JP2020166258A - Coloring composition, and color filter substrate and display device including the same - Google Patents

Abstract

To provide a coloring composition that reduces residues during development, has excellent patterning properties, prevents pattern peeling from occurring during a recoating process even when fired at low temperature, and can suppress color mixture of the patterns, and a color filter substrate and a display device using the coloring composition.SOLUTION: A coloring composition contains a green colorant having a metal phthalocyanine skeleton, an epoxy resin having a specific structure, a binder resin, a radical-polymerizable compound and a photopolymerization initiator.SELECTED DRAWING: None

Description

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

Liquid crystal display devices are used in various applications such as televisions, notebook computers, personal digital assistants, smartphones, and digital cameras, taking advantage of their characteristics such as light weight, thinness, and low power consumption. The liquid crystal display device is required to have the optimum colors of 3 to 6 primary colors depending on the application, and a color filter substrate having various color performances is used.

The color filter substrate is generally manufactured by exposing and developing colored pixels at the time of formation and further firing at a temperature of 200 ° C. or higher. On the other hand, in color filter type electronic paper, silicon OLED, etc., in order to form colored pixels on a film or a light emitting element, in order to suppress deterioration of the film or the light emitting element, the temperature is 100 ° C. or lower. It is required to be fired.

For green pixels, combinations of various pigments have been studied, but it is common to combine a green color material having a metal phthalocyanine skeleton and a yellow color material. A green coloring composition containing an epoxy compound is known for the purpose of improving developability, solvent resistance, heat resistance, electrical characteristics, spectral characteristics, etc. (for example, Patent Document 1, Patent Document 2, Patent Document 2). 3). However, even when these coloring compositions are used, if the residue of the unexposed portion during development is insufficiently suppressed or the firing temperature is low, the green pixels are mixed while the pixels are repeatedly formed. There was a problem.

Japanese Unexamined Patent Publication No. 2011-22371 Japanese Unexamined Patent Publication No. 2012-212051 International Publication No. 2015/182285

The present invention comprises a coloring composition that suppresses residues during development, has excellent patterning properties, is less likely to cause pattern peeling during recoating even when fired at a low temperature, and can further suppress pattern color mixing. An object of the present invention is to provide a color filter substrate and a display device using a coloring composition.

The present invention provides the following.
(1) A coloring composition containing a green color material having a metallic phthalocyanine skeleton, a compound represented by the 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 represent hydrogen atoms or alkyl groups having 1 to 3 carbon atoms independently of each other, and n represents an integer of 1 to 30.)

(2) The coloring composition according to (1), wherein the epoxy equivalent of the compound represented by the general formula (1) is 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 of moles K of carboxyl groups contained in the solid content is 0 <E / K <0.20 (1) or (1) or ( The coloring composition according to 2).
(4) The green color material having the metal phthalocyanine skeleton is C.I. I. Pigment Green 58 and / or C.I. I. The coloring composition according to any one of (1) to (3), which comprises Pigment Green 59.
(5) C. I. Pigment Yellow 150 and / or C.I. I. The coloring composition according to any one of (1) to (4), which further comprises Pigment Yellow 185.
(6) The coloring 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) After applying the coloring composition according to any one of (A) (1) to (6) on a substrate, (B) a pattern is formed by exposure and development, and then (C) a further formed pattern is formed. A method for manufacturing a color filter substrate, which includes an exposure step.
(10) A display device having the color filter substrate according to (7) or (8).

According to the coloring composition of the present invention, a coloring composition that suppresses residues during development, has excellent patterning properties, is less likely to cause pattern peeling during recoating even when fired at a low temperature, and further suppresses pattern color mixing. Can be provided.

The coloring composition of the present invention contains a green color material having a metal phthalocyanine skeleton, a compound represented by the 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 represent hydrogen atoms or alkyl groups having 1 to 3 carbon atoms independently of each other, and n represents an integer of 1 to 30).

The coloring composition of the present invention contains a green color material having a metallic phthalocyanine skeleton. As a green color material having a metallic phthalocyanine skeleton, from the viewpoint of further improving the light transmittance, C.I. I. Pigment Green 58, C.I. I. Pigment Green 59 is preferred. In addition, C.I. I. Pigment Green 58, C.I. I. Pigment Green 59 may be used alone or in combination.

