TW201840744A - Coloring composition, and color filter substrate and display device using same - Google Patents

Abstract

The purpose of the present invention is to provide a coloring composition, which has a high color purity and high light transmittance and can suppress a decrease in the light transmittance caused by light irradiation, and a color filter substrate using the coloring composition. The coloring composition according to the present invention comprises a green coloring material having a metal phthalocyanine skeleton and a yellow coloring material comprising C.I. Pigment Yellow 138 and/or C.I. Pigment Yellow 185, wherein the total content of the green coloring material having a metal phthalocyanine skeleton, C.I. Pigment Yellow 138 and C.I. Pigment Yellow 185 is 2-16 mass% inclusive relative to solids.

Description

   Coloring composition, color filter substrate using the same, and display device   

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

The liquid crystal display device uses characteristics such as light weight, thinness, and low power consumption, and is used in various applications such as televisions, notebook computers, mobile information terminals, smart phones, and digital cameras. In the liquid crystal display device, a color filter substrate is used which requires an optimal color of 3 to 6 primary colors according to the application, and performs various color performances.

In green pixels, although various combinations of pigments are discussed, generally, a green color material and a yellow color material having a metal phthalocyanine skeleton are combined. This technique is known to contain, for example, a coloring agent selected from the group consisting of Pigment Green 7, Pigment Green 36, and Pigment Green 58 and a pigment selected from the group consisting of Pigment Yellow 129, Pigment Yellow 138, and Pigment Yellow 150. A group of yellow colorants and green colorant compositions (for example, refer to Patent Document 1).

On the other hand, it is known that if phthalocyanin is irradiated with light in a state of blocking oxygen, the transmittance of the green pixel formed by phthalocyanin will decrease due to a change in the absorption spectrum (for example, refer to Non-Patent Document 1) . That is, if a liquid crystal display device having a green pixel formed by phthalocyanine is irradiated with light in an oxygen-blocking state, the transmittance of the green pixel is reduced, and the brightness of the liquid crystal display device is dimmed.

Prior art literature Patent literature

Patent Document 1 Japanese Patent Application Publication No. 2014-41341

Non-patent literature

Non-Patent Document 1 Journal of Photopolymer Science and Technology, Volume 7, Number 1 (1994) p. 151-158

When a green color material having a metal phthalocyanin skeleton as described in Patent Document 1 and a specific yellow color material are combined, if light is irradiated in an oxygen-blocking state, light transmittance is greatly reduced, and display performance is changed. Topic. In view of this situation, an object of the present invention is to provide a colored composition having high color purity and light transmittance and capable of suppressing a decrease in light transmittance caused by light irradiation, and a color filter substrate and a display device using the colored composition. .

The invention is a coloring composition, which is a coloring composition containing a green coloring material having a metal phthalocyanin skeleton and a yellow coloring material containing CI Pigment Yellow 138 and / or CI Pigment Yellow 185, wherein the metal phthalocyanin skeleton is provided. The total content of the green color material, CI Pigment Yellow 138 and CI Pigment Yellow 185 is 2% by mass or more and 16% by mass or less in the solid content.

According to the coloring composition of the present invention, it is possible to provide a color filter substrate and a display device having high color purity and light transmittance, and having color pixels that suppress the decrease in light transmittance caused by light irradiation.

Implementation of the invention

The coloring composition of the present invention includes a green color material having a metal phthalocyanin skeleton and a yellow color material including C.I. Pigment Yellow 138 and / or C.I. Pigment Yellow 185. By including a green color material having a metal phthalocyanin skeleton and a yellow color material including C.I. Pigment Yellow 138 and / or C.I. Pigment Yellow 185, color purity and light transmittance can be improved. "Improved color purity" in this context refers to colors that can appear farther away from the light source (for example, in the case of C light source, coordinates x = 0.310, y = 0.316) in the CIE 1931 color system. In addition, since the light transmittance of the colored composition changes greatly depending on the chromaticity thereof, the phrase "the transmittance can be improved" means that the transmittance is increased when the chromaticity coordinates are the same. On the other hand, as described above, if a green color material having a metal phthalocyanine skeleton is irradiated with light in an oxygen-blocking state, there is a problem that light transmittance is greatly reduced and display performance is changed. The present invention has found that by including CI Pigment Yellow 138 and / or CI Pigment Yellow 185 as a yellow color material, and a total content of a green color material having a metal phthalocyanin skeleton and CI Pigment Yellow 138 and CI Pigment Yellow 185, set It is 2% by mass or more and 16% by mass or less of the solid content, which can improve color purity and light transmittance, and at the same time suppress the decrease in light transmittance caused by light irradiation.

