JP2021117498A - Coloring composition, color filter substrate using the same and method for manufacturing the same, and display device - Google Patents

Abstract

To provide a color filter substrate using a coloring composition which prevents pattern peeling in overcoating processing even when being baked at low temperature, can suppress color mixture of a pattern, and prevents pin unevenness.SOLUTION: A coloring composition contains a colorant, a binder resin, a radical polymerizable compound, a photopolymerization initiator and an organic solvent. The radical polymerizable compound contains dipentaerythritol hexa(meth)acrylate and pentaerythritol tri(meth)acrylate, a ratio of a weight (A) of the dipentaerythritol hexa(meth)acrylate to a weight (B) of the pentaerythritol tri(meth)acrylate is 0.16<A/B<3, and a ratio of a weight (P) of a component excluding the colorant, the radical polymerizable compound, the photopolymerization initiator and the organic solvent to a weight (R) of the radical polymerizable compound is 0.5<P/R<1.2.SELECTED DRAWING: None

Description

The present invention relates to a coloring composition, a color filter substrate using the coloring composition, a method for producing the same, 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 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.

As a coloring composition for a color filter, a coloring composition containing an epoxy compound is known (see, for example, Patent Document 1, Patent Document 2, and Patent Document 3). When an epoxy compound is blended, cross-linking due to thermosetting progresses, and even when the firing temperature is low, color mixing of pixels is less likely to occur when forming a color filter, but there are problems such as insufficient color mixing suppression and storage stability. , Improvement was required.

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

INDUSTRIAL APPLICABILITY According to the present invention, a coloring composition that is less likely to cause pattern peeling during recoating even when fired at a low temperature, can suppress color mixing of patterns, and is less likely to cause pin unevenness, and a color using such a coloring composition. An object of the present invention is to provide a filter substrate and a display device.

In order to solve the above problems, the coloring composition of the present invention has the following constitution. That is,
A coloring composition containing a coloring material, a binder resin, a radically polymerizable compound, a photopolymerization initiator and an organic solvent, wherein the radically polymerizable compound is dipentaerythritol hexa (meth) acrylate and pentaerythritol tri (meth) acrylate. The ratio of the weight (A) of the dipentaerythritol hexa (meth) acrylate to the weight (B) of the pentaerythritol tri (meth) acrylate is 0.16 <A / B <3, and the colorant The ratio of the weight (P) of the components excluding the radically polymerizable compound, the photopolymerization initiator and the organic solvent to the weight (R) of the radically polymerizable compound is 0.5 <P / R <1.2. A coloring composition.

The color filter substrate of the present invention has the following configuration. That is,
A color filter substrate having pixels made of a photocured product of the coloring composition.

The method for manufacturing a color filter substrate of the present invention has the following configuration. That is,
(A) A method for manufacturing a color filter substrate, which comprises a step of applying the coloring composition onto a substrate, (B) forming a pattern by exposure and development, and (C) further exposing the formed pattern. be.

The display device of the present invention has the following configuration. That is, it is a display device having the color filter substrate.

The coloring composition of the present invention preferably further contains a photosensitizer.

The coloring composition further containing a photosensitizer, which is a preferred embodiment of the present invention, is the weight (P) of the components excluding the coloring material, the radically polymerizable compound, the photopolymerization initiator, the organic solvent, and the photosensitizer. The ratio of the weight (R) of the radically polymerizable compound to the radically polymerizable compound is more preferably 0.5 <P / R <1.2.

In the coloring composition of the present invention, it is preferable that the number of moles of double bonds M contained in the solid content Tgram excluding the coloring material satisfies 160 <T / M <220.

In the coloring composition of the present invention, it is preferable that the coloring material contains a diketopyrrolopyrrole pigment having a bromine group.

In the coloring composition of the present invention, it is preferable that the photosensitizer is a thioxanthone-based sensitizer.

In the coloring composition of the present invention, the ratio of the weight (K) of the photosensitizer to the weight (L) of the photopolymerization initiator is preferably 0.3 <K / L <0.6.

The coloring composition of the present invention preferably has a total content of dipentaerythritol hexa (meth) acrylate and pentaerythritol tri (meth) acrylate in the radically polymerizable compound of 70% by mass or more.

According to the coloring composition of the present invention, it is possible to provide a coloring composition in which pattern peeling during recoating is less likely to occur even when fired at a low temperature, color mixing of patterns can be suppressed, and pin unevenness is less likely to occur. Can be done.

The coloring composition of the present invention is a coloring composition containing a coloring material, a binder resin, a radically polymerizable compound, a photopolymerization initiator and an organic solvent, and the radically polymerizable compound is a dipentaerythritol hexa (meth) acrylate. And pentaerythritol tri (meth) acrylate, the ratio of the weight (A) of dipentaerythritol hexa (meth) acrylate to the weight (B) of pentaerythritol tri (meth) acrylate is 0.16 <A / B <. The ratio of the weight (P) of the component excluding the coloring material, the radically polymerizable compound, the photopolymerization initiator, and the organic solvent to the weight (R) of the radically polymerizable compound is 0.5 <P. It is a coloring composition with / R <1.2, and even if it is fired at a low temperature, pattern peeling during recoating is unlikely to occur, and it is possible to suppress pattern color mixing and suppress the occurrence of pin unevenness. can.

The coloring composition of the present invention contains a 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, diketopyrrolopyrrole coloring material having a bromine group, and the like. From the viewpoint of pixel brightness characteristics, PR254, PR177, and diketopyrrolopyrrole coloring material having a bromine group are preferable, and from the viewpoint of brightness, vividness, and color mixing prevention, a diketopyrrolopyrrole coloring material having a bromine group is used. Is preferable.

