JP7593126B2 - Coloring composition, color filter substrate using the same, method for producing the same, and display device - Google Patents

Description

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

Liquid crystal display devices are used in a variety of applications, including televisions, laptops, mobile information terminals, smartphones, and digital cameras, taking advantage of their characteristics of being lightweight, thin, and low power consumption. Depending on the application, LCD devices are required to display the optimal colors out of three to six primary colors, and color filter substrates that provide a variety of color performance are used.

Color filter substrates are generally manufactured by forming colored pixels through exposure and development, followed by baking at a temperature of 200°C or higher. On the other hand, in color filter-type electronic paper and silicon OLEDs, etc., colored pixels are formed on a film or light-emitting element, so baking at a temperature of 100°C or lower is required to prevent deterioration of the film or light-emitting element.

Coloring compositions containing epoxy compounds are known as coloring compositions for color filters (see, for example, Patent Document 1, Patent Document 2, and Patent Document 3). When an epoxy compound is added, crosslinking due to thermal curing proceeds, and color mixing of pixels is less likely to occur during color filter formation even when the baking temperature is low. However, color mixing is insufficiently suppressed and there are problems with storage stability, so improvements have been required.

JP 2011-22371 A JP 2012-212051 A International Publication No. 2015/182285

The present invention aims to provide a coloring composition that is unlikely to cause pattern peeling during overcoating processing even when baked at a low temperature, and that can further suppress color mixing in the pattern and is unlikely to cause pin unevenness, as well as a color filter substrate and a display device that use such a coloring composition.

In order to solve the above problems, the coloring composition of the present invention has the following configuration.
The coloring composition contains a colorant, a binder resin, a radically polymerizable compound, a photopolymerization initiator, and an organic solvent, wherein the radically polymerizable compound contains 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 ratio of the weight (P) of components excluding the colorant, 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.

The color filter substrate of the present invention has the following configuration.
and a color filter substrate having pixels formed of a photocured product of the coloring composition.

The method for producing a color filter substrate of the present invention has the following configuration.
The method for producing a color filter substrate includes the steps of (A) applying the colored composition onto a substrate, (B) forming a pattern by exposure and development, and (C) further exposing the formed pattern to light.

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

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

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

The coloring composition of the present invention preferably satisfies the relationship 160<T/M<220 in terms of the number of moles of double bonds contained per gram of solids excluding coloring material, T.

In the coloring composition of the present invention, the coloring material preferably contains a diketopyrrolopyrrole pigment having a bromine group.

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

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

In the coloring composition of the present invention, the total content of dipentaerythritol hexa(meth)acrylate and pentaerythritol tri(meth)acrylate in the radical polymerizable compound is preferably 70 mass% or more.

The coloring composition of the present invention is able to provide a coloring composition that is less likely to cause pattern peeling during overcoating even when baked at low temperatures, and that can also suppress color mixing in the pattern and is less likely to cause pin unevenness.

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, the radically polymerizable compound contains 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<3, and the ratio of the weight (P) of the components 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/R<1.2, and the coloring composition is less likely to cause pattern peeling during overcoating processing even when baked at a low temperature, and furthermore, it is possible to suppress color mixing of the pattern and the occurrence of pin unevenness.

The coloring composition of the present invention contains a coloring material. Examples of the coloring material include organic pigments, inorganic pigments, dyes, etc., and two or more of these may be contained. Among these, organic pigments and dyes are preferred from the viewpoint of further improving the transmittance.

Examples of red colorants include C.I. Pigment Red (hereinafter referred to as "PR") 9, PR48, PR97, PR122, PR123, PR144, PR149, PR166, PR168, PR177, PR179, PR180, PR192, PR209, PR215, PR216, PR217, PR220, PR223, PR224, PR226, PR227, PR228, PR240, PR254, and diketopyrrolopyrrole colorants having bromine groups. From the viewpoint of pixel brightness characteristics, PR254, PR177, and diketopyrrolopyrrole colorants having bromine groups are preferred, and from the viewpoints of brightness, vividness, and prevention of color mixing, it is preferable to use diketopyrrolopyrrole colorants having bromine groups.

Examples of yellow colorants include organic pigments, inorganic pigments, dyes, and the like, such as C.I. Pigment Yellow (hereinafter referred to as "PY") 12, PY13, PY17, PY20, PY24, PY83, PY86, PY93, PY95, PY109, PY110, PY117, PY125, PY129, PY137, PY139, PY147, PY148, PY150, PY153, PY154, PY166, and PY168 (all numbers are color index numbers). Two or more of these may be contained. From the viewpoints of color purity, light transmittance, and contrast, PY129, PY139, PY150, and PY185 are preferred, and PY150 and PY185 are more preferred.

Examples of green colorants include organic pigments, inorganic pigments, and dyes, such as C.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, and PG59 (all numbers are color index numbers). Two or more of these may be contained.

Examples of orange colorants include C.I. Pigment Orange (hereinafter referred to as "PO") 13, PO31, PO36, PO38, PO40, PO42, PO43, PO51, PO55, PO59, PO61, PO64, PO65, and PO71.

Examples of blue colorants include C.I. Pigment Blue (hereinafter referred to as "PB") 15, PB15:3, PB15:4, PB15:6, PB21, PB22, PB60, and PB64.

Examples of purple colorants include C.I. Pigment Violet (hereinafter referred to as "PV") 19, PV23, PV29, PV30, PV32, PV37, PV40, and PV50 (all numbers are color index numbers).

Examples of dyes include oil-soluble dyes, acid dyes, direct dyes, basic dyes, and acid mordant dyes. The dyes may also be made into lakes or salt-forming compounds of the dyes and nitrogen-containing compounds.

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

To improve resistance to heat, light, acid, alkali, organic solvents, etc., salt-forming compounds consisting of organic acids such as organic sulfonic acids and organic carboxylic acids or perchloric acid are preferred as basic dyes, and salt-forming compounds consisting of naphthalenesulfonic acids such as Tobias acid or perchloric acid are more preferred. Similarly, to improve resistance to heat, light, acid, alkali, organic solvents, etc., salt-forming compounds consisting of quaternary ammonium salts, primary to tertiary amines, or sulfonamides are preferred as acid dyes and direct dyes.

