing a color filter substrate is a method of forming a pattern of pixels made of a resin composition on a substrate. The manufacturing method will be explained below using as an example a color filter substrate having pixels made of the colored composition of the present invention. A color filter substrate can be obtained by applying the colored composition of the present invention onto a substrate, patterning it by selective exposure using a photomask and development, and baking to form pixels.

Methods for applying the coloring composition of the present invention onto a substrate include, for example, a spin coater, a bar coater, a blade coater, a roll coater, a die coater, an inkjet printing method, a screen printing method, and immersing the substrate in the coloring composition. method, a method of spraying a colored composition onto a substrate, and the like. Subsequently, the substrate coated with the colored composition is dried to form a coating film of the colored composition on the substrate. Examples of the drying method include air drying, heat drying, vacuum drying, and the like. Two or more of these may be used in combination; for example, it is preferable to dry under reduced pressure and then heat dry. The heating drying temperature is preferably 80 to 130°C, and the heating drying device is preferably a hot air oven or a hot plate. In the case of a color filter substrate having a black matrix, it is preferable to form a coating film of the coloring composition on the substrate on which the black matrix has been formed in advance.

Next, a photomask is placed on the coating film of the colored composition, and selective exposure is performed. Examples of the exposure machine include a proximity exposure machine, a mirror projection exposure machine, a lens scan exposure machine, and a stepper. From the viewpoint of accuracy, a lens scan exposure machine is preferred. Furthermore, examples of the light source used for exposure include an ultra-high pressure mercury lamp, a chemical lamp, and a high-pressure mercury lamp.

Thereafter, unexposed areas are removed by development with an alkaline developer to form a coating film pattern. Examples of the alkaline substances used in the alkaline developer include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, ethylamine, n-propylamine, etc. Examples include primary amines, secondary amines such as diethylamine and di-n-propylamine, tertiary amines such as triethylamine and methyldiethylamine, and organic alkalis such as tetramethylammonium hydroxide. Examples of the alkaline developer include 0.02 to 1% by mass of potassium hydroxide or tetramethylammonium hydroxide. Examples of the developing method include a method in which the coated film after exposure is immersed in an alkaline developer for 20 to 300 seconds.

Thereafter, the obtained coating film pattern is heat-treated to obtain a color filter substrate on which pixels are patterned. The heat treatment may be performed in air, in a nitrogen atmosphere, or in vacuum. The heating temperature is preferably 80 to 250°C. The heating time is preferably 5 minutes to 5 hours. As the heat treatment device, a hot air oven or a hot plate is preferable. The heat treatment may be performed continuously or in stages.

Further, after applying the colored composition of the present invention onto a substrate, it is preferable to form a pattern by exposure and development, and then further expose the formed pattern to light before performing heat treatment to form a pattern. . By exposing the formed pattern to light before heat treatment, crosslinking can be further enhanced.

Pixel formation is performed sequentially using the above method for each of the three to six color pixels that the color filter substrate has. Although the order in which each color is formed is not particularly limited, when forming a pixel containing a dye, it is preferable to form the pixel containing the dye after forming other pixels, from the viewpoint of further suppressing color transfer of the coloring material.

The color filter substrate of the present invention can be used as a component of display devices such as liquid crystal displays, organic EL displays, and electronic paper. That is, the display device of the present invention includes the color filter substrate and display element of the present invention. Furthermore, the display device may include a light source such as an external light source and various films such as a brightness enhancement film and a diffuser plate. A display device refers to a device that displays an image by making a part of the screen visible. Examples of the display element include a liquid crystal element, an organic EL element, an inorganic EL element, a display element using MEMS, a display element using quantum dots, electronic ink, electronic powder, and an electrophoretic element. Examples of the display device include a transmissive liquid crystal display, a transflective liquid crystal display, a reflective liquid crystal display, an organic EL display, an inorganic EL display, a quantum dot display, and electronic paper. Examples of reflective display devices include devices that display using outdoor light or indoor light, such as wearable terminals, electronic signboards, digital signage, and electronic shelf labels.

As an example of the method for manufacturing a display device of the present invention, a method for manufacturing a liquid crystal display device will be shown below. A color filter substrate and an array substrate are bonded to face each other via a liquid crystal alignment film provided on those substrates and a spacer for maintaining a cell gap. Note that a TFT liquid crystal display device or a TFD liquid crystal display device can be manufactured by providing a thin film transistor (TFT) element, a thin film diode (TFD) element, a scanning line, a signal line, etc. on an array substrate. Next, after liquid crystal is injected through the injection port provided in the seal portion, the injection port is sealed. Furthermore, by attaching a backlight and mounting IC drivers, etc., a liquid crystal display device is completed. Note that a 2-wavelength LED, a 3-wavelength LED, a CCFL, etc. can be used as the backlight, but a 3-wavelength LED is preferable because it can expand the color reproduction range of the liquid crystal display device and keep power consumption low. .