Examples of the yellow color material include organic pigments, inorganic pigments, dyes and the like, and examples thereof include C.I. 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.

Examples of the green color material include organic pigments, inorganic pigments, dyes and the like, and examples thereof include C.I. I. Pigment Green (hereinafter referred to as "PG") PG1, PG2, PG4, PG7, PG8, PG10, PG13, PG14, PG15, PG17, PG18, PG19, PG26, PG36, PG38, PG39, PG45, PG48, PG50, PG51, PG54 , PG55, PG58, PG59 (all of the above numbers are color index Nos.) and the like. Two or more of these may be contained.

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 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. 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 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. Acrylic vinyl compounds such as unsaturated carboxylic acid alkyl esters, styrene, p-methyl styrene, o-methyl styrene, m-methyl styrene, α-methyl styrene, unsaturated carboxylic acid amino alkyl esters such as amino ethyl acrylate, and 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, and the radically polymerizable compound contains dipentaerythritol hexa (meth) acrylate and pentaerythritol tri (meth) acrylate. The total content of dipentaerythritol hexa (meth) acrylate and pentaerythritol tri (meth) acrylate in the radically polymerizable compound is such as prevention of color mixing, suppression of color transfer, suppression of pin unevenness, solubility during recoating, and processability. From the viewpoint, it is preferably 70% by mass or more. The radically polymerizable compound referred to here refers to a compound that reacts by radical polymerization, and refers to a compound having a weight average molecular weight of 1,000 or less. 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. In addition, the coloring composition of the present invention may contain a radically polymerizable compound other than dipentaerythritol hexa (meth) acrylate and pentaerythritol tri (meth) acrylate.

Examples of radically polymerizable compounds other than dipentaerythritol hexa (meth) acrylate and pentaerythritol tri (meth) acrylate include dipentaerythritol penta (meth) acrylate, tetratrimethylol propanthry (meth) acrylate, and pentaerythritol tetra (pentaerythritol tetra (meth) acrylate. Ethylene oxide or propylene oxide modified products such as meta) acrylate, penta (meth) acryloyloxydipentaerythritol monosuccinate, styrene derivatives, polyfunctional maleimide compounds, poly (meth) acrylate carbamate, adipic acid 1,6- Oligomers such as hexanediol (meth) acrylic acid ester, propylene oxide (meth) acrylic acid ester anhydride, diethylene glycol (meth) acrylic acid ester of trimellitic acid, rosin-modified epoxydi (meth) acrylate, and alkyd-modified (meth) acrylate. Bifunctional (meth) acrylates such as tripropylene glycol di (meth) acrylate and 1,6-hexanediol di (meth) acrylate, trimethylpropantri (meth) acrylate, triacrylic formal, bisphenoxyethanol full orange acrylate, di Cyclopentanedienyldiacrylates, alkyl modified products thereof, alkyl ether modified products, alkyl ester modified products and the like can be mentioned.

The coloring composition of the present invention contains dipentaerythritol hexa (meth) acrylate and pentaerythritol tri (meth) acrylate, and contains the weight (A) of dipentaerythritol hexa (meth) acrylate and pentaerythritol tri (meth) acrylate. A coloring composition having a weight (B) ratio of 0.16 <A / B <3. When the ratio (A / B) of the weight (A) of the dipentaerythritol hexa (meth) acrylate to the weight (B) of the pentaerythritol tri (meth) acrylate is 0.16 or less, the patterning property is poor and the temperature is low. When fired, pattern peeling is likely to occur during recoating, while when (A / B) is 3 or more, color mixing of the pattern cannot be suppressed. The ratio (A / B) of the weight (A) of the dipentaerythritol hexa (meth) acrylate to the weight (B) of the pentaerythritol tri (meth) acrylate is determined from the viewpoint of further improving the suppression of pattern peeling during the recoating process. It is preferably 0.24 or more, and more preferably 0.3 or more. The ratio (A / B) of the weight (A) of the dipentaerythritol hexa (meth) acrylate to the weight (B) of the pentaerythritol tri (meth) acrylate is 2.4 or less from the viewpoint of further improving color mixing prevention. Is preferable, and more preferably 1.6 or less.

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.

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-based compounds, and titanosen-based 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 Japan 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 Japan 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 compound include 2-mercaptobenzothiazole and the like. 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, and it is more preferable to use a photosensitizer described later in combination from the viewpoint of suppressing color transfer and preventing color mixing.

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 further contains a dispersant, a chain transfer agent, a photosensitizer, an organic solvent, a polymerization inhibitor, an adhesion improver, a surfactant, an organic acid, an organic amino compound, a curing agent and the like. You may.