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

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

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

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

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

It is preferable that the acrylic resin has an ethylenically unsaturated group in the side chain, which can improve sensitivity. Examples of the ethylenically unsaturated group include a vinyl group, an allyl group, an acrylic group, and a methacrylic group. Examples of the acrylic resin having an ethylenically unsaturated group in the side chain include "Cyclomer" (registered trademark) P (Daicel Chemical Industries, Ltd.) and 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 chromatography.

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

The coloring composition of the present invention contains a radical polymerizable compound, and the radical 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 radical polymerizable compound is preferably 70% by mass or more from the viewpoints of preventing color mixing, suppressing color transfer, suppressing pin unevenness, and solubility and processability during overcoating processing. The radical 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 radical polymerizable compound is preferably a compound having an unsaturated hydrocarbon group. Examples of unsaturated hydrocarbon groups include a (meth)acryloyl group, a vinyl group, and a maleimide group. Two or more of these may be included. The coloring composition of the present invention may also contain a radical polymerizable compound other than dipentaerythritol hexa(meth)acrylate and pentaerythritol tri(meth)acrylate.

Examples of radical polymerizable compounds other than dipentaerythritol hexa(meth)acrylate and pentaerythritol tri(meth)acrylate include ethylene oxide modified compounds or propylene oxide modified compounds such as dipentaerythritol penta(meth)acrylate, tetratrimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, penta(meth)acryloyloxydipentaerythritol monosuccinic acid ester, styrene derivatives, polyfunctional maleimide compounds, poly(meth)acrylate carbamates, adipic acid 1,6-hexanediol (meth)acrylic acid ester, and phthalic anhydride. Examples include oligomers such as propylene oxide (meth)acrylic acid ester, diethylene glycol trimellitic acid (meth)acrylic acid ester, rosin-modified epoxy di(meth)acrylate, and alkyd-modified (meth)acrylate, bifunctional (meth)acrylates such as tripropylene glycol di(meth)acrylate and 1,6-hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, triacrylformal, bisphenoxyethanol fluorene diacrylate, dicyclopentadienyl diacrylate, and alkyl-modified, alkyl ether-modified, and alkyl ester-modified products of these.

The coloring composition of the present invention contains dipentaerythritol hexa(meth)acrylate and pentaerythritol tri(meth)acrylate, and 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<3. When the ratio (A/B) of the weight (A) of dipentaerythritol hexa(meth)acrylate to the weight (B) of pentaerythritol tri(meth)acrylate is 0.16 or less, the patterning property is poor, and when baked at a low temperature, pattern peeling is likely to occur during overcoating processing. On the other hand, when (A/B) is 3 or more, color mixing of the pattern cannot be suppressed. The ratio (A/B) of the weight (A) of dipentaerythritol hexa(meth)acrylate to the weight (B) of pentaerythritol tri(meth)acrylate is preferably 0.24 or more, more preferably 0.3 or more, from the viewpoint of further improving the suppression of pattern peeling during overcoating processing. Also, the ratio (A/B) of the weight (A) of dipentaerythritol hexa(meth)acrylate to the weight (B) of pentaerythritol tri(meth)acrylate is preferably 2.4 or less, more preferably 1.6 or less, from the viewpoint of further improving the prevention of color mixing.

From the viewpoint of patterning properties, the content of the radical polymerizable compound in the coloring composition of the present invention is preferably 40% by mass or more in the solid content. On the other hand, from the viewpoint of suppressing unevenness in the film thickness during film formation and suppressing deformation of the pattern due to flow during baking, the content of the radical polymerizable compound is preferably 90% by mass or less in the solid content, more preferably 70% by mass or less, and even more preferably 60% by mass or less. Also, from the viewpoint of patterning properties, the content of the radical polymerizable compound having three or more (meth)acryloyl groups and carboxyl groups is preferably 50% by mass or more in the radical polymerizable compound, and even more preferably 60% by mass or more.

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

More specifically, examples of oxime ester compounds include 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzoyloxime), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime), ethanone, 1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylmethoxybenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime), ethanone, Examples of the benzophenone compounds include 1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzoyl}-9H-carbazol-3-yl]-, 1-(O-acetyloxime), 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzoyloxime)], "ADEKA ARCLES" (registered trademark) N-1919, NCI-930 (manufactured by ADEKA Corporation), "IRGACURE" (registered trademark) OXE01, OXE02 (manufactured by BASF Japan Co., Ltd.), etc. Examples of the benzophenone compounds include benzophenone, N,N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, etc. Examples of acetophenone compounds include 2,2-diethoxyacetophenone, benzoin, benzoin methyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, α-hydroxyisobutylphenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propane, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, and "IRGACURE" (registered trademark) 369, 379, and 907 (manufactured by BASF Japan Ltd.). Examples of anthraquinone compounds include t-butylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-2-methylanthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 1,2-benzoanthraquinone, 1,4-dimethylanthraquinone, and 2-phenylanthraquinone. Examples of imidazole compounds include 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer. Examples of benzothiazole compounds include 2-mercaptobenzothiazole. Examples of benzoxazole compounds include 2-mercaptobenzoxazole. Examples of triazine compounds include 4-(p-methoxyphenyl)-2,6-di-(trichloromethyl)-s-triazine. Two or more of these may be contained, and it is even more preferable to use a photosensitizer, which will be described later, in order to suppress color transfer and prevent color mixing.

From the viewpoints of sensitivity, patterning ability, and processability, the content of the photopolymerization initiator is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 5% by mass or more, of the solid content of the coloring composition excluding the coloring material. On the other hand, from the viewpoints of sensitivity, patterning ability, processability, and heat resistance, the content of the photopolymerization initiator is preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less, of the solid content of the coloring composition excluding the coloring material.

The coloring composition of the present invention may further contain 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, etc.

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

The content of the colorant 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 proportion (mass %) of the solid content in the coloring composition can be calculated from the mass of the colorant obtained and the contents of other components. When the blending ratio of the raw materials of the coloring composition is known, the proportion (mass %) of the solid content in the coloring composition can be calculated from the blending amount of the colorant and the blending amount of the other components.

The coloring composition of the present invention may contain a dispersant such as a pigment derivative together with the colorant. Examples of dispersants include low molecular weight dispersants such as pigment intermediates and derivatives, and polymeric dispersants. Examples of pigment derivatives include alkylamine-modified pigment skeletons, carboxylic acid derivatives, and sulfonic acid derivatives, which contribute to the appropriate wetting and stabilization of the pigment. Sulfonic acid derivatives of pigment skeletons are preferred, as they have a significant effect on stabilizing fine pigments.