The content of the green color material having a metallic phthalocyanine skeleton (the total amount when two or more kinds are used in combination, hereinafter the same in the present 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. Further, from the viewpoint of patterning property, it is preferably 40% by mass or less in the solid content.

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

The coloring 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 mixing and residue suppression. 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 property.

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 mixing. Further, from the viewpoint of residue suppression, it is preferably 1.4% by mass or less, and more preferably 1% by mass or less. Further, the compound represented by the general formula (1) can be used alone or in combination of two or more.

The coloring composition of the present invention contains a binder resin. By containing the binder resin, uneven film thickness during film formation can be suppressed, and deformation of the pattern due to flow during firing can be suppressed.

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 of these may be contained. Acrylic resin is preferably used from the viewpoint of stability.

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

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

Examples of the ethylenically unsaturated compound include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and ( Se-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 such as styrene, p-methyl styrene, o-methyl styrene, m-methyl styrene, α-methyl styrene, etc., unsaturated carboxylic acid amino alkyl esters such as amino ethyl acrylate, glycidyl Unsaturated carboxylic acid glycidyl ester such as acrylate and glycidyl methacrylate, carboxylic acid vinyl ester such as vinyl acetate and vinyl propionate, vinyl cyanide compound such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, 1,3-butadiene, isoprene Examples thereof include aliphatic conjugated diene such as, polystyrene having a (meth) acryloyl group at the terminal, polymethylacrylate, polymethylmethacrylate, polybutylacrylate, polybutylmethacrylate, and macromonomer such as polysilicone. Two or more of these may be used.

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

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 the 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 glomatography.

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

The coloring 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 of these.

Examples of the radically polymerizable compound include dipentaerythritol penta (meth) acrylate, tetratrimethylolpropantri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and penta (meth) acryloyloxy. Ethylene oxide-modified or propylene oxide-modified products such as dipentaerythritol monosuccilate, dipentaerythritol hexa (meth) acrylate, styrene derivatives, polyfunctional maleimide compounds, poly (meth) acrylate carbamate, adipate 1,6-hexane Oligolites such as diol (meth) acrylic acid ester, propylene oxide (meth) acrylic acid ester anhydride, diethylene glycol (meth) acrylic acid ester of trimellitic acid, rosin-modified epoxy di (meth) acrylate, and alkyd-modified (meth) acrylate, tri Bifunctional (meth) acrylates such as propylene glycol di (meth) acrylate and 1,6-hexanediol di (meth) acrylate, trimethylpropantri (meth) acrylate, triacrylic formal, bisphenoxyethanol full orange acrylate, dicyclo Examples thereof include pentanedienyldiacrylate, these alkyl modified products, alkyl ether modified products and alkyl ester modified products. Two or more of these may be contained.

Among these, a compound having a (meth) acryloyl group is preferable, and a polyfunctional compound having three or more (meth) acryloyl groups is preferable from the viewpoint of solubility and patterning property. By using a polyfunctional compound having three or more (meth) acryloyl groups, a film having excellent heat resistance and being sufficiently cured can be formed. Further, from the viewpoint of alkali developability, a compound having a carboxyl group is preferable. A compound having three or more (meth) acryloyl groups and a carboxyl group is more preferable. Examples of such a compound include penta (meth) acryloyloxydipentaerythritol monosuccinate.

Among these, as the radically polymerizable compound, it is preferable to use dipentaerythritol hexaacrylate and pentaerythritol triacrylate in combination from the viewpoint of color mixing suppression and patterning property. When dipentaerythritol hexaacrylate and pentaerythritol triacrylate are used in combination as the radically polymerizable compound, the content of pentaerythritol triacrylate in the radically polymerizable compound is preferably 20% by mass or more from the viewpoint of suppressing color mixing. More preferably, it is 40% by mass or more. When dipentaerythritol hexaacrylate and pentaerythritol triacrylate are used in combination as the radically polymerizable compound, the content of dipentaerythritol hexaacrylate in the radically polymerizable compound is 20% by mass or more from the viewpoint of patterning property. Is preferable, and 40% by mass or more is more preferable.