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 time-of-flight 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 small molecule dispersants such as pigment intermediates and derivatives, and polymer 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. Commercially available polymer dispersants having a basic group include, for example, "Solspers" (registered trademark) (manufactured by Nippon Loubrisol Co., Ltd.), "Efka" (registered trademark) (manufactured by BASF), and "Ajispar". (Registered trademark) (manufactured by Ajinomoto Fine-Techno Co., Ltd.), "BYK" (registered trademark) (manufactured by Big Chemie Japan Co., Ltd.) can be mentioned. Two or more of these may be contained. Among them, "Solspers" (registered trademark) 24000 (manufactured by Nippon Loubrizol Co., Ltd.), "EFKA" (registered trademark) 4300, 4330 (manufactured by BASF), 4340 (manufactured by BASF), "Ajispar" (registered trademark) PB821, PB822 (manufactured by Ajinomoto Fine-Techno Co., Ltd.) and "BYK" (registered trademark) 161 to 163, 2000, 2001, 6919, 21116 (manufactured by Big Chemie Japan Co., Ltd.) 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-mercaptobutyryloxy) 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.), "Karenzu" (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 preferably further contains a photosensitizer from the viewpoint of preventing color mixing. Examples of the photosensitizer 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. A thioxanthone-based sensitizer is preferable from the viewpoint of suppressing color transfer and preventing color mixing of the coloring composition of the present invention. Further, the ratio of the weight (K) of the photosensitizer to the weight (L) of the photopolymerization initiator is 0.3 <K / L <0.6 from the viewpoint of suppressing color transfer and preventing color mixing. preferable.

The coloring composition of the present invention contains 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, solvent naphtha, etc. Can be mentioned. Two or more of these may be contained.

In the coloring composition of the present invention, the weight (P) of the components excluding the coloring material, the radically polymerizable compound, the photopolymerization initiator, and the organic solvent contained in the coloring composition and the weight (R) of the radically polymerizable compound. The ratio is 0.5 <P / R <1.2. When the P / R is 1.2 or more, the color transfer suppression, the solubility at the time of the recoating process, and the processability become insufficient. P / R <1.1, more preferably P / R <0.9. Further, when the P / R is 0.5 or less, the film forming property and the suppression of pin unevenness become insufficient. P / R> 0.4 is preferable, P / R> 0.5 is more preferable, and P / R> 0.65 is particularly preferable.

When the coloring composition of the present invention has a preferred embodiment containing a photosensitizer, the components excluding the coloring material, the radically polymerizable compound, the photopolymerization initiator, the organic solvent, and the photosensitizer contained in the coloring composition. More preferably, the ratio of the weight (P) to the weight (R) of the radically polymerizable compound is 0.5 <P / R <1.2. By setting P / R to 0.5 <P / R <1.2, a composition preferable from the viewpoints of dye color transfer suppression, film formation property, pin unevenness suppression, solubility during recoating process, and processability can be obtained. Obtainable. From the viewpoint of suppressing color transfer, the weight (P) of the components excluding the coloring material, the radically polymerizable compound, the photopolymerization initiator, the organic solvent, and the photosensitizer contained in the coloring composition and the weight of the radically polymerizable compound. The ratio P / R of (R) is more preferably P / R <1.1, and even more preferably P / R <0.9. In addition, from the viewpoint of solubility and processability during recoating, the weight of the components excluding the coloring material, radically polymerizable compound, photopolymerization initiator, organic solvent, and photosensitizer contained in the coloring composition ( The ratio P / R of P) to the weight (R) of the radically polymerizable compound is more preferably P / R <1.1, still more preferably P / R <0.9. Further, from the viewpoint of film forming property and suppression of pin unevenness, P / R> 0.65 is more preferable.

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. Used for polymerization termination, etc. 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 improver, 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.

In the coloring composition of the present invention, when the number of moles of double bonds M contained in the solid content Tgram excluding the coloring material satisfies 160 <T / M <220, color transfer is suppressed and recoating is performed. It is preferable from the viewpoint of solubility and processability. The solid content referred to here refers to all the components contained in the coloring composition except the organic solvent. From the viewpoint of color transfer suppression, solubility during recoating, and processability, the ratio T / M of the number of moles of the double bond contained to the solid content Tgram excluding the coloring material is T / M <220. Is preferable, and T / M <200 is more preferable. Further, from the viewpoint of suppressing pin unevenness, the ratio T / M of the number of moles M of the double bond contained in the solid content Tgram excluding the coloring material is preferably T / M> 160, more preferably T / M>. It is 170.

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. 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. Even if the coloring composition of the present invention is fired at 100 ° C. or lower, pattern peeling is unlikely to occur during recoating, and pattern color mixing can be suppressed. Therefore, a film that may be deformed by heat can be used as a substrate. However, it is possible to form pixels, and it can be suitably used for manufacturing a film-like color filter substrate in which each colored pixel is formed on a film.

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 or 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 provides a certain gap between the photo spacer and the substrate and can be filled with a liquid crystal compound or the like between the gaps, the step of arranging the spacer can be omitted when manufacturing the liquid crystal display device. 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 the 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. When the coloring composition of the present invention is used, even if it is fired at 100 ° C. or lower, pattern peeling during recoating is unlikely to occur, and color mixing of the pattern can be suppressed. Therefore, (A) the coloring composition of the present invention. It can be suitably used for manufacturing a color filter substrate through the steps of (B) forming a pattern by exposure and development after coating the substance on the substrate and then (D) heat-treating at 100 ° C. or lower. can. In particular, when the coloring composition of the present invention is used, a color filter substrate can be produced in a process of heat treatment at 100 ° C. or lower, so that a film that is easily denatured or deteriorated by heat or a film that is easily denatured or deteriorated by heat occurs. A color filter substrate can be manufactured by using a substrate including a device element such as an easy organic EL element.

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. The 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 electrophoretic 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 such as wearable terminals, electronic signboards, digital signage, and electronic shelf labels that display with outdoor light or indoor light. Since the coloring composition of the present invention can form colored pixels on a film, it can be suitably used for electronic paper, curved displays, and flexible displays using a film-like color filter substrate. Further, even if the coloring composition of the present invention is fired at 100 ° C. or lower, pattern peeling is unlikely to occur during recoating, and color mixing of the pattern can be suppressed. Therefore, the organic EL may be deteriorated by heat. Since it can be formed on a substrate containing an element, it can be suitably used for an organic EL display such as a silicon OLED.