From the viewpoint of further improving the light transmittance, as the green color material having a metal phthalocyanin skeleton, C.I. Pigment Green 58 and C.I. Pigment Green 59 are preferable. The total content of C.I. Pigment Green 58 and C.I. Pigment Green 59 is preferably 80% by mass or more, and more preferably 90% by mass or more in the green color material. From the viewpoint of further improving the light transmittance, it is preferable to use C.I. Pigment Green 58 or C.I. Pigment Green 59 as the green color material alone. From the viewpoint of further improving the transmittance retention rate, C.I. Pigment Green 58 is more preferred. From the viewpoint of further improving the transmittance retention rate, the content of C.I. Pigment Green 58 is preferably 80% by mass or more, and more preferably 90% by mass or more in the green color material.

The yellow color material includes C.I. pigment yellow 138 and / or C.I. pigment yellow 185, and may further contain other color materials. From the viewpoint of further improving light transmittance and light transmittance retention, C.I. Pigment Yellow 185 is more preferable. From the viewpoint of improving light transmittance, the total content of CI Pigment Yellow 138 and CI Pigment Yellow 185 is preferably 60% by mass or more, more preferably 80% by mass, and particularly preferably 90% by mass or more in the yellow color material. . The content of C.I. Pigment Yellow 185 is preferably 60% by mass or more in the yellow color material, more preferably 80% by mass or more, and particularly preferably 90% by mass or more. From the viewpoint of improving light transmittance, it is preferable to use C.I. Pigment Yellow 185 alone as a yellow color material.

From the viewpoint of improving transmittance, it is preferable to contain CI Pigment Yellow 185 as a yellow coloring material. In general, if the content of CI Pigment Yellow 185 in the coloring material is 50% by mass or more and 90% by mass or less , There is a tendency that the light transmittance tends to decrease due to light irradiation. As described later, the present invention sets the total content of a green color material having a metal phthalocyanin skeleton, CI Pigment Yellow 138, and CI Pigment Yellow 185 to a specific range, because the reduction in transmittance due to light irradiation can be suppressed, so When the content of CI Pigment Yellow 185 in the color material whose light transmittance is easily reduced is 50% by mass or more and 90% by mass or less, a higher effect can be exhibited.

Examples of yellow coloring materials other than CI Pigment Yellow 138 and CI Pigment Yellow 185 include organic pigments, inorganic pigments, and dyes, and examples thereof include CI Pigment Yellow (hereinafter, "PY") 12, PY13, PY17, PY20, PY24, PY83, PY86, PY93, PY95, PY109, PY110, PY117, PY125, PY129, PY137, PY139, PY147, PY148, PY150, PY153, PY154, PY166, PY168 (the above numbers are color index No.), etc. . It may contain two or more of these. From the viewpoints of color purity, light transmittance, and contrast, PY129, PY139, or PY150 is preferable, and PY150 is more preferable.

The coloring composition of the present invention is characterized in that the total content of the green coloring material having a metal phthalocyanin skeleton, C.I. Pigment Yellow 138 and C.I. Pigment Yellow 185 is 2% by mass or more and 16% by mass or less of the solid content. If the total content of the green coloring material having a metal phthalocyanin skeleton, C.I. Pigment Yellow 138, and C.I. Pigment Yellow 185 is less than 2% by mass in the solid content, the color purity decreases. The total content of these is preferably 3% by mass or more, and more preferably 5% by mass or more. On the other hand, if the total content of the green color material having a metal phthalocyanin skeleton, CI Pigment Yellow 138, and CI Pigment Yellow 185 exceeds 16% by mass of the solid content, the light transmittance is reduced due to light irradiation, and The rate retention rate decreases.