Examples of polymer dispersants 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 mg KOH/g and an acid value of 1 to 100 mg KOH/g in terms of solid content are preferred. Among them, polymer dispersants having basic groups are preferred, and can improve the storage stability of the pigment dispersion and the coloring composition. Examples of commercially available polymer dispersants having basic groups include "Solsperse" (registered trademark) (manufactured by Lubrizol Japan Co., Ltd.), "Efka" (registered trademark) (manufactured by BASF Corporation), "Ajisper" (registered trademark) (manufactured by Ajinomoto Fine-Techno Co., Ltd.), and "BYK" (registered trademark) (manufactured by BYK Japan Co., Ltd.). Two or more of these may be contained. Among these, "Solsperse" (registered trademark) 24000 (manufactured by Lubrizol Japan Co., Ltd.), "EFKA" (registered trademark) 4300, 4330 (manufactured by BASF Corporation), 4340 (manufactured by BASF Corporation), "Ajisper" (registered trademark) PB821, PB822 (manufactured by Ajinomoto Fine-Techno Co., Ltd.), "BYK" (registered trademark) 161-163, 2000, 2001, 6919, 21116 (manufactured by BYK Japan Co., Ltd.) are preferred.

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

The coloring composition of the present invention may contain a chain transfer agent in addition to the photopolymerization initiator, which can further improve the sensitivity. Examples of chain transfer agents include thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N-(2-mercaptopropionyl)glycine, 2-mercaptonicotinic acid, 3-[N-(2-mercaptoethyl)carbamoyl]propionic acid, 3-[N-(2-mercaptoethyl)amino]propionic acid, N-(3-mercaptopropionyl)alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, dodecyl(4-methylthio)phenyl ether, 2-mercaptoethanol, 3-mercapto-1,2 -propanediol, 1-mercapto-2-propanol, 3-mercapto-2-butanol, mercaptophenol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercapto-3-pyridinol, 2-mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropane tris(3-mercaptopropionate), 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione), pentaerythritol tetrakis(3-mercaptopropionate), 1,4-bis(3-mercaptobutyryloxy)butane, Karenz (registered trademark) MT Examples of such mercapto compounds include PE-1 (manufactured by Showa Denko K.K.), Karenz (registered trademark) MT NR-1 (manufactured by Showa Denko K.K.), Karenz (registered trademark) MT BD-1 (manufactured by Showa Denko K.K.), and the like; disulfide compounds obtained by oxidizing such mercapto compounds; and iodized alkyl compounds such as iodoacetic acid, iodopropionic acid, 2-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 photosensitizers include thioxanthone-based sensitizers and aromatic or aliphatic tertiary amines. Examples of thioxanthone-based sensitizers include thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthen-9-one, "KAYACURE" (registered trademark) DETX-S (manufactured by Nippon Kayaku Co., Ltd.). Two or more of these may be contained. From the viewpoint of suppressing color transfer and preventing color mixing of the coloring composition of the present invention, thioxanthone-based sensitizers are preferred. In addition, from the viewpoint of suppressing color transfer and preventing color mixing, it is preferred that the ratio of the weight (K) of the photosensitizer to the weight (L) of the photopolymerization initiator is 0.3<K/L<0.6.

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, 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 Examples of the ethylene glycol monomethyl ether include 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, isopentyl butanol acetate, 3-methyl-2-butanol, 3-methyl-3-methoxybutanol, cyclopentanone, cyclohexanone, xylene, ethylbenzene, and solvent naphtha. Two or more of these may be contained.

In the coloring composition of the present invention, the ratio of the weight (P) of the components excluding the coloring material, the radical polymerizable compound, the photopolymerization initiator, and the organic solvent contained in the coloring composition to the weight (R) of the radical polymerizable compound is 0.5<P/R<1.2. If P/R is 1.2 or more, the color transfer inhibition, solubility during overcoating, and processability are insufficient. Preferably, P/R<1.1, and more preferably, P/R<0.9. Also, if P/R is 0.5 or less, the film-forming properties and pin unevenness inhibition are insufficient. Preferably, P/R>0.4, more preferably, P/R>0.5, and particularly preferably, P/R>0.65.

In the case of a preferred embodiment in which the coloring composition of the present invention contains a photosensitizer, it is more preferable that the ratio of the weight (P) of the components excluding the coloring material, radical polymerizable compound, photopolymerization initiator, organic solvent, and photosensitizer contained in the coloring composition to the weight (R) of the radical polymerizable compound is 0.5<P/R<1.2. By setting P/R to 0.5<P/R<1.2, a composition that is preferable in terms of suppression of dye color transfer, film-forming properties, suppression of pin unevenness, solubility during overcoating processing, and processability can be obtained. From the viewpoint of suppression of color transfer, the ratio P/R of the weight (P) of the components excluding the coloring material, radical polymerizable compound, photopolymerization initiator, organic solvent, and photosensitizer contained in the coloring composition to the weight (R) of the radical polymerizable compound is more preferably P/R<1.1, and even more preferably P/R<0.9. Also, from the viewpoint of solubility and processability during overcoating, the ratio P/R of the weight (P) of the components excluding the colorant, radical polymerizable compound, photopolymerization initiator, organic solvent, and photosensitizer contained in the coloring composition to the weight (R) of the radical polymerizable compound is more preferably P/R<1.1, and even more preferably P/R<0.9. Also, from the viewpoint of film-forming properties and pin unevenness suppression, it is more preferably P/R>0.65.

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

The coloring composition of the present invention may further contain an adhesion improver, which can improve the adhesion of the coating film of the coloring composition to the substrate. Examples of adhesion improvers include silane coupling agents such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 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, which can improve the applicability of the coloring composition and the uniformity of the coating surface. Examples of the surfactant include anionic surfactants such as ammonium lauryl sulfate and polyoxyethylene alkyl ether triethanolamine sulfate, cationic surfactants such as stearylamine acetate and lauryl trimethylammonium chloride, amphoteric surfactants such as lauryl dimethylamine oxide and lauryl carboxymethyl hydroxyethyl imidazolium betaine, nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether and sorbitan monostearate, fluorine-based surfactants and silicon-based surfactants. Two or more of these may be contained. The content of the surfactant in the coloring composition is preferably 0.001 to 10% by mass from the viewpoint of the in-plane uniformity of the coating film.