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, the 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. First, the evaluation methods in Examples and Comparative Examples will be described. The other components used in each of the examples and comparative examples are as follows.

Radical polymerizable compound solution D1: Propropylene glycol monomethyl ether acetate solution in which dipentaerythritol hexaacrylate is diluted to 50% by mass D2: Propropylene glycol monomethyl ether acetate solution in which pentaerythritol triacrylate is diluted to 50% by mass Photopolymerization initiator E1: "ADEKA Acrylate" (registered trademark) NCI831 (manufactured by ADEKA Corporation)
E2: "Irgacure" (registered trademark) 379 (manufactured by BASF Japan Ltd.)
Photosensitizer F1: 2,4-diethylthioxanthone Organic solvent G1: Propylene glycol monomethyl ether acetate <Peeling evaluation>
The coloring compositions obtained in Examples 1 to 8 and Comparative Examples 1 to 5 described later 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 a line & space pattern of 20 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 coloring composition (J1) obtained in Production Example 5 described later was applied onto the obtained film-coated substrate to a thickness of 2.3 μm, 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. The presence or absence of a pattern on the substrate was confirmed with a microscope and evaluated according to the following evaluation criteria.
A: No pattern peeling B: With pattern peeling <Color mixing evaluation>
The coloring compositions obtained in Examples 1 to 8 and Comparative Examples 1 to 5 described later were applied onto a glass substrate and dried at 90 ° C. for 10 minutes. Then, it was exposed with ^{i-line 40 mJ / cm 2} through a photomask having a line & space pattern of 20 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. With respect to the obtained film, the transmittance T0 at 650 nm was measured using a microspectrophotometer LCF-100MA manufactured by Otsuka Electronics Co., Ltd.

Next, the coloring composition (J1) obtained in Production Example 5 described later 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 650 nm was measured using a microspectrophotometer 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. In the color mixing evaluation, when the pattern did not remain, it was set as "-".

<Pin unevenness evaluation>
The composition for black matrix (J2) obtained in Production Example 6 described later was spin-coated on a glass substrate and dried at 120 ° C. for 120 seconds. The obtained coating film was exposed to i-ray 200 mJ / cm ² and then immersed in a 2.0 mass% sodium hydroxide aqueous solution for 2 minutes, washed with pure water, and fired in an oven at 230 ° C. for 30 minutes. A black matrix substrate having a 1.5 μm film formed was obtained.

After applying the coloring compositions obtained in Examples 1 to 8 and Comparative Examples 1 to 5 described later on the obtained black matrix substrate, a cylindrical pedestal (material polyethylene) having a diameter of 1.5 cm and a height of 1 cm. It was dried under reduced pressure until it reached 40 Pa. Then, the substrate was dried on a hot plate at 100 ° C. for 3 minutes. The obtained substrate was visually confirmed under a Na lamp to confirm the presence or absence of unevenness derived from the cylindrical pedestal, and evaluated according to the following evaluation criteria.
A: No unevenness derived from the pedestal B: Unevenness derived from the pedestal <Color transfer resistance>
The photosensitive compositions for color filters obtained in Examples 1 to 8 and Comparative Examples 1 to 5 described later were spin-coated on a glass substrate and dried at 90 ° C. for 10 minutes. The obtained coating film was exposed to i-line 40 mJ / cm ² and then shower-developed with a 0.3 mass% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 50 seconds and washed with pure water. The substrate was fired at 230 ° C. for 30 minutes to obtain a substrate having a thickness of 2.3 μm. The coloring composition (J3) obtained in Production Example 7 described later was spin-coated on the obtained substrate and dried at 90 ° C. for 10 minutes. ^{The obtained coating film was exposed to i-line 200 mJ / cm 2} via a photomask having a circular pattern with a diameter of 30 μm, and then shower-developed with a 0.3 mass% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 50 seconds. Was washed with pure water to obtain a coated substrate having a circular hole having a thickness of 2 μm and a diameter of 30 μm. The brightness Y0 at the center of the circular hole was measured using a microspectrophotometer LCF-100MA manufactured by Otsuka Electronics Co., Ltd. Next, after firing the coated substrate at 230 ° C. for 30 minutes, the brightness Y1 at the center of the circular hole is measured and Y1 / Y0 is calculated. The color transfer resistance, which is an index of the difficulty of the phenomenon of permeation of the color material inside, was evaluated. The closer the value of Y1 / Y0 is to 1, the less likely it is that color transfer will occur, which is preferable.

<Solubility evaluation>
The coloring compositions obtained in Examples 1 to 8 and Comparative Examples 1 to 5 described later were applied onto a glass substrate and dried at 90 ° C. for 10 minutes. Then, it was exposed to i-line 40 mJ through a photomask, shower-developed with a 0.3 mass% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 50 seconds, and then washed with pure water. Next, the substrate was fired at 100 ° C. for 30 minutes to obtain a film-coated substrate having a thickness of 2.3 μm.