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

In the coloring 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, E / K, which is a quotient of E and K, is , 0 <E / K <0.27. The solid content referred to here refers to all the components contained in the coloring composition except the organic solvent. The number of moles E of the epoxy group can be calculated from the epoxy equivalent of the compound having an epoxy group and the weight thereof in the coloring composition. Further, the number of moles K of the carboxyl group can be calculated from the acid value of the binder resin containing the carboxyl group, the radically polymerizable compound, and the like in the coloring composition, and the weight thereof. From the viewpoint of preventing color mixing, 0 <E / K is preferable, and 0.04 <E / K is more preferable. Further, from the viewpoint of residue suppression, E / K <0.27 is preferable, and E / K <0.20 is more preferable.

The coloring composition of the present invention contains a photopolymerization initiator. By containing the photopolymerization initiator, the sensitivity at the time of 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 the photopolymerization initiator include oxime ester compounds, benzophenone compounds, acetophenone compounds, oxantone compounds, anthraquinone compounds, imidazole compounds, benzothiazole compounds, benzoxazole compounds, carbazole compounds, and triazine compounds. Examples thereof include compounds, phosphorus compounds and titanosen compounds.

More specifically, examples of the oxime ester compound include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), etanone, 1- [9-ethyl. -6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime), etanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxy) Benzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime), etanone, 1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3) -Dioxolanyl) methoxybenzoyl} -9H-carbazole-3-yl]-, 1- (O-acetyloxime), 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime) ], "Adeca Arcurus" (registered trademark) N-1919, NCI-930 (manufactured by ADEKA Co., Ltd.), "IRGACURE" (registered trademark) OXE01, OXE02 (manufactured by BASF Co., Ltd.) and the like. Examples of the benzophenone compound include benzophenone, N, N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone and the like. Examples of the acetophenone compound include 2,2-diethoxyacetophenone, benzoin, benzoin methyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, α-hydroxyisobutylphenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- [ 4- (Methylthio) Phenyl] -2-morpholino-1-propane, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (dimethylamino) -2-[(4-4-) Methylphenyl) Methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, "IRGACURE" "(Registered trademark) 369, 379, 907 (manufactured by BASF Co., Ltd.) and the like. Examples of anthraquinone compounds include t-butyl anthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-2-methylanthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone, and 9,10-fe. Examples thereof include nantraquinone, 1,2-benzoanthraquinone, 1,4-dimethylanthraquinone and 2-phenylanthraquinone. Examples of the imidazole compound include 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer. Examples of the benzothiazole-based compound include 2-mercaptobenzothiazole. Examples of the benzoxazole-based compound include 2-mercaptobenzoxazole. Examples of the triazine-based compound include 4- (p-methoxyphenyl) -2,6-di- (trichloromethyl) -s-triazine. Two or more of these may be contained. Among these, the green color material having the metallic phthalocyanine skeleton of the present invention and Pigment Yellow 138 and C.I. I. 2-Methyl-1- [4- (methylthio) phenyl] from the viewpoint of patterning sensitivity and pattern processability in a coloring composition in which the total content with Pigment Yellow 185 is 2% by mass or more and 16% by mass or less in the solid content. -2-Molphorinopropane-1-one is preferable, and in addition to 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, a sensitizer described later is used in combination. Is even more preferable. Further, from the viewpoint of patterning property and color mixing suppression in the coloring composition of the present invention, as a photopolymerization initiator, an oxime ester compound such as "ADEKA Benzyl" (registered trademark) NCI831 (manufactured by ADEKA Corporation) and "Irgacure" It is more preferable to use an acetophenone compound such as "(registered trademark) 379 (manufactured by BASF Japan Co., Ltd.) in combination, and the acetophenone compound is 2-dimethylamino-2- (4-methylbenzyl) -1-(. It is more preferable to use 4-morpholinophenyl) butane-1-one in combination.

From the viewpoint of sensitivity, patterning property, 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, based on the solid content of the coloring composition excluding the coloring material. 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, based on the solid content of the coloring composition excluding the coloring material, from the viewpoints of sensitivity, patterning property, processability, and heat resistance. It is preferable, and 15% by mass or less is more preferable.

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

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

Examples of the red color material include C.I. I. Pigment Red (hereinafter "PR") 9, PR48, PR97, PR122, PR123, PR144, PR149, PR166, PR168, PR177, PR179, PR180, PR192, PR209, PR215, PR216, PR217, PR220, PR223, PR224, PR226 , PR227, PR228, PR240, PR254 and the like.

Examples of the orange color material include C.I. I. Pigment orange (hereinafter, "PO") 13, PO31, PO36, PO38, PO40, PO42, PO43, PO51, PO55, PO59, PO61, PO64, PO65, PO71 and the like.