The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples. Other components used in each Example and Comparative Example are as follows.

Epoxy compound solution C1: Propylene glycol monomethyl ether acetate solution C2 in which a compound represented by general formula (1) (R ¹ to R ⁸ are hydrogen atoms, n is about 23, epoxy equivalent 169 g/mol) is diluted to 50% by mass : Propylene glycol monomethyl ether acetate solution C3 in which bisphenol A type epoxy resin (epoxy equivalent: 925 g/mol) was diluted to 50% by mass: "jER" (registered trademark) 630 (manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 98 g/mol) Propylene glycol monomethyl ether acetate solution diluted to 50% by mass

Radical polymerizable compound solution D1: Propylene glycol monomethyl ether acetate solution in which dipentaerythritol hexaacrylate was diluted to 50% by mass D2: Propylene glycol monomethyl ether acetate solution in which pentaerythritol triacrylate was diluted to 50% by mass

Photopolymerization initiator E1: “ADEKA Arkles” (registered trademark) NCI831 (manufactured by ADEKA Co., Ltd.)
E2: “Irgacure” (registered trademark) 379 (manufactured by BASF Japan Co., Ltd.)

Organic solvent F1: Propylene glycol monomethyl ether acetate

Evaluation methods in Examples and Comparative Examples will be explained.
<Residue evaluation>
The colored compositions obtained in Examples 1 to 9 and Comparative Examples 1 to 5 were spin-coated onto a 10 cm square glass substrate and dried at 90° C. for 10 minutes to obtain a coating film with a thickness of 2.3 μm. The resulting coating film was immersed for 50 seconds in a 0.3% by mass tetramethylammonium hydroxide aqueous solution at 23°C, then washed with pure water, and the presence or absence of residue on the substrate was visually confirmed, and evaluated according to the following evaluation criteria. evaluated.

A: No residue on the board B: There is a residue on the edge of the board C: There is a residue on the board

<Patternability evaluation>
The colored compositions obtained in Examples 1 to 9 and Comparative Examples 1 to 5 were applied onto a glass substrate and dried at 90° C. for 10 minutes. Thereafter, exposure was performed with i-line at 40 mJ through a photomask having line and space patterns of 10 μm, 15 μm, 20 μm, and 25 μm. Next, shower development was performed for 50 seconds with a 0.3 mass % tetramethylammonium hydroxide aqueous solution at 23° C., followed by washing with pure water. A substrate with a film having a thickness of 2.3 μm was obtained by baking at 100° C. for 30 minutes. The formation of line and space patterns of each size was observed using an optical microscope, and the minimum size that could be formed was confirmed.

<Pattern peeling evaluation>
The colored composition H1 obtained in Production Example 5 was applied onto the film-coated substrate obtained by patterning evaluation and dried at 90° C. for 10 minutes. Shower development was performed for 90 seconds with a 0.3% by mass aqueous tetramethylammonium hydroxide solution at 23°C. The processed substrates were observed using an optical microscope to see if line and space patterns of each size were formed, and the minimum size of the formed patterns was confirmed.

<Color mixture evaluation>
The colored compositions obtained in Examples 1 to 9 and Comparative Examples 1 to 5 were applied onto a glass substrate and dried at 90° C. for 10 minutes. After exposure to 40 mJ of i-line, shower development was performed for 50 seconds with a 0.3 mass % tetramethylammonium hydroxide aqueous solution at 23° C., and washed with pure water. A substrate with a film having a thickness of 2.3 μm was obtained by baking at 100° C. for 30 minutes. The transmittance T0 of the obtained film at 520 nm was measured using a microspectrometer LCF-100MA manufactured by Otsuka Electronics Co., Ltd.

Next, the colored composition H1 obtained in Production Example 5 was applied onto the obtained film-coated substrate under conditions such that the film thickness after drying at 90° C. for 10 minutes was 2.3 μm. Subsequently, after drying at 90° C. for 10 minutes, shower development was performed for 90 seconds with a 0.3 mass % tetramethylammonium hydroxide aqueous solution at 23° C. to obtain a film-coated substrate. Regarding the obtained film, transmittance T1 at 520 nm was measured using a microspectrometer LCF-100MA manufactured by Otsuka Electronics Co., Ltd., and color mixture was evaluated using T1/T0. The closer the value of T1/T0 is to 1, the less likely color mixture will occur, which is preferable.