The coloring composition (J1) obtained in Production Example 5 described later was applied onto the obtained film-coated substrate to a thickness of 2.3 μm, and dried at 90 ° C. for 10 minutes. Shower development was carried out with a 0.3 mass% tetramethylammonium hydroxide aqueous solution at 23 ° C., and the time until the coloring derived from the coloring composition (J1) disappeared was confirmed and evaluated according to the following evaluation criteria.
A: Time until the coloring derived from the coloring composition (J1) disappears within 30 seconds B: Time until the coloring derived from the coloring composition (J1) disappears 30 to 60 seconds C: Derived from the coloring composition (J1) Production Example 1 (Preparation of dispersion liquid (A1))
176.3 g of anhydrous tert-amyl alcohol (2.0 mol) and 114.7 g of sodium-tert-amyl alkoxide (1.1 mol) were charged in a 500 mL three-necked flask under a nitrogen atmosphere, and the internal temperature was raised to 100 while stirring. The temperature was raised to ° C. and the reaction was carried out to prepare an alcoholate solution.

In another 500 mL three-necked flask, 84.9 g of diisopropyl succinate (0.4 mol) and 145.6 g of 4-bromobenzonitrile (0.8 mol) were charged, and the internal temperature was raised to 85 ° C. with stirring. To dissolve and prepare a mixed solution.

The above mixed solution was added dropwise over 3 hours while stirring at an internal temperature of a three-necked flask containing the above alcoholate solution at 100 ° C. After completion of the dropping, the mixture was heated and stirred at an internal temperature of 90 ° C. for 12 hours to obtain a suspension.

In yet another 500 mL three-necked flask, 640 g of methanol (20.0 mol), 720 g of water (40.0 mol) and 300 g of acetic acid (10.0 mol) were charged, and the mixture was stirred while cooling the internal temperature to -10 ° C. To obtain the mixture.

The above suspension was added dropwise over 3 hours while maintaining the internal temperature of the three-necked flask containing the above mixture at −5 ° C. or lower and stirring at high speed. After the completion of the dropping, the mixture was further stirred for 7 hours, and then the reaction solution was washed and filtered until the filtrate was not colored and the salt was not precipitated. The collected filtrate was dried at 80 ° C. for 24 hours, and the obtained solid substance was pulverized to obtain 112 g of a diketopyrrolopyrrole pigment (formula (1)) having a bromine group. A diketopyrrolopyrrole pigment having a bromine group was further synthesized by the same method, and 150 g of a diketopyrrolopyrrole pigment having a bromine group was prepared.

The obtained diketopyrrolopyrrole pigment having a bromine group 150 g, "BYK" (registered trademark) LPN6919 (manufactured by Big Chemie Japan Co., Ltd., polymer dispersant solution (60 mass% propylene glycol monomethyl ether solution)) 66.6 g , "Cyclomer" (registered trademark) ACA250 (manufactured by Daicel Chemical Co., Ltd., 45% by mass dipropylene glycol monomethyl ether solution) 88.9 g and propylene glycol monomethyl ether (PMA) 694.5 g were mixed to prepare a slurry. .. 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 to disperse a diketopyrrolopyrrole pigment having a bromine group. Liquid (A1) was prepared.

Production Example 2 (Preparation of dispersion (A2))
Instead of the diketopyrrolopyrrole pigment having a bromine group, C.I. I. Pigment Red 177 was used in the same manner as in Production Example 1 except that 150 g of Pigment Red 177 was used. I. Pigment Red 177 dispersion (A2) was prepared.

Production Example 3 (Preparation of dispersion (A3))
Instead of the diketopyrrolopyrrole pigment having a bromine group, C.I. I. Pigment Blue 15: 6 was used in the same manner as in Production Example 1 except that 150 g of Pigment Blue 15: 6 was used. I. Pigment Blue 15: 6 dispersion (A3) was prepared.

Production Example 4 (Synthesis of binder resin solution (B1))
In a 500 mL three-necked flask, 33 g (0.3 mol) of methyl methacrylate, 33 g (0.3 mol) of styrene, 35 g (0.5 mol) of methacrylic acid, 2,2'-azobis (2-methylbutyronitrile). 3 g (0.02 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 prepare the reaction solution. Obtained. 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 to 90 ° C. After stirring for 4 hours, 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 (J1))
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, and 2 radically polymerizable compound solutions (D1). .87 g, 0.57 g of "Irgacure" (registered trademark) 907 (manufactured by BASF Japan Ltd.) and 18.80 g of the organic solvent propylene glycol monomethyl ether acetate (G1) were added, and the mixture was stirred for 3 hours to prepare a coloring composition. (J1) was prepared.

Production Example 6 (Preparation of composition for black matrix (J2))
30 g of carbon powder (MA-8, manufactured by Mitsubishi Materials Co., Ltd.), 20 g of acrylic copolymer solution ("Cyclomer" (registered trademark) PACA-250, manufactured by Daicel Chemical Industry Co., Ltd.), 37 g of cyclohexanone. After mixing and dispersing for 1 hour with a homogenizer, 10 g of dipentaerythritol hexaacrylate and 3 g of photopolymerization initiator "IRGACURE" (registered trademark) 369 (manufactured by Ciba Specialty Chemicals Co., Ltd.) were mixed and black. A matrix composition (J2) was obtained.

Production Example 7 (Preparation of coloring composition (J3))
To a three-necked flask, 15 g of Acid Red 289, 150 g of chloroform, and 8.9 g of N, N-dimethylformamide were added. Then, the mixture was cooled to 20 ° C. or lower, and 10.9 g of thionyl chloride was added dropwise. After completion of the dropping, the temperature was raised to 50 ° C. and stirred for 5 hours, then cooled to 20 ° C., a mixture of 12.5 g of 2-ethylhexylamine and 22.1 g of triethylamine was added, and the mixture was stirred at 20 ° C. for 5 hours for reaction. A mixture was obtained. The solvent was distilled off from the obtained reaction mixture by a rotary evaporator and purified to obtain 10 g of a xanthene dye.