From the viewpoint of further improving color purity, the total content of the green color material having a metal phthalocyanin skeleton, CI Pigment Yellow 138, and CI Pigment Yellow 185 is preferably 60% by mass or more, and more preferably 80% by weight in the color material. % Or more, particularly preferably 90% by mass or more.

From the viewpoint of further improving the light transmittance, the green color material having a metal phthalocyanin skeleton preferably contains CI Pigment Green 58 or CI Pigment Green 59. From the viewpoint of further improving color purity, CI Pigment Green 58 The total content of CI Pigment Green 59, CI Pigment Yellow 138, and CI Pigment Yellow 185 is preferably 60% by mass or more in the color material, more preferably 80% by mass or more, and particularly preferably 90% by mass or more.

In addition, the total content of the color material containing C.I. Pigment Green 58, C.I. Pigment Green 59, C.I. Pigment Yellow 138, and C.I. Pigment Yellow 185 is preferably 2% by mass or more and 16% by mass or less in the solid content.

Furthermore, from the viewpoint of further improving color purity, the total content of CI Pigment Green 58 and CI Pigment Yellow 185 is preferably 60% by mass or more, more preferably 80% by mass or more, and 90% by mass in the color material. %the above.

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

The coloring composition of the present invention may contain a color material other than the aforementioned green color material or yellow color material. Examples of the color material include organic pigments, inorganic pigments, and dyes, and may contain two or more of these. From the viewpoint of further improving the transmittance, among these, organic pigments and dyes are preferred.

Examples of the red pigment include CI 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, etc.

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

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

Examples of the purple pigment include C.I. Pigment Violet (hereinafter referred to as "PV") 19, PV23, PV29, PV30, PV32, PV37, PV40, PV50, etc. (the above numbers are all color index No.).

Examples of the dye include oil-soluble dyes, acid dyes, direct dyes, basic dyes, and acid mordant dyes. The dye may be laked as a salt-forming compound between the dye and a nitrogen-containing compound.

Examples of the red, green, blue, purple, or yellow dyes include direct dyes, acid dyes, and basic dyes. Specific examples of these dyes include, for example, azo-based dyes, benzoquinone-based dyes, naphthoquinone-based dyes, anthraquinone-based dyes, xanthene-based dyes, cyanine-based dyes, and squarylium-based dyes. Dyes, Croconium-based dyes, merocyanin-based dyes, stilbene-based dyes, diarylmethane-based dyes, triarylmethane-based dyes, fluorescent fluoran-based dyes, spiropyrine Spiropyran dyes, phthalocyanin dyes, indigo dyes, fulgide dyes, nickel complex dyes, fluorene dyes, and the like. Dyes can be dissolved in the coloring composition and dispersed as particles.

In order to improve resistance to heat, light, acids, alkalis, organic solvents, etc., the basic dye is preferably a salt-forming compound containing an organic acid such as an organic sulfonic acid, an organic carboxylic acid, or a perchloric acid, and more preferably contains Salt-forming compounds such as naphthalenesulfonic acid or perchloric acid such as tobias acid. Similarly, in order to improve resistance to heat, light, acids, alkalis, organic solvents, etc., as the acid dye and direct dye, a quaternary ammonium salt and a salt-forming compound containing primary to tertiary amines or sulfonamides are preferred.

The coloring composition of the present invention preferably contains a radical polymerizable compound. By containing a radical polymerizable compound, pattern moldability can be provided. As the radical polymerizable compound in the present invention, a compound having an unsaturated hydrocarbon group is preferred. Examples of the unsaturated hydrocarbon group include a (meth) acrylfluorenyl group, a vinyl group, and a maleimide group. There may be two or more of these.