Production example 1 (preparation of dispersion liquid (A1))
C. I. Pigment Green 58 (“FASTGEN” (registered trademark) Green A110 manufactured by DIC Corporation) 150 g, “BYK” (registered trademark) LPN6919 (manufactured by BYK Chemie, polymer dispersant solution (60% by mass propylene glycol monomethyl ether solution)) A slurry was prepared by mixing 125 g of "Cyclomer" (registered trademark) ACA250 (manufactured by Daicel Chemical Co., Ltd., 45% by mass dipropylene glycol monomethyl ether solution), and 625 g of propylene glycol monomethyl ether (PMA). A beaker containing the slurry was connected to a dyno mill with a tube, and dispersion treatment was performed for 8 hours at a circumferential speed of 14 m/s using zirconia beads with a diameter of 0.5 mm as the media. I. Pigment Green 58 dispersion (A1) was prepared.

Production example 2 (preparation of dispersion liquid (A2))
C. I. Pigment Green 58 instead of C. I. Pigment Yellow 150 (“Chromofine” (registered trademark) Yellow 6266EC manufactured by Dainichiseika Chemical Co., Ltd.) 150 g was used in the same manner as in Production Example 1, except that C.I. I. Pigment Yellow 150 dispersion (A2) was prepared.

Production example 3 (preparation of dispersion liquid (A3))
C. I. Pigment Green 58 instead of C. I. Pigment Blue 15:6 (“FASTGEN” (registered trademark) EP193 manufactured by DIC Corporation) in the same manner as in Production Example 1 except that 150 g of C.I. I. Pigment Blue 15:6 dispersion (A3) was prepared.

Production example 4 (synthesis of binder resin solution (B1))
In a 500 mL three-neck flask, add 33 g (0.3 mol) of methyl methacrylate, 33 g (0.3 mol) of styrene, 35 g (0.5 mol) of methacrylic acid, and 3 g (0.0 mol) of 2,2'-azobis(2-methylbutyronitrile). 02 mol) and 150 g of propylene glycol monomethyl ether acetate (PGMEA) were charged and stirred at 90°C for 2 hours, then the internal temperature was raised to 100°C and further stirred for 1 hour to obtain a reaction solution. To the obtained reaction solution, 33 g (0.2 mol) of glycidyl methacrylate, 1.2 g (0.009 mol) of dimethylbenzylamine, and 0.2 g (0.002 mol) of p-methoxyphenol were added, and the mixture was heated at 90°C. After stirring for a period of time, PGMEA was added to obtain a binder resin solution (B1) with a solid content concentration of 40% by mass. When the acid value of the binder resin was measured for a 0.1 mol/L potassium hydroxide/ethanol solution using an automatic potential difference measuring device AT-610 manufactured by Kyoto Electronics Industry Co., Ltd., the acid value was 119 (mgKOH/g). Met. Further, when the weight average molecular weight was calculated in terms of polystyrene using a GPC device, the weight average molecular weight was 22,000.

Production Example 5 (Preparation of colored composition (H1))
In a 50 mL plastic bottle, 4.71 g of dispersion A3 obtained in Production Example 3, 3.05 g of binder resin solution B1 obtained in Production Example 4, 2.87 g of radically polymerizable compound solution D1, "Irgacure" (registered trademark) ) 907 (manufactured by BASF Japan Ltd.) and 18.80 g of solvent F1 were added and stirred for 3 hours to prepare a colored composition (H1).

Production example 6 (preparation of dispersion liquid (A4))
C. I. Pigment Green 58 instead of C. I. Pigment Yellow 185 (“Paliotol” (registered trademark) Yellow D1155 manufactured by BASF) in the same manner as in Production Example 1 except that 150 g of C.I. I. Pigment Yellow 185 dispersion (A4) was prepared.

Example 1
In a 50 mL plastic bottle, 10.19 g of dispersion A1 obtained in Production Example 1, 1.39 g of Dispersion A2 obtained in Production Example 2, 2.04 g of binder resin solution B1 obtained in Production Example 4, and epoxy compound. 0.02 g of solution C1, 2.16 g of radically polymerizable compound solution D1, 0.18 g of photoinitiator E1, 0.18 g of photoinitiator E2, and 13.83 g of organic solvent F1 were added and stirred for 3 hours. A colored composition (G1) was prepared. When the obtained colored composition was evaluated for residue by the method described above, no residue was observed on the substrate (A). Furthermore, patterning properties were evaluated and it was confirmed that a 10 μm pattern was formed. Further, a pattern peelability evaluation was performed and it was confirmed that a 10 μm pattern remained. Further, when color mixture evaluation was performed, T1/T0 was 0.78.