A slurry was prepared by mixing 10 g of the obtained xanthene dye, 90 g of PB15: 6, 67 g of "BYK" (registered trademark) 6919, 67 g of "Cyclomer" ACA250, and 766 g of PMA. A beaker containing the slurry is connected to a dyno mill with a tube, and zirconia beads having a diameter of 0.3 mm are used as a medium for dispersion treatment at a peripheral speed of 10 m / s for 8 hours to prepare a dispersion liquid (A4) containing a dye. did.

In a 200 mL plastic bottle, 19.8 g of the obtained dispersion (A4), 23.16 g of the binder resin solution (B1) obtained in Production Example 4, "Kayarad" (registered trademark) DPHA (Nippon Kayaku Co., Ltd.) ), Polyfunctional radical-polymerizable compound) (23.50 g), "ADEKA ARCULDS" (registered trademark) N-1919 (ADEKA Corporation, oxime ester-based photopolymerization initiator) 0.31 g, dipropylene glycol 60.00 g of methyl ether acetate (DPMA) was added and stirred for 3 hours to prepare a coloring composition (J3).
(Example 1)
In a 50 mL plastic bottle, 11.09 g of the dispersion liquid (A1) obtained in Production Example 1, 4.75 g of the dispersion liquid (A2) obtained in Production Example 2, and the binder resin solution obtained in Production Example 4 ( 1.19 g of B1), 2.99 g of radically polymerizable compound solution (D1), 1.28 g of radically polymerizable compound solution (D2), 0.07 g of photopolymerization initiator (E1), photopolymerization initiator ( 0.14 g of E2), 0.07 g of photosensitizer 2,4-diethylthioxanthone (F1), and 23.43 g of organic solvent propylene glycol monomethyl ether acetate (G1) were added, and the mixture was stirred for 3 hours to obtain a coloring composition. The product (H1) was prepared. When the obtained colored composition was evaluated for peeling by the above method, no pattern peeling was confirmed. Further, when the color mixing evaluation was carried out by the above method, T1 / T0 was 0.94. Moreover, when the pin unevenness was evaluated by the above method, the unevenness derived from the pedestal was not confirmed. Further, when the color transfer evaluation was carried out by the above method, Y1 / Y0 was 0.99.
(Example 2)
The coloring composition (H2) was prepared in the same manner as in Example 1 except that the addition amount of the radically polymerizable compound (D1) was changed to 2.13 g and the addition amount of the radically polymerizable compound solution (D2) was changed to 2.13 g. Prepared. When the peeling evaluation was performed by the above method using the obtained coloring composition, no pattern peeling was confirmed. Further, when the color mixing evaluation was carried out by the above method, T1 / T0 was 0.96. Moreover, when the pin unevenness was evaluated by the above method, the unevenness derived from the pedestal was not confirmed. Further, when the color transfer evaluation was carried out by the above method, Y1 / Y0 was 0.99.
(Example 3)
The coloring composition (H3) was prepared in the same manner as in Example 1 except that the addition amount of the radically polymerizable compound (D1) was changed to 1.07 g and the addition amount of the radically polymerizable compound solution (D2) was changed to 3.20 g. Prepared. When the peeling evaluation was performed by the above method using the obtained coloring composition, no pattern peeling was confirmed. Further, when the color mixing evaluation was carried out by the above method, T1 / T0 was 0.98. Moreover, when the pin unevenness was evaluated by the above method, the unevenness derived from the pedestal was not confirmed. Further, when the color transfer evaluation was carried out by the above method, Y1 / Y0 was 0.99.
(Example 4)
The coloring composition (H4) was prepared in the same manner as in Example 1 except that the addition amount of the radically polymerizable compound (D1) was changed to 0.64 g and the addition amount of the radically polymerizable compound solution (D2) was changed to 3.63 g. Prepared. When the peeling evaluation was performed by the above method using the obtained coloring composition, no pattern peeling was confirmed. Further, when the color mixing evaluation was carried out by the above method, T1 / T0 was 0.99. Moreover, when the pin unevenness was evaluated by the above method, the unevenness derived from the pedestal was not confirmed. Further, when the color transfer evaluation was carried out by the above method, Y1 / Y0 was 0.99.
(Example 5)
The amount of the binder resin solution (B1) obtained in Production Example 4 was 0.71 g, the amount of the radically polymerizable compound (D1) was 3.26 g, and the amount of the radically polymerizable compound solution (D2) was 1. A coloring composition (H5) was prepared in the same manner as in Example 1 except that the weight was changed to 40 g. When the peeling evaluation was performed by the above method using the obtained coloring composition, no pattern peeling was confirmed. Further, when the color mixing evaluation was carried out by the above method, T1 / T0 was 0.95. Moreover, when the pin unevenness was evaluated by the above method, the unevenness derived from the pedestal was not confirmed. Further, when the color transfer evaluation was carried out by the above method, Y1 / Y0 was 1.00.
(Example 6)
The addition amount of the binder resin solution (B1) obtained in Production Example 4 was 0.71 g, the addition amount of the radically polymerizable compound (D1) was 1.86 g, and the addition amount of the radically polymerizable compound solution (D2) was 2. A coloring composition (H6) was prepared in the same manner as in Example 1 except that the weight was changed to 79 g. When the peeling evaluation was performed by the above method using the obtained coloring composition, no pattern peeling was confirmed. Further, when the color mixing evaluation was carried out by the above method, T1 / T0 was 0.98. Moreover, when the pin unevenness was evaluated by the above method, the unevenness derived from the pedestal was not confirmed. Further, when the color transfer evaluation was carried out by the above method, Y1 / Y0 was 1.00.