In the coloring composition of the present invention, it is preferable that the number of moles M of double bonds contained per gram of solid content T excluding coloring materials satisfies 160<T/M<220 from the viewpoints of suppressing color transfer, solubility during overcoating, and processability. The solid content referred to here refers to all components contained in the coloring composition except for the organic solvent. From the viewpoints of suppressing color transfer, solubility during overcoating, and processability, the ratio T/M of the number of moles M of double bonds contained per gram of solid content T excluding coloring materials is preferably T/M<220, more preferably T/M<200. In addition, from the viewpoint of suppressing pin unevenness, the ratio T/M of the number of moles M of double bonds contained per gram of solid content T excluding coloring materials is preferably T/M>160, more preferably T/M>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 a substrate. It may further have a black matrix, a photospacer, an overcoat layer, an alignment film, a polarizing plate, a retardation plate, an anti-reflection film, a transparent electrode, a diffusion plate, etc.

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

The organic plastic film or sheet may be a free-standing film, or may be a film formed by coating on a substrate such as a glass substrate. In the case of such a coating film, the adhesion between the substrate and the film can be appropriately adjusted by a laser or the like to peel off the film. Examples of organic plastic materials include polyesters such as polypropylene, polyethylene, polystyrene, and polyethylene terephthalate (PET), fluorine-containing polymers such as polyphenylene sulfide (PPS), polyimide, polyamide, polyamideimide, polyethersulfone, and polytetrafluoroethylene (PTFE), polyetheretherketone, polyphenylene ether, polyarylate, and polysulfone. Even when baked at 100°C or less, the colored composition of the present invention is unlikely to peel off during overcoating processing, and furthermore, color mixing of the pattern can be suppressed. Therefore, pixels can be formed even if a film that is likely to be deformed by heat is used as a substrate, and the color filter substrate 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.

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

The black matrix prevents a decrease in contrast and color purity due to light leakage between pixels, and is preferably disposed between pixels or in the frame. Examples of materials constituting the black matrix include a photosensitive composition containing a binder resin such as an acrylic resin or a polyimide resin and a radical polymerizable compound, and a non-photosensitive resin composition colored black. From the viewpoint of light blocking properties, the film thickness of the black matrix is preferably 0.5 μm or more, and more preferably 1.0 μm or more. On the other hand, from the viewpoint of processability, it is preferably 2.0 μm or less, and more preferably 1.5 μm or less.

The photospacer provides a certain gap between the opposing substrates, and since the gap can be filled with a liquid crystal compound or the like, the step of arranging the spacers can be omitted when manufacturing the liquid crystal display device. It is preferable that the photospacer is fixed to a specific location of the color filter substrate so as to be in contact with the opposing substrate when the liquid crystal display device is manufactured. Examples of materials constituting the photospacer include a photosensitive composition containing a binder resin such as an acrylic resin or a polyimide resin and a radical polymerizable compound. Examples of the shape of the photospacer include a cylindrical shape, a rectangular column shape, a truncated cone shape, and a truncated pyramid shape. The diameter of the photospacer is not particularly specified, but is preferably 2 to 20 μm, and more preferably 3 to 10 μm. The height of the photospacer 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 materials constituting the overcoat layer include epoxy resin, acrylic epoxy resin, acrylic resin, siloxane resin, polyimide resin, and photosensitive or non-photosensitive materials commercially available as flattening materials. From the viewpoint of processability, the film thickness of the overcoat layer is preferably 0.5 μm or more, and more preferably 1.0 μm or more. On the other hand, from the viewpoint of flatness of the color filter substrate, it is preferably 5.0 μm or less, and more preferably 3.0 μm or less.

Examples of materials that can be used to form transparent electrodes include metals such as aluminum, chromium, tantalum, titanium, neodymium, or molybdenum, indium-tin-oxide (ITO), and indium-zinc-oxide (InZnO).

As a method for producing a color filter substrate, for example, there is a method for forming a pattern of pixels made of a resin composition on a substrate. Below, the production method is explained using an example of a color filter substrate having pixels made of the coloring composition of the present invention. The coloring composition of the present invention is applied onto a substrate, patterned by selective exposure and development using a photomask, and baked to form pixels, thereby obtaining a color filter substrate.

Examples of methods for applying the coloring composition of the present invention onto a substrate include a spin coater, a bar coater, a blade coater, a roll coater, a die coater, an inkjet printing method, a screen printing method, a method for immersing a substrate in a coloring composition, and a method for spraying a coloring composition onto a substrate. Subsequently, the substrate onto which the coloring composition has been applied is dried to form a coating film of the coloring composition on the substrate. Examples of drying methods include air drying, heat drying, and vacuum drying. Two or more of these may be combined, and for example, it is preferable to perform reduced pressure drying followed by 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 a substrate on which a black matrix has been formed in advance.

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

Thereafter, the unexposed areas are removed by development with an alkaline developer to form a coating film pattern. Examples of alkaline substances used in the alkaline developer include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia; primary amines such as ethylamine and n-propylamine; 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 development method include a method in which the exposed coating film is immersed in an alkaline developer for 20 to 300 seconds.

Then, the obtained coating film pattern is heated to obtain a color filter substrate having a patterned pixel. The heating treatment may be performed in air, a nitrogen atmosphere, or a vacuum. The heating temperature is preferably 80 to 250°C. The heating time is preferably 5 minutes to 5 hours. As the heat treatment device, a hot air oven or a hot plate is preferable. The heating treatment may be performed continuously or stepwise. When the coloring composition of the present invention is used, even if it is baked at 100°C or less, the pattern is less likely to peel off during overcoating processing, and further, color mixing of the pattern can be suppressed. Therefore, it can be suitably used for manufacturing a color filter substrate by (A) applying the coloring composition of the present invention onto a substrate, (B) forming a pattern by exposure and development, and (D) performing a heat treatment at 100°C or less. In particular, when the coloring composition of the present invention is used, a color filter substrate can be produced by a heat treatment process at 100°C or less, so that a color filter substrate can be produced using a film that is prone to thermal denaturation and deterioration, or a substrate including a device element such as an organic EL element that is prone to thermal denaturation and deterioration.