Examples of the blue color material include C.I. I. Pigment blue (hereinafter, “PB”) 15, PB15: 3, PB15: 4, PB15: 6, PB21, PB22, PB60, PB64 and the like.

Examples of the purple color material include C.I. I. Pigment Violet (hereinafter "PV") 19, PV23, PV29, PV30, PV32, PV37, PV40, PV50 and the like (all of the above numbers are color index Nos.).

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

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

In order to enhance resistance to heat, light, acid, alkali or organic solvent, the basic dye is preferably a salt-forming compound composed of an organic acid such as an organic sulfonic acid or an organic carboxylic acid or a perchloric acid, such as tobias acid. A salt-forming compound composed of naphthalene sulfonic acid or perchloric acid is more preferable. Similarly, as the acid dye and the direct dye, a salt-forming compound composed of a quaternary ammonium salt, a primary to tertiary amine or a sulfonamide is preferable in order to enhance resistance to heat, light, acid, alkali or an organic solvent.

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 and the like. May be good.

The coloring material contained in the coloring composition of the present invention shall be identified by mass spectrometry by laser Raman spectroscopy (Ar + laser (457.9 nm)), MALDI mass spectrometer or time-of-flight secondary ion mass spectrometer. Can be done.

Further, the content of the coloring material in the coloring composition can be quantified by mass spectrometry using a MALDI mass spectrometer or a flight time type secondary ion mass spectrometer, and the mass of the obtained coloring material and other components can be quantified. From the content of, the ratio (mass%) to the solid content in the coloring composition can be determined. When the blending ratio of the raw materials of the coloring composition is known, the ratio (mass%) of the solid content in the coloring composition is obtained from the blending amount of the coloring material and the blending amount of other components. Can be done.

The coloring 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 weight dispersants such as pigment intermediates and derivatives, and high molecular weight dispersants. Examples of the pigment derivative include an alkylamine modified product of the pigment skeleton, a carboxylic acid derivative, a sulfonic acid derivative, and the like, which contribute to appropriate wetting and stabilization of the pigment. A sulfonic acid derivative having a pigment skeleton, which has a remarkable effect on stabilizing the fine pigment, is preferable.

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

When the coloring composition of the present invention contains a polymer dispersant, the total content of the polymer dispersant and the binder resin is 10% by mass or more in the solid content from the viewpoint of suppressing uneven film thickness during film formation. Is preferable, 20% by mass or more is more preferable, and 30% by mass or more is further preferable. On the other hand, from the viewpoint of patterning property, 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 coloring composition of the present invention may contain a chain transfer agent in combination with the photopolymerization initiator, and the sensitivity can be further improved. Examples of the chain transfer agent include thioglycolic acid, thioapple 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-Mercaptopropane sulfonic acid, 4-mercaptobutane sulfonic 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, trimethylpropanthris (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-mercaptobutylyloxy) butane, "Karenzu" (registered trademark) MT PE-1 (manufactured by Showa Denko Co., Ltd.), "Karenzu" (registered trademark) MT NR-1 (Showa Denko (Showa Denko) (Manufactured by Co., Ltd.), "Carens" (registered trademark) MT BD-1 (manufactured by Showa Denko Co., Ltd.), etc., a disulfide compound obtained by oxidizing the mercapto compound, iodoacetic acid, iodopropionic acid, 2, Examples thereof include alkyl iodide compounds such as −iodoethanol, 2-iodoethanesulfonic acid, and 3-iodopropanesulfonic acid. Two or more of these may be contained.

The coloring composition of the present invention may further contain a sensitizer, and the sensitivity can be further improved. Examples of the sensitizer include thioxanthone-based sensitizers, aromatic or aliphatic tertiary amines and the like. Examples of the thioxanthone-based sensitizer 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 of these may be contained.

The coloring 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, and the like. 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, solventnaphtha, etc. Can be mentioned. Two or more of these may be contained.