(Example 7)
The amount of the binder resin solution (B1) obtained in Production Example 4 was 1.68 g, the amount of the radically polymerizable compound (D1) was 2.71 g, and the amount of the radically polymerizable compound solution (D2) was 1. A coloring composition (H7) was prepared in the same manner as in Example 1 except that the weight was changed to 16 g. When the peeling evaluation was performed by the above method using the obtained coloring composition, no pattern peeling was confirmed. Further, when the color mixing evaluation was carried out by the above method, T1 / T0 was 0.94. Moreover, when the pin unevenness was evaluated by the above method, the unevenness derived from the pedestal was not confirmed. Further, when the color transfer evaluation was carried out by the above method, Y1 / Y0 was 0.98.
(Example 8)
The addition amount of the binder resin solution (B1) obtained in Production Example 4 was 1.68 g, the addition amount of the radically polymerizable compound (D1) was 1.55 g, and the addition amount of the radically polymerizable compound solution (D2) was 2. A coloring composition (H8) was prepared in the same manner as in Example 1 except that the weight was changed to 33 g. When the peeling evaluation was performed by the above method using the obtained coloring composition, no pattern peeling was confirmed. Further, when the color mixing evaluation was carried out by the above method, T1 / T0 was 0.98. Moreover, when the pin unevenness was evaluated by the above method, the unevenness derived from the pedestal was not confirmed. Further, when the color transfer evaluation was carried out by the above method, Y1 / Y0 was 0.98.
(Comparative Example 1)
The coloring composition (H9) was prepared in the same manner as in Example 1 except that the addition amount of the radically polymerizable compound (D1) was changed to 3.28 g and the addition amount of the radically polymerizable compound solution (D2) was changed to 0.98 g. Prepared. When the peeling evaluation was performed by the above method using the obtained coloring composition, no pattern peeling was confirmed. Further, when the color mixing evaluation was carried out by the above method, T1 / T0 was 0.71. Moreover, when the pin unevenness was evaluated by the above method, the unevenness derived from the pedestal was not confirmed. Further, when the color transfer evaluation was carried out by the above method, Y1 / Y0 was 0.99.
(Comparative Example 2)
The coloring composition (H10) was prepared in the same manner as in Example 1 except that the addition amount of the radically polymerizable compound (D1) was changed to 0.00 g and the addition amount of the radically polymerizable compound solution (D2) was changed to 4.26 g. Prepared. When the peeling evaluation was performed by the above method using the obtained coloring composition, pattern peeling was confirmed. Moreover, when the color mixing evaluation was carried out by the above method, no pattern remained. Moreover, when the pin unevenness was evaluated by the above method, the unevenness derived from the pedestal was not confirmed. Further, when the color transfer evaluation was carried out by the above method, Y1 / Y0 was 0.99.
(Comparative Example 3)
The amount of the binder resin solution (B1) obtained in Production Example 4 was 1.68 g, the amount of the radically polymerizable compound (D1) was 3.10 g, and the amount of the radically polymerizable compound solution (D2) was 0. A coloring composition (H11) was prepared in the same manner as in Example 1 except that the weight was changed to 78 g. When the peeling evaluation was performed by the above method using the obtained coloring composition, no pattern peeling was confirmed. Further, when the color mixing evaluation was carried out by the above method, T1 / T0 was 0.63. Moreover, when the pin unevenness was evaluated by the above method, the unevenness derived from the pedestal was not confirmed. Further, when the color transfer evaluation was carried out by the above method, Y1 / Y0 was 0.98.
(Comparative Example 4)
The addition amount of the binder resin solution (B1) obtained in Production Example 4 was 0.03 g, the addition amount of the radically polymerizable compound (D1) was 3.64 g, and the addition amount of the radically polymerizable compound solution (D2) was 1. A coloring composition (H12) was prepared in the same manner as in Example 1 except that the weight was changed to 56 g. When the peeling evaluation was performed by the above method using the obtained coloring composition, no pattern peeling was confirmed. Further, when the color mixing evaluation was carried out by the above method, T1 / T0 was 0.95. Moreover, when the pin unevenness was evaluated by the above method, unevenness derived from the pedestal was confirmed. Further, when the color transfer evaluation was carried out by the above method, Y1 / Y0 was 1.00.
(Comparative Example 5)
The amount of the binder resin solution (B1) obtained in Production Example 4 was 2.16 g, the amount of the radically polymerizable compound (D1) was 2.44 g, and the amount of the radically polymerizable compound solution (D2) was 1. A coloring composition (H13) was prepared in the same manner as in Example 1 except that the weight was changed to 05 g. When the peeling evaluation was performed by the above method using the obtained coloring composition, no pattern peeling was confirmed. Further, when the color mixing evaluation was carried out by the above method, T1 / T0 was 0.94. Moreover, when the pin unevenness was evaluated by the above method, the unevenness derived from the pedestal was not confirmed. Further, when the color transfer evaluation was carried out by the above method, Y1 / Y0 was 0.97.

Table 1 shows the addition amount of each additive component in the above Examples and Comparative Examples, and Table 2 summarizes the results of evaluating each of the obtained coloring compositions by the above method.