In addition, after applying the coloring composition of the present invention onto a substrate, a pattern is formed by exposure and development, and then, before performing a heat treatment, it is preferable to further expose the formed pattern to form a pattern. By exposing the formed pattern before performing a heat treatment, it is possible to further enhance crosslinking.

The pixels of three to six colors on the color filter substrate are sequentially formed by the above method. The order of forming each color is not particularly limited, but when forming pixels containing dye, it is preferable to form the pixels containing dye after the formation of other pixels in order to further suppress 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 of the present invention and a display element. Furthermore, the display device may have a light source such as an external light source, or various films such as a brightness enhancing film or a diffusion plate. The display device refers to a device that displays an image by allowing a part of the screen to be viewed. Examples of the display element include a liquid crystal element, an organic EL element, an inorganic EL element, a display element using MEMS, a display element using quantum dots, electronic ink, electronic liquid powder, an electrophoretic element, and the like. Examples of the display device include a transmissive liquid crystal display, a semi-transmissive 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 signs, digital signage, and electronic shelf labels. The coloring composition of the present invention can form colored pixels on a film, and therefore can be suitably used for electronic paper, curved displays, and flexible displays using a film-like color filter substrate. In addition, even if the coloring composition of the present invention is baked at 100°C or less, the pattern is unlikely to peel off during overcoating processing, and color mixing of the pattern can be suppressed. Therefore, it can be formed on a substrate including an organic EL element that is susceptible to deterioration due to heat, and is therefore suitable for use in organic EL displays such as silicon OLEDs.

As an example of the manufacturing method of the display device of the present invention, a manufacturing method of a liquid crystal display device is shown below. A color filter substrate and an array substrate are bonded together facing each other via a liquid crystal alignment film and a spacer for maintaining a cell gap provided on the substrates. 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 or a signal line, etc. on the array substrate. Next, liquid crystal is injected from an injection port provided in the seal portion, and the injection port is sealed. Furthermore, a backlight is attached and an IC driver, etc. are mounted to complete the liquid crystal display device. As the backlight, a two-wavelength LED, a three-wavelength LED, or a CCFL can be used, but a three-wavelength LED is preferred because it can expand the color reproduction range of the liquid crystal display device and keep power consumption 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 used in the examples and comparative examples will be described. The other components used in each example and comparative example are as follows.

Radical polymerizable compound solution D1: Dipentaerythritol hexaacrylate diluted to 50% by mass in propylene glycol monomethyl ether acetate solution D2: Pentaerythritol triacrylate diluted to 50% by mass in propylene glycol monomethyl ether acetate solution Photopolymerization initiator E1: "ADEKA ARCLES" (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 colored compositions obtained in Examples 1 to 8 and Comparative Examples 1 to 5 described below were applied onto a glass substrate and dried at 90° C. for 10 minutes. Thereafter, the substrate was exposed to 40 mJ of i-line through a photomask having a 20 μm line and space pattern. Next, the substrate was shower-developed with a 0.3% by mass aqueous solution of tetramethylammonium hydroxide at 23° C. for 50 seconds, and then washed with pure water. The substrate was baked at 100° C. for 30 minutes to obtain a substrate with a film having a thickness of 2.3 μm.

On the obtained substrate with the film, the colored composition (J1) obtained by Production Example 5 described later was applied to a thickness of 2.3 μm, and dried for 10 minutes at 90° C. Shower development was performed 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: Pattern peeling <Color mixing evaluation>
The colored 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. Thereafter, the substrate was exposed to i-line at 40 mJ/cm ² through a photomask having a 20 μm line and space pattern. Next, the substrate was shower-developed for 50 seconds with a 0.3% by mass aqueous solution of tetramethylammonium hydroxide at 23° C., and then washed with pure water. The substrate was baked at 100° C. for 30 minutes to obtain a substrate with a film having a thickness of 2.3 μm. The transmittance T0 at 650 nm of the obtained film was measured using a microspectrophotometer LCF-100MA manufactured by Otsuka Electronics Co., Ltd.

Next, the colored composition (J1) obtained in Production Example 5 described later was applied onto the obtained substrate with the coating under conditions that the film thickness after drying at 90°C for 10 minutes would be 2.3 μm. Next, after drying at 90°C for 10 minutes, shower development was performed with a 0.3% by mass aqueous solution of tetramethylammonium hydroxide at 23°C for 90 seconds to obtain a substrate with the coating. For the obtained coating, the transmittance T1 at 650 nm was measured using a microspectrophotometer LCF-100MA manufactured by Otsuka Electronics Co., Ltd., and color mixing was evaluated by T1/T0. The closer the value of T1/T0 is to 1, the less likely color mixing occurs, and this is preferable. In the color mixing evaluation, when no pattern remains, it is marked as "-".

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

The colored compositions obtained in Examples 1 to 8 and Comparative Examples 1 to 5 described below were applied onto the obtained black matrix substrate, and then the substrate was placed on a cylindrical base (made of polyethylene) having a diameter of 1.5 cm and a height of 1 cm and dried under reduced pressure until the pressure reached 40 Pa. The substrate was then dried on a hot plate at 100° C. for 3 minutes. The obtained substrate was visually observed under a Na lamp to check for the presence or absence of unevenness resulting from the cylindrical base, and evaluated according to the following evaluation criteria.
A: No unevenness due to the base B: Unevenness due to the base <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 resulting coating film was exposed to 40 mJ/ ^cm2 of i-line, then shower-developed for 50 seconds with a 0.3% by mass aqueous solution of tetramethylammonium hydroxide at 23°C, and washed with pure water. The substrate was baked for 30 minutes at 230°C to obtain a substrate on which a film having a thickness of 2.3 μm was formed. The colored composition (J3) obtained in Production Example 7 described later was spin-coated on the resulting substrate, and dried at 90°C for 10 minutes. The resulting coating film was exposed to 200 mJ/ ^cm2 of i-line through a photomask having a circular pattern with a diameter of 30 μm, then shower-developed for 50 seconds with a 0.3% by mass aqueous solution of tetramethylammonium hydroxide at 23°C, and washed with pure water to obtain a substrate with a film having a thickness of 2 μm and a circular hole with a diameter of 30 μm. The brightness Y0 at the center of the circular hole was measured using a microspectrometer LCF-100MA manufactured by Otsuka Electronics Co., Ltd. Next, the substrate with the coating was baked at 230°C for 30 minutes, after which the brightness Y1 at the center of the circular hole was measured, and Y1/Y0 was calculated to evaluate color transfer resistance, which is an index of the resistance to the phenomenon in which a coloring material in a pixel formed later penetrates into a pixel formed earlier. The closer the value of Y1/Y0 is to 1, the less likely color transfer is to occur, and this is preferable.