The coloring composition of the present invention may further contain a polymerization inhibitor, and its stability can be improved. Polymerization inhibitors generally have the effect of prohibiting or stopping polymerization by radicals generated by heat, light, radical initiators, etc., and generally prevent gelation of thermosetting resins or during polymer production. It is used to stop polymerization. Examples of the polymerization inhibitor include hydroquinone, tert-butylhydroquinone, 2,5-bis (1,1,3,3-tetramethylbutyl) hydroquinone, and 2,5-bis (1,1-dimethylbutyl) hydroquinone. Examples thereof include catechol and tert-butylcatechol. Two or more of these may be contained. From the viewpoint of the balance between stability and photosensitive characteristics, 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 the balance between stability and photosensitive characteristics, 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 coloring composition of the present invention may further contain an adhesion improving agent, and can improve the adhesion of the coating film of the coloring composition to the substrate. Examples of the adhesion improver include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, and N- (2-amino). Ethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl Examples thereof include silane coupling agents such as trimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane. Two or more of these may be contained.

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

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

Next, the color filter substrate of the present invention will be described. The color filter substrate of the present invention has pixels made of the coloring composition of the present invention on the substrate. It may have other pixels such as red and blue. Further, 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.

As the substrate, for example, a plate of inorganic glass such as soda glass, non-alkali glass, borosilicate glass, quartz glass, aluminosilicate glass, aluminosilicate glass, alkalialuminosilicate glass, and soda lime glass whose surface is silica-coated. , Silicon wafers, organic plastic films and sheets, and the like. Two or more kinds of these may be laminated. When the display device provided with the color filter substrate of the present invention is a reflection type 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-standing film, or may be a film formed by coating or the like on a substrate such as a glass substrate. In the case of such a coating film, the adhesion between the substrate and the film can be appropriately adjusted and peeled off by a laser or the like. Examples of the material of the organic plastic include polypropylene such as polypropylene, polyethylene, polystyrene and polyethylene terephthalate (PET), polyphenylene sulfide (PPS), polyimide, polyamide, polyamideimide, polyethersulfone and polytetrafluoroethylene (PTFE). Fluorine-containing polymers, polyether ether ketones, polyphenylene ethers, polyarylates, polysulfones and the like can be mentioned.

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

Examples of the pixel include colored pixels such as red and blue and transparent pixels. Examples of the material constituting the pixel include the coloring composition of the present invention, a colored photosensitive composition containing a binder resin such as an acrylic resin and a polyimide resin, and a radically polymerizable compound. From the viewpoint of improving color purity, the pixel film thickness 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, 3.0 μm or less is preferable, and 2.8 μm or less is more preferable.

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

Since the photo spacer is provided with a certain gap between the photo spacer and the opposite substrate and a liquid crystal compound or the like can be filled between the gaps, the step of arranging the spacer can be omitted when manufacturing the liquid crystal display device. it can. It is preferable that the color filter substrate is fixed at a specific location so as to be in contact with the facing substrate when the liquid crystal display device is manufactured. Examples of the material constituting the photospacer 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 columnar shape, a prismatic shape, a truncated cone shape, and a truncated cone shape. The diameter of the photo spacer is not particularly specified, but is preferably 2 to 20 μm, more preferably 3 to 10 μm. 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 an epoxy resin, an acrylic epoxy resin, an acrylic resin, a siloxane resin, a polyimide resin, and a photosensitive or non-photosensitive material commercially available as a flattening material. The film thickness of the overcoat layer is preferably 0.5 μm or more, more preferably 1.0 μm or more, from the viewpoint of workability. On the other hand, from the viewpoint of flatness of the color filter substrate, 5.0 μm or less is preferable, and 3.0 μm or less is more preferable.

Examples of the material constituting the transparent electrode include metals such as aluminum, chromium, tantalum, titanium, neodymium or molybdenum, Indium-Tin-Oxide (ITO), Indium-Zinc-Oxide (InZNO) and the like.

Examples of the method for manufacturing the color filter substrate include a method of forming a pattern of pixels made of a resin composition on the substrate. Hereinafter, a manufacturing method will be described using a color filter substrate having pixels made of the coloring composition of the present invention as an example. A color filter substrate can be obtained by applying the coloring composition of the present invention onto a substrate, patterning it by selective exposure and development using a photomask, and firing it to form pixels.

As a method of applying the coloring composition of the present invention on a substrate, 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, or a substrate is immersed in the coloring composition. Examples thereof include a method and a method of spraying a coloring composition onto a substrate. Subsequently, the substrate coated with the coloring composition is dried to form a coating film of the coloring 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 combined, and for example, it is preferable to perform vacuum drying and then heat drying. The heat-drying temperature is preferably 80 to 130 ° C., and the heat-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 is formed in advance.