Examples 2 to 9, Comparative Examples 1 to 5
A colored composition was prepared in the same manner as in Example 1, except that the types and charging ratios of the dispersion liquid, binder resin solution, epoxy compound solution, radically polymerizable compound, photopolymerization initiator, and organic solvent were changed as shown in Table 1. (G2 to G14) were obtained. Table 2 summarizes the results of evaluation by the method described above using the obtained colored composition. In the patterning evaluation, if no pattern was formed, it was marked as "-", and in the subsequent pattern peeling evaluation, if no pattern remained, it was marked as "-".

Example 10
The colored composition (G5) obtained in Example 5 was applied onto a glass substrate and dried at 90° C. for 10 minutes. After exposure to 40 mJ of i-line, shower development was performed for 50 seconds with a 0.3 mass % tetramethylammonium hydroxide aqueous solution at 23° C., and washed with pure water. Thereafter, the substrate was exposed to i-line at 40 mJ, and then baked at 100° C. for 30 minutes to obtain a substrate with a film having a thickness of 2.3 μm. The transmittance T0 of the obtained film at 520 nm was measured using a microspectrometer LCF-100MA manufactured by Otsuka Electronics Co., Ltd.

Next, the colored composition H1 obtained in Production Example 5 was applied onto the obtained film-coated substrate under conditions such that the film thickness after drying at 90° C. for 10 minutes was 2.3 μm. Subsequently, after drying at 90° C. for 10 minutes, shower development was performed for 90 seconds with a 0.3 mass % tetramethylammonium hydroxide aqueous solution at 23° C. to obtain a film-coated substrate. Regarding the obtained film, the transmittance T1 at 520 nm was measured using a microspectrometer LCF-100MA manufactured by Otsuka Electronics Co., Ltd., and it was confirmed that T1/T0 was 0.97.

Example 11
In a 50 mL plastic bottle, 10.19 g of dispersion A1 obtained in Production Example 1, 1.39 g of Dispersion A4 obtained in Production Example 6, 2.04 g of binder resin solution B1 obtained in Production Example 4, and epoxy compound. 0.11 g of solution C1, 2.08 g of radically polymerizable compound solution D1, 0.18 g of photoinitiator E1, 0.18 g of photoinitiator E2, and 13.83 g of organic solvent F1 were added and stirred for 3 hours. A colored composition (G15, E/K=0.187) was prepared. When the obtained colored composition was evaluated for residue by the method described above, no residue was observed on the substrate (A). Furthermore, patterning property evaluation was carried out and it was confirmed that a 10 μm pattern was formed. Furthermore, a pattern peelability evaluation was performed and it was confirmed that a 10 μm pattern remained. Further, when color mixture evaluation was performed, T1/T0 was 0.81.

The colored composition of the present invention can be suitably used for color filter substrates and display devices.

Claims (10)

A colored composition containing a green colorant having a metal phthalocyanine skeleton, a compound represented by general formula (1), a binder resin, a radically polymerizable compound, and a photopolymerization initiator ,
The epoxy equivalent of the compound represented by general formula (1) is 100 g/mol or more and 300 g/mol or less, and the number of moles E of epoxy groups contained in the solid content and the number of moles of carboxyl groups contained in the solid content A colored composition having a ratio of 0<E/K<0.27 .

(In the above general formula (1), R ¹ to R ⁸ independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and n represents an integer of 1 to 30.) The colored composition according to claim 1, wherein the compound represented by the general formula (1) has an epoxy equivalent of 150 g/mol or more and 200 g/mol or less. 3. The method according to claim 1, wherein the ratio of the number of moles E of epoxy groups contained in the solid content to the number K of moles of carboxyl groups contained in the solid content is 0<E/K<0.20. Colored composition. The green coloring material having a metal phthalocyanine skeleton is C.I. I. Pigment Green 58 and/or C.I. I. The colored composition according to any one of claims 1 to 3, comprising Pigment Green 59. C. I. Pigment Yellow 150 and/or C.I. I. The colored composition according to any one of claims 1 to 4, further comprising Pigment Yellow 185. The colored composition according to any one of claims 1 to 5, wherein the radically polymerizable compound contains dipentaerythritol hexaacrylate and pentaerythritol triacrylate. A color filter substrate having pixels made of a photocured product of the coloring composition according to any one of claims 1 to 6. The color filter substrate according to claim 7, wherein the substrate is a film. (A) after applying the colored composition according to any one of claims 1 to 6 on a substrate, (B) forming a pattern by exposure and development, and (C) further exposing the formed pattern to light. , a method for manufacturing a color filter substrate. A display device comprising the color filter substrate according to claim 7 or 8.