<Solubility Evaluation>
The colored compositions obtained in Examples 1 to 8 and Comparative Examples 1 to 5 described below were applied onto a glass substrate and dried at 90° C. for 10 minutes. Thereafter, the substrate was exposed to 40 mJ of i-line through a photomask, and shower-developed with a 0.3% by mass aqueous solution of tetramethylammonium hydroxide at 23° C. for 50 seconds, followed by washing with pure water. Next, the substrate was baked at 100° C. for 30 minutes to obtain a substrate with a film having a thickness of 2.3 μm.

On the obtained substrate with the film, the colored composition (J1) obtained by Production Example 5 described later was applied to a thickness of 2.3 μm, and dried for 10 minutes at 90° C. Shower development was performed with a 0.3 mass% tetramethylammonium hydroxide aqueous solution at 23° C., and the time until the coloring derived from the colored composition (J1) disappeared was confirmed, and the result was evaluated according to the following evaluation criteria.
A: The time until the coloring derived from the coloring composition (J1) disappears is within 30 seconds. B: The time until the coloring derived from the coloring composition (J1) disappears is 30 to 60 seconds. C: The time until the coloring derived from the coloring composition (J1) disappears is 60 seconds or more. Production Example 1 (Preparation of Dispersion (A1))
In a 500 mL three-neck flask under a nitrogen atmosphere, 176.3 g of anhydrous tert-amyl alcohol (2.0 mol) and 114.7 g of sodium tert-amyl alkoxide (1.1 mol) were placed, and the internal temperature was raised to 100° C. with stirring to react them, thereby preparing an alcoholate solution.

In a separate 500 mL three-neck 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 while stirring to dissolve the mixture, preparing a mixed solution.

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

In another 500 mL three-neck 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 stirred while cooling the internal temperature to -10°C to obtain a mixture.

The suspension was added dropwise over a period of 3 hours while stirring at high speed and keeping the internal temperature of the three-necked flask containing the mixture below -5°C. After the addition was completed, the mixture was stirred for an additional 7 hours, and then the reaction liquid was washed and filtered until the filtrate was no longer colored and no salt precipitated. The collected filtrate was dried at 80°C for 24 hours, and the resulting solid was pulverized to obtain 112 g of diketopyrrolopyrrole pigment having bromine groups (formula (1)). Further diketopyrrolopyrrole pigment having bromine groups was synthesized in the same manner, and 150 g of diketopyrrolopyrrole pigment having bromine groups was prepared.

150 g of the obtained diketopyrrolopyrrole pigment having bromine groups, 66.6 g of "BYK" (registered trademark) LPN6919 (manufactured by BYK Japan Co., Ltd., polymer dispersant solution (60 mass% propylene glycol monomethyl ether solution)), 88.9 g of "Cyclomer" (registered trademark) ACA250 (manufactured by Daicel Chemical Industries, Ltd., 45 mass% dipropylene glycol monomethyl ether solution), and 694.5 g of propylene glycol monomethyl ether (PMA) were mixed to prepare a slurry. The beaker containing the slurry was connected to a Dyno Mill with a tube, and a dispersion treatment was carried out for 8 hours at a peripheral speed of 14 m/s using zirconia beads with a diameter of 0.5 mm as a medium, to prepare a diketopyrrolopyrrole pigment dispersion liquid (A1) having bromine groups.

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

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

Production Example 4 (Synthesis of Binder Resin Solution (B1))
In a 500 mL three-neck flask, 33 g (0.3 mol) of methyl methacrylate, 33 g (0.3 mol) of styrene, 35 g (0.5 mol) of methacrylic acid, 3 g (0.02 mol) of 2,2'-azobis (2-methylbutyronitrile) and 150 g of propylene glycol monomethyl ether acetate (PGMEA) were charged, and the mixture was stirred at 90 ° C. for 2 hours, and then the internal temperature was raised to 100 ° C. and stirred for another 1 hour to obtain a reaction solution. To the resulting reaction solution, 33 g (0.2 mol) of glycidyl methacrylate, 1.2 g (0.009 mol) of dimethylbenzylamine and 0.2 g (0.002 mol) of p-methoxyphenol were added, and the mixture was stirred at 90 ° C. for 4 hours, and then PGMEA was added to obtain a binder resin solution (B1) having a solid content concentration of 40% by mass. The acid value of the binder resin was measured in a 0.1 mol/L potassium hydroxide-ethanol solution using an automatic potentiometer AT-610 manufactured by Kyoto Electronics Manufacturing Co., Ltd., and was found to be 119 (mgKOH/g). The weight average molecular weight calculated in terms of polystyrene was calculated using a GPC device, and was found to be 22,000.

Production Example 5 (Preparation of Colored Composition (J1))
Into 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 radical polymerizable compound solution (D1), 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 stirred for 3 hours to prepare a colored composition (J1).

Production Example 6 (Preparation of Black Matrix Composition (J2))
30 g of carbon powder (MA-8, manufactured by Mitsubishi Materials Corporation), 20 g of acrylic copolymer solution ("Cyclomer" (registered trademark) P ACA-250, manufactured by Daicel Chemical Industries, Ltd.), and 37 g of cyclohexanone were mixed and dispersed for 1 hour using a homogenizer. Then, 10 g of dipentaerythritol hexaacrylate and 3 g of a photopolymerization initiator "IRGACURE" (registered trademark) 369 (manufactured by Ciba Specialty Chemicals, Inc.) were mixed therewith to obtain a composition for black matrix (J2).

Production Example 7 (Preparation of Colored Composition (J3))
Into a three-neck flask, 15 g of Acid Red 289, 150 g of chloroform, and 8.9 g of N,N-dimethylformamide were added. The mixture was then cooled to 20° C. or lower, and 10.9 g of thionyl chloride was added dropwise. After completion of the dropwise addition, the mixture was heated to 50° C. and stirred for 5 hours, then cooled to 20° C., and a mixture of 12.5 g of 2-ethylhexylamine and 22.1 g of triethylamine was added, and stirred at 20° C. for 5 hours to obtain a reaction mixture. The solvent was removed from the obtained reaction mixture using a rotary evaporator, and the mixture was purified to obtain 10 g of a xanthene dye.