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

Then, the unexposed portion is removed by development with an alkaline developer to form a coating film pattern. Examples of the alkaline substance used in the alkaline developing solution include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine and the like. Examples thereof 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 of immersing the coating film after exposure in an alkaline developer for 20 to 300 seconds.

Then, the obtained coating film pattern is heat-treated to obtain a color filter substrate in 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 apparatus, a hot air oven and a hot plate are preferable. The heat treatment may be performed continuously or stepwise.

Further, it is preferable that after the coloring composition of the present invention is applied onto a substrate, a pattern is formed by exposure and development, and then the formed pattern is further exposed before heat treatment to form the pattern. .. By exposing the formed pattern before the heat treatment, the cross-linking can be further enhanced.

Pixels are sequentially formed for each of the 3 to 6 color pixels of the color filter substrate by the above method. The formation order of each color is not particularly limited, but when forming the pixels containing the dye, it is preferable to form the pixels containing the dye after the formation of the other pixels from the viewpoint of further suppressing the color transfer of the color material.

The color filter substrate of the present invention can be a component of a display device such as a liquid crystal display, an organic EL display, or electronic paper. That is, the display device of the present invention has the color filter substrate and the display element of the present invention. Further, the display device may include a light source such as an external light source, various films such as a brightness improving film and a diffuser plate, and the like. A display device refers to a device that displays an image by visually recognizing a part of the screen. 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, an electronic ink, an electronic powder fluid, an electrophoresis element, and the like. 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 the reflective display device include devices that display with outdoor light or indoor light, such as wearable terminals, electronic signboards, digital signage, and electronic shelf labels.

As an example of the manufacturing method of the display device of the present invention, the manufacturing method of the liquid crystal display device is shown below. The color filter substrate and the array substrate are attached to each other so as to face each other via a liquid crystal alignment film provided on the substrate and a spacer for holding a cell gap. A TFT liquid crystal display device or a TFD liquid crystal display device can be manufactured by providing a thin film transistor (TFT) element or a thin film diode (TFD) element, a scanning line, a signal line, or the like on an array substrate. Next, after injecting the liquid crystal from the injection port provided in the seal portion, the injection port is sealed. Further, a liquid crystal display device is completed by attaching a backlight and mounting an IC driver or the like. As the backlight, a two-wavelength LED, a three-wavelength LED, a CCFL, or the like can be used, but a three-wavelength LED is preferable because the color reproduction range of the liquid crystal display device can be expanded and the power consumption can be suppressed low. ..

The present invention will be described 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: A propylene glycol monomethyl ether acetate solution C2 obtained by diluting a compound represented by the general formula (1) (R ^{1 to} R ⁸ are hydrogen atoms, n is about 23, epoxy equivalent is 169 g / mol) to 50% by mass. : A propylene glycol monomethyl ether acetate solution obtained by diluting a bisphenol A type epoxy resin (epoxy equivalent 925 g / mol) to 50% by mass C3: "jER" (registered trademark) 630 (manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 98 g / mol) Epoxy 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 is diluted to 50% by mass D2: Propylene glycol monomethyl ether acetate solution in which pentaerythritol triacrylate is diluted to 50% by mass

Photopolymerization Initiator E1: "ADEKA ARKULS" (registered trademark) NCI831 (manufactured by ADEKA Corporation)
E2: "Irgacure" (registered trademark) 379 (manufactured by BASF Japan Ltd.)

Organic solvent F1: Propylene glycol monomethyl ether acetate

The evaluation method in Examples and Comparative Examples will be described.
<Residual evaluation>
The coloring compositions obtained in Examples 1 to 9 and Comparative Examples 1 to 5 were spin-coated on a 10 cm square glass substrate and dried at 90 ° C. for 10 minutes to obtain a coating film having a thickness of 2.3 μm. The obtained coating film was immersed in a 0.3 mass% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 50 seconds, washed with pure water, visually confirmed for the presence of residues on the substrate, and according to the following evaluation criteria. evaluated.