(Example 9)
In a 50 mL plastic bottle, 11.09 g of the dispersion liquid (A1) obtained in Production Example 1, 4.75 g of the dispersion liquid (A2) obtained in Production Example 2, and the binder resin solution obtained in Production Example 4 ( 1.19 g of B1), 1.07 g of radically polymerizable compound solution (D1), 3.20 g of radically polymerizable compound solution (D2), 0.07 g of photopolymerization initiator (E1), and photopolymerization initiator (D1). 0.14 g of E2) and 23.43 g of the organic solvent propylene glycol monomethyl ether acetate (G1) were added, and the mixture was stirred for 3 hours to prepare a coloring composition (H14). When the obtained colored composition was evaluated for peeling by the above method, no pattern peeling was confirmed. Further, when the color mixing evaluation was carried out by the above method, T1 / T0 was 0.97. Moreover, when the pin unevenness was evaluated by the above method, the unevenness derived from the pedestal was not confirmed. Further, when the color transfer evaluation was carried out by the above method, Y1 / Y0 was 0.99.
(Example 10)
In a 50 mL plastic bottle, 11.09 g of the dispersion liquid (A1) obtained in Production Example 1, 4.75 g of the dispersion liquid (A2) obtained in Production Example 2, and the binder resin solution obtained in Production Example 4 ( 1.19 g of B1), 1.07 g of radically polymerizable compound solution (D1), 3.20 g of radically polymerizable compound solution (D2), 0.07 g of photopolymerization initiator (E1), and photopolymerization initiator (D1). 0.14 g of E2), 0.11 g of photosensitizer 2,4-diethylthioxanthone (F1), and 23.43 g of organic solvent propylene glycol monomethyl ether acetate (G1) were added, and the mixture was stirred for 3 hours to obtain a coloring composition. The product (H15) was prepared. When the obtained colored composition was evaluated for peeling by the above method, no pattern peeling was confirmed. Further, when the color mixing evaluation was carried out by the above method, T1 / T0 was 0.98. Moreover, when the pin unevenness was evaluated by the above method, the unevenness derived from the pedestal was not confirmed. Further, when the color transfer evaluation was carried out by the above method, Y1 / Y0 was 0.99.
(Example 11)
In a 50 mL plastic bottle, 11.09 g of the dispersion liquid (A1) obtained in Production Example 1, 4.75 g of the dispersion liquid (A2) obtained in Production Example 2, and the binder resin solution obtained in Production Example 4 ( 1.19 g of B1), 1.07 g of radically polymerizable compound solution (D1), 3.20 g of radically polymerizable compound solution (D2), 0.07 g of photopolymerization initiator (E1), and photopolymerization initiator (D1). 0.14 g of E2), 0.15 g of photosensitizer 2,4-diethylthioxanthone (F1), and 23.43 g of organic solvent propylene glycol monomethyl ether acetate (G1) were added, and the mixture was stirred for 3 hours to obtain a coloring composition. The product (H16) was prepared. When the obtained colored composition was evaluated for peeling by the above method, no pattern peeling was confirmed. Further, when the color mixing evaluation was carried out by the above method, T1 / T0 was 0.97. Moreover, when the pin unevenness was evaluated by the above method, the unevenness derived from the pedestal was not confirmed. Further, when the color transfer evaluation was carried out by the above method, Y1 / Y0 was 0.98.

The amount of each additive component added in the above examples is shown in Table 3, and the results of evaluating each of the obtained coloring compositions by the above method are summarized in Table 4.

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

Claims (12)

A coloring composition containing a coloring material, a binder resin, a radically polymerizable compound, a photopolymerization initiator and an organic solvent, wherein the radically polymerizable compound is dipentaerythritol hexa (meth) acrylate and pentaerythritol tri (meth) acrylate. The ratio of the weight (A) of the dipentaerythritol hexa (meth) acrylate to the weight (B) of the pentaerythritol tri (meth) acrylate is 0.16 <A / B <3, and the colorant The ratio of the weight (P) of the component excluding the radically polymerizable compound, the photopolymerization initiator, and the organic solvent to the weight (R) of the radically polymerizable compound is 0.5 <P / R <1.2. Coloring composition. The coloring composition according to claim 1, further containing a photosensitizer. The ratio of the weight (P) of the components excluding the coloring material, the radically polymerizable compound, the photopolymerization initiator, the organic solvent, and the photosensitizer to the weight (R) of the radically polymerizable compound is 0.5 <P. The coloring composition according to claim 2, wherein / R <1.2. The coloring composition according to any one of claims 1 to 3, wherein the number of moles of the double bond contained in the solid content Tgram excluding the coloring material satisfies 160 <T / M <220. The coloring composition according to any one of claims 1 to 4, wherein the coloring material contains a diketopyrrolopyrrole pigment having a bromine group. The coloring composition according to any one of claims 1 to 5, wherein the photosensitizer is a thioxanthone-based sensitizer. The coloring composition according to any one of claims 1 to 6, wherein the ratio of the weight (K) of the photosensitizer to the weight (L) of the photopolymerization initiator is 0.3 <K / L <0.6. thing. The coloring composition according to any one of claims 1 to 7, wherein the total content of dipentaerythritol hexa (meth) acrylate and pentaerythritol tri (meth) acrylate in the radically polymerizable compound is 70% by mass or more. A color filter substrate having pixels made of a photocurable product of the coloring composition according to any one of claims 1 to 8. The color filter substrate according to claim 9, wherein the substrate is a film. A step of (A) applying the coloring composition according to any one of claims 1 to 8 onto a substrate, (B) forming a pattern by exposure and development, and (C) further exposing the formed pattern. A method of manufacturing a color filter substrate, including. A display device having the color filter substrate according to claim 9 or 10.