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 were mixed to prepare a slurry. The beaker containing the slurry was connected to a Dyno Mill via a tube, and a dispersion process was carried out for 8 hours at a peripheral speed of 10 m/s using zirconia beads with a diameter of 0.3 mm as the medium, to prepare a dispersion liquid (A4) containing the dye.

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, 23.50 g of "Kayarad" (registered trademark) DPHA (manufactured by Nippon Kayaku Co., Ltd., polyfunctional radical polymerizable compound), 0.31 g of "ADEKA ARCLES" (registered trademark) N-1919 (manufactured by ADEKA Corporation, oxime ester photopolymerization initiator), and 60.00 g of dipropylene glycol methyl ether acetate (DPMA) were added and stirred for 3 hours to prepare a colored composition (J3).
Example 1
In a 50 mL plastic bottle, 11.09 g of the dispersion (A1) obtained in Production Example 1, 4.75 g of the dispersion (A2) obtained in Production Example 2, 1.19 g of the binder resin solution (B1) obtained in Production Example 4, 2.99 g of the radical polymerizable compound solution (D1), 1.28 g of the radical polymerizable compound solution (D2), 0.07 g of the photopolymerization initiator (E1), 0.14 g of the photopolymerization initiator (E2), 0.07 g of the photosensitizer 2,4-diethylthioxanthone (F1), and 23.43 g of the organic solvent propylene glycol monomethyl ether acetate (G1) were added and stirred for 3 hours to prepare a colored composition (H1). When the obtained colored composition was subjected to a peeling evaluation by the above method, no pattern peeling was observed. In addition, when a color mixing evaluation was performed by the above method, T1/T0 was 0.94. Furthermore, when pin unevenness was evaluated by the above-mentioned method, unevenness due to the base was not confirmed. Furthermore, when color transfer was evaluated by the above-mentioned method, Y1/Y0 was 0.99.
Example 2
A colored composition (H2) was prepared in the same manner as in Example 1, except that the amount of radical polymerizable compound (D1) added was changed to 2.13 g, and the amount of radical polymerizable compound solution (D2) added was changed to 2.13 g. The obtained colored composition was used to perform peeling evaluation by the above method, and no pattern peeling was observed. In addition, when color mixing evaluation was performed by the above method, T1/T0 was 0.96. In addition, when pin unevenness evaluation was performed by the above method, no unevenness due to the base was observed. In addition, when color transfer evaluation was performed by the above method, Y1/Y0 was 0.99.
Example 3
A colored composition (H3) was prepared in the same manner as in Example 1, except that the amount of radical polymerizable compound (D1) added was changed to 1.07 g, and the amount of radical polymerizable compound solution (D2) added was changed to 3.20 g. The obtained colored composition was used to evaluate peeling by the above method, and no pattern peeling was observed. In addition, when color mixing evaluation was performed by the above method, T1/T0 was 0.98. In addition, when pin unevenness evaluation was performed by the above method, no unevenness due to the base was observed. In addition, when color transfer evaluation was performed by the above method, Y1/Y0 was 0.99.
Example 4
A colored composition (H4) was prepared in the same manner as in Example 1, except that the amount of radical polymerizable compound (D1) added was changed to 0.64 g, and the amount of radical polymerizable compound solution (D2) added was changed to 3.63 g. The obtained colored composition was used to perform peeling evaluation by the above method, and no pattern peeling was observed. In addition, when color mixing evaluation was performed by the above method, T1/T0 was 0.99. In addition, when pin unevenness evaluation was performed by the above method, no unevenness due to the base was observed. In addition, when color transfer evaluation was performed by the above method, Y1/Y0 was 0.99.
Example 5
A colored composition (H5) was prepared in the same manner as in Example 1, except that the amount of binder resin solution (B1) obtained in Production Example 4 was changed to 0.71 g, the amount of radical polymerizable compound (D1) was changed to 3.26 g, and the amount of radical polymerizable compound solution (D2) was changed to 1.40 g. Using the obtained colored composition, peeling evaluation was performed by the above method, and no pattern peeling was observed. In addition, color mixing evaluation was performed by the above method, and T1/T0 was 0.95. In addition, pin unevenness evaluation was performed by the above method, and no unevenness due to the base was observed. In addition, color transfer evaluation was performed by the above method, and Y1/Y0 was 1.00.
Example 6
A colored composition (H6) was prepared in the same manner as in Example 1, except that the amount of binder resin solution (B1) obtained in Production Example 4 was changed to 0.71 g, the amount of radical polymerizable compound (D1) was changed to 1.86 g, and the amount of radical polymerizable compound solution (D2) was changed to 2.79 g. Using the obtained colored composition, peeling evaluation was performed by the above method, and no pattern peeling was observed. In addition, color mixing evaluation was performed by the above method, and T1/T0 was 0.98. In addition, pin unevenness evaluation was performed by the above method, and no unevenness due to the base was observed. In addition, color transfer evaluation was performed by the above method, and Y1/Y0 was 1.00.
(Example 7)
A colored composition (H7) was prepared in the same manner as in Example 1, except that the amount of binder resin solution (B1) obtained in Production Example 4 was changed to 1.68 g, the amount of radical polymerizable compound (D1) was changed to 2.71 g, and the amount of radical polymerizable compound solution (D2) was changed to 1.16 g. Using the obtained colored composition, peeling evaluation was performed by the above method, and no pattern peeling was observed. In addition, color mixing evaluation was performed by the above method, and T1/T0 was 0.94. In addition, pin unevenness evaluation was performed by the above method, and no unevenness due to the base was observed. In addition, color transfer evaluation was performed by the above method, and Y1/Y0 was 0.98.
(Example 8)
A colored composition (H8) was prepared in the same manner as in Example 1, except that the amount of binder resin solution (B1) obtained in Production Example 4 was changed to 1.68 g, the amount of radical polymerizable compound (D1) was changed to 1.55 g, and the amount of radical polymerizable compound solution (D2) was changed to 2.33 g. Using the obtained colored composition, peeling evaluation was performed by the above method, and no pattern peeling was observed. In addition, color mixing evaluation was performed by the above method, and T1/T0 was 0.98. In addition, pin unevenness evaluation was performed by the above method, and no unevenness due to the base was observed. In addition, color transfer evaluation was performed by the above method, and Y1/Y0 was 0.98.
(Comparative Example 1)
A colored composition (H9) was prepared in the same manner as in Example 1, except that the amount of radical polymerizable compound (D1) was changed to 3.28 g, and the amount of radical polymerizable compound solution (D2) was changed to 0.98 g. The obtained colored composition was used to evaluate peeling by the above method, and no pattern peeling was observed. In addition, when color mixing evaluation was performed by the above method, T1/T0 was 0.71. In addition, when pin unevenness evaluation was performed by the above method, no unevenness due to the base was observed. In addition, when color transfer evaluation was performed by the above method, Y1/Y0 was 0.99.
(Comparative Example 2)
A colored composition (H10) was prepared in the same manner as in Example 1, except that the amount of radical polymerizable compound (D1) added was changed to 0.00 g, and the amount of radical polymerizable compound solution (D2) added was changed to 4.26 g. The obtained colored composition was used to perform peeling evaluation by the above method, and pattern peeling was confirmed. In addition, when color mixing evaluation was performed by the above method, no pattern remained. In addition, when pin unevenness evaluation was performed by the above method, unevenness due to the base was not confirmed. In addition, when color transfer evaluation was performed by the above method, Y1/Y0 was 0.99.
(Comparative Example 3)
A colored composition (H11) was prepared in the same manner as in Example 1, except that the amount of binder resin solution (B1) obtained in Production Example 4 was changed to 1.68 g, the amount of radical polymerizable compound (D1) was changed to 3.10 g, and the amount of radical polymerizable compound solution (D2) was changed to 0.78 g. Using the obtained colored composition, peeling evaluation was performed by the above method, and no pattern peeling was observed. In addition, color mixing evaluation was performed by the above method, and T1/T0 was 0.63. In addition, pin unevenness evaluation was performed by the above method, and no unevenness due to the base was observed. In addition, color transfer evaluation was performed by the above method, and Y1/Y0 was 0.98.
(Comparative Example 4)
A colored composition (H12) was prepared in the same manner as in Example 1, except that the amount of binder resin solution (B1) obtained in Production Example 4 was changed to 0.03 g, the amount of radical polymerizable compound (D1) was changed to 3.64 g, and the amount of radical polymerizable compound solution (D2) was changed to 1.56 g. Using the obtained colored composition, peeling evaluation was performed by the above method, and no pattern peeling was observed. In addition, color mixing evaluation was performed by the above method, and T1/T0 was 0.95. In addition, pin unevenness evaluation was performed by the above method, and unevenness due to the pedestal was confirmed. In addition, color transfer evaluation was performed by the above method, and Y1/Y0 was 1.00.
(Comparative Example 5)
A colored composition (H13) was prepared in the same manner as in Example 1, except that the amount of binder resin solution (B1) obtained in Production Example 4 was changed to 2.16 g, the amount of radical polymerizable compound (D1) was changed to 2.44 g, and the amount of radical polymerizable compound solution (D2) was changed to 1.05 g. Using the obtained colored composition, peeling evaluation was performed by the above method, and no pattern peeling was observed. In addition, color mixing evaluation was performed by the above method, and T1/T0 was 0.94. In addition, pin unevenness evaluation was performed by the above method, and no unevenness due to the base was observed. In addition, color transfer evaluation was performed by the above method, and Y1/Y0 was 0.97.