A: No residue on the substrate B: Residue on the edge of the substrate C: Residue on the substrate

<Evaluation of patterning property>
The coloring compositions obtained in Examples 1-9 and Comparative Examples 1-5 were applied onto a glass substrate and dried at 90 ° C. for 10 minutes. Then, it was exposed with i-line 40 mJ through a photomask having line & space patterns of 10 μm, 15 μm, 20 μm, and 25 μm. Next, it was shower-developed with a 0.3 mass% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 50 seconds, and then washed with pure water. A substrate with a film having a thickness of 2.3 μm was obtained by firing at 100 ° C. for 30 minutes. The minimum size that can be formed was confirmed by observing with an optical microscope whether a line & space pattern of each size was formed.

<Pattern peeling evaluation>
The coloring composition H1 obtained in Production Example 5 was applied onto the coated substrate obtained by the patterning property evaluation, and dried at 90 ° C. for 10 minutes. Shower development was carried out for 90 seconds with a 0.3 mass% tetramethylammonium hydroxide aqueous solution at 23 ° C. With respect to the treated substrate, it was observed with an optical microscope whether line & space patterns of each size were formed, and the minimum size of the formed patterns was confirmed.

<Color mixing evaluation>
The coloring 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 with i-line 40 mJ, the mixture was shower-developed with a 0.3 mass% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 50 seconds and washed with pure water. A substrate with a film having a thickness of 2.3 μm was obtained by firing at 100 ° C. for 30 minutes. The transmittance T0 at 520 nm was measured for the obtained film using a microspectroscopy LCF-100MA manufactured by Otsuka Electronics Co., Ltd.

Next, the coloring composition H1 obtained in Production Example 5 was applied onto the obtained coated substrate under the condition 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 carried out for 90 seconds with a 0.3 mass% tetramethylammonium hydroxide aqueous solution at 23 ° C. to obtain a coated substrate. With respect to the obtained film, the transmittance T1 at 520 nm was measured using a microspectroscopy LCF-100MA manufactured by Otsuka Electronics Co., Ltd., and the color mixing was evaluated at T1 / T0. The closer the value of T1 / T0 is to 1, the less likely it is that color mixing will occur, which is preferable.

Production Example 1 (Preparation of dispersion (A1))
C. I. Pigment Green 58 (“FASTGEN” (registered trademark) Green A110 manufactured by DIC Co., Ltd.) 150 g, “BYK” (registered trademark) LPN6919 (manufactured by Big Chemie, polymer dispersant solution (60 mass% propylene glycol monomethyl ether solution)) A slurry was prepared by mixing 125 g, 100 g of "Cyclomer" (registered trademark) ACA250 (45 mass% dipropylene glycol monomethyl ether solution manufactured by Daicel Chemical Co., Ltd.), and 625 g of propylene glycol monomethyl ether (PMA). A beaker containing the slurry was connected to a dyno mill with a tube, and zirconia beads having a diameter of 0.5 mm were used as a medium for dispersion treatment at a peripheral speed of 14 m / s for 8 hours. I. Pigment Green 58 dispersion (A1) was prepared.

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

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

Production Example 4 (Synthesis of binder resin solution (B1))
Methyl methacrylate 33 g (0.3 mol), styrene 33 g (0.3 mol), methacrylic acid 35 g (0.5 mol), 2,2'-azobis (2-methylbutyronitrile) 3 g (0) in a 500 mL three-necked flask. .02 mol) and 150 g of propylene glycol monomethyl ether acetate (PGMEA) were charged, and the mixture was stirred at 90 ° C. for 2 hours, the internal temperature was raised to 100 ° C., and the mixture was 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 4 at 90 ° C. After stirring for a time, PGMEA was added to obtain a binder resin solution (B1) having 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 Denshi Kogyo Co., Ltd., the acid value was 119 (mgKOH / g). Met. Moreover, when the polystyrene-equivalent weight average molecular weight was calculated using a GPC apparatus, the weight average molecular weight was 22,000.

Production Example 5 (Preparation of coloring composition (H1))
In a 50 mL plastic bottle, 4.71 g of the dispersion liquid A3 obtained in Production Example 3, 3.05 g of the binder resin solution B1 obtained in Production Example 4, 2.87 g of the radically polymerizable compound solution D1, "Irgacure" (registered trademark). 907 (manufactured by BASF Japan Ltd.) 0.57 g and 18.80 g of solvent F1 were added and stirred for 3 hours to prepare a coloring composition (H1).