The amounts of each additive component added in the above examples and comparative examples are shown in Table 1, and the results of evaluating each of the resulting coloring compositions using the above methods are shown in Table 2.

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

The amounts of each additive component added in the above examples are shown in Table 3, and the results of evaluating each of the resulting coloring compositions using the above methods are shown in Table 4.

The coloring composition of the present invention can be suitably used for color filter substrates, display devices, decorative ink materials, etc.

Claims (13)

1. A coloring composition comprising a coloring material, a binder resin, a radically polymerizable compound, a photopolymerization initiator and an organic solvent, wherein the radically polymerizable compound comprises 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 components excluding the coloring material, the radically polymerizable compound, the photopolymerization initiator and the organic solvent to a weight (R) of the radically polymerizable compound is 0.5<P/R< 0.9 . The colored composition according to claim 1, wherein the photopolymerization initiator is a photopolymerization initiator having a partial structure represented by the following general formula (1), a photopolymerization initiator represented by the following general formulas (2) to (5), or a photopolymerization initiator other than 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole.

In the general formula (1), R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, or an alkoxy group. R ³ and R ⁴ may form a ring together. X represents OR ⁵ , SR ⁶ , or NR ¹⁷ R ^18. R ⁵ , R ⁶ , R ¹⁷ , and R ¹⁸ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heteroaryl group. R ¹⁷ and R ¹⁸ may form a ring directly or via a divalent linking group.

The coloring composition according to claim 1 or 2, wherein the number of moles M of double bonds contained per gram of solid content T excluding coloring materials satisfies 160<T/M<220. The coloring composition according to any one of claims 1 to 3, wherein the coloring material includes a diketopyrrolopyrrole pigment having a bromine group. The coloring composition according to any one of claims 1 to 4, wherein the total content of dipentaerythritol hexa(meth)acrylate and pentaerythritol tri(meth)acrylate in the radical polymerizable compound is 70 mass% or more. The coloring composition according to any one of claims 1 to 5, further comprising a photosensitizer. The coloring composition according to claim 6, wherein the photosensitizer is a thioxanthone-based sensitizer. 8. The colored composition according to claim 6, wherein a ratio of a weight (P) of components excluding the colorant, the radical polymerizable compound, the photopolymerization initiator, the organic solvent, and the photosensitizer to a weight (R) of the radical polymerizable compound satisfies 0.5<P/R< 0.9 . The coloring composition according to any one of claims 6 to 8, 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. A color filter substrate having pixels made of a photocured product of the coloring composition according to any one of claims 1 to 9. The color filter substrate according to claim 10, wherein the substrate is a film. A method for producing a color filter substrate, comprising the steps of (A) applying the coloring composition according to any one of claims 1 to 9 onto a substrate, (B) forming a pattern by exposure and development, and (C) further exposing the formed pattern to light. A display device comprising the color filter substrate according to claim 10.