Production Example 6 (Preparation of dispersion (A4))
C. I. Instead of Pigment Green 58, C.I. I. Pigment Yellow 185 (BASF's "Pariodol" (registered trademark) Yellow D1155), except that 150 g was used, as in Production Example 1, C.I. I. Pigment Yellow 185 dispersion (A4) was prepared.

Example 1
In a 50 mL plastic bottle, 10.19 g of the dispersion solution A1 obtained in Production Example 1, 1.39 g of the dispersion solution A2 obtained in Production Example 2, 2.04 g of the binder resin solution B1 obtained in Production Example 4, and an epoxy compound. Add 0.02 g of solution C1, 2.16 g of radically polymerizable compound solution D1, 0.18 g of photopolymerization initiator E1, 0.18 g of photopolymerization initiator E2, and 13.83 g of organic solvent F1 and stir for 3 hours. A coloring composition (G1) was prepared. When the residue of the obtained colored composition was evaluated by the above method, no residue was confirmed on the substrate (A). In addition, a patterning property evaluation was carried out, and it was confirmed that a pattern of 10 μm was formed. Further, a pattern peelability evaluation was carried out, and it was confirmed that a pattern of 10 μm remained. Moreover, when the color mixing evaluation was carried out, T1 / T0 was 0.78.

Examples 2-9, Comparative Examples 1-5
The coloring composition is the same as in Example 1 except that the types and charging ratios of the dispersion liquid, the binder resin solution, the epoxy compound solution, the radically polymerizable compound, the photopolymerization initiator, and the organic solvent are changed as shown in Table 1. (G2 to G14) were obtained. Table 2 summarizes the results of evaluation by the above method using the obtained coloring composition. In the patterning property evaluation, when a pattern was not formed, it was set as "-", and in the subsequent pattern peeling evaluation, it was set as "-" when no pattern remained.

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

Next, the coloring composition H1 obtained in Production Example 5 was applied onto the obtained coated substrate under the condition 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 carried out for 90 seconds with a 0.3 mass% tetramethylammonium hydroxide aqueous solution at 23 ° C. to obtain a coated substrate. With respect to the obtained film, the transmittance T1 at 520 nm was measured using a microspectroscopy 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 the dispersion solution A1 obtained in Production Example 1, 1.39 g of the dispersion solution A4 obtained in Production Example 6, 2.04 g of the binder resin solution B1 obtained in Production Example 4, and an epoxy compound. Add 0.11 g of solution C1, 2.08 g of radically polymerizable compound solution D1, 0.18 g of photopolymerization initiator E1, 0.18 g of photopolymerization initiator E2, and 13.83 g of organic solvent F1 and stir for 3 hours. A coloring composition (G15, E / K = 0.187) was prepared. When the residue of the obtained colored composition was evaluated by the above method, no residue was confirmed on the substrate (A). In addition, a patterning property evaluation was carried out, and it was confirmed that a pattern of 10 μm was formed. Further, a pattern peelability evaluation was carried out, and it was confirmed that a pattern of 10 μm remained. Moreover, when the color mixing evaluation was carried out, T1 / T0 was 0.81.

The coloring composition of the present invention can be suitably used for a color filter substrate and a display device.

Claims (10)

A coloring composition containing a green color material having a metallic phthalocyanine skeleton, a compound represented by the 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 represent hydrogen atoms or alkyl groups having 1 to 3 carbon atoms independently of each other, and n represents an integer of 1 to 30.) The coloring composition according to claim 1, wherein the epoxy equivalent of the compound represented by the general formula (1) is 150 g / mol or more and 200 g / mol or less. The method 1 or 2 according to claim 1 or 2, wherein the ratio of the number of moles E of epoxy groups contained in the solid content to the number of moles K of carboxyl groups contained in the solid content is 0 <E / K <0.20. Coloring composition. The green color material having the metal phthalocyanine skeleton is C.I. I. Pigment Green 58 and / or C.I. I. The coloring composition according to any one of claims 1 to 3, which comprises Pigment Green 59. C. I. Pigment Yellow 150 and / or C.I. I. The coloring composition according to any one of claims 1 to 4, further comprising Pigment Yellow 185. The coloring 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 photocurable 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) The step of applying the coloring composition according to any one of claims 1 to 6 onto a substrate, (B) forming a pattern by exposure and development, and (C) further exposing to the formed pattern is included. , How to manufacture a color filter substrate. A display device having the color filter substrate according to claim 7 or 8.