Examples of the radically polymerizable compound include dipentaerythritol penta (meth) acrylate, tetratrimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol tetra (methyl) ) Acrylate, penta (meth) acryloxydipentaerythritol monosuccinate, dipentaerythritol hexa (meth) acrylate and other ethylene oxide or propylene oxide modifiers, styrene derivatives, polyfunctional Maleimide compound, poly (meth) acrylate urethane, adipic acid 1,6-hexanediol (meth) acrylate, phthalic anhydride propylene oxide (meth) acrylate , Oligomers such as trimellitic acid diethylene glycol (meth) acrylate, rosin modified epoxy di (meth) acrylate, alkyd modified (meth) acrylate, tripropylene glycol di (methyl) ) Acrylate, 1,6-hexanediol di (meth) acrylate and other bifunctional (meth) acrylates, trimethylolpropane tri (meth) acrylate, tripropenyl methylal, Bisphenoxyethanol, diacrylate, dicyclopentadienyl diacrylate, alkyl modified products, alkyl ether modified products, or alkane Modification and the like. It may contain two or more of these.

From the viewpoint of solubility and pattern formability, among these, a compound having a (meth) acrylfluorenyl group is preferable, and a polyfunctional compound having three or more kinds of (meth) acrylfluorenyl groups is preferable. . By using a polyfunctional compound having three or more (meth) acrylfluorene groups, a film that is excellent in heat resistance and sufficiently hardened can be formed. From the viewpoint of alkali developability, a compound having a carboxyl group is preferred. More preferred is a compound having three or more (meth) acrylfluorenyl groups and a carboxyl group. Examples of the compound include penta (meth) acryloxydipentaerythritol monosuccinate.

From the viewpoint of pattern formability, 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, the content of the radical polymerizable compound is preferably 90% by mass of the solid content from the viewpoint of suppressing uneven film thickness during film formation and suppressing deformation of the pattern due to flow during firing. Hereinafter, it is more preferably 70% by mass or less, and still more preferably 60% by mass or less. From the viewpoint of pattern formability, the content of a radical polymerizable compound having three or more (meth) acrylfluorenyl groups and a carboxyl group is preferably 50% by mass or more and 100% by mass of the radical polymerizable compound. Hereinafter, it is more preferably 60% by mass or more and 100% by mass or less.

The coloring composition of the present invention may further contain a binder resin, a dispersant, a photopolymerization initiator, a chain transfer agent, a sensitizer, an organic solvent, a polymerization inhibitor, an adhesion improver, a surfactant, and an organic acid. , Organic amine compounds, hardeners, etc.

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

Examples of the binder resin include an acrylic resin, an epoxy resin, a polyimide resin, a urethane resin, a urea resin, a polyvinyl alcohol resin, a melamine resin, a polyimide resin, and a polyimide resin. Imine resin, polyester resin, polyolefin resin, etc. It may contain two or more of these. From the viewpoint of stability, an acrylic resin is preferably used.

The acrylic resin is preferably a copolymer of an unsaturated carboxylic acid and an ethylenically unsaturated compound.

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

Examples of ethylenically unsaturated compounds include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and (meth) N-butyl acrylate, secondary butyl (meth) acrylate, isobutyl (meth) acrylate, tertiary butyl (meth) acrylate, n-amyl (meth) acrylate, (meth) acrylic acid 2- Unsaturated carboxylic acid alkyl esters such as benzyl hydroxyethyl (meth) acrylate, styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, α-methylstyrene, etc. Unsaturated carboxylic acid amine alkyl esters such as aromatic vinyl compounds, amine ethyl acrylate, propylene acrylate acrylic acid, propylene methacrylic acid unsaturated propylene glycol esters, vinyl acetate, vinyl propionate, etc. Vinyl carboxylates, acrylonitrile, methacrylonitrile, α-chloroacrylonitrile and other cyanide vinyl compounds, aliphatic conjugated diene such as 1,3-butadiene, isoprene, etc. ) Acrylic acid-based polystyrene, polymethyl acrylate, polymethyl methacrylate, polybutyl acrylate, polybutyl methacrylate, polysiloxane, etc.体 等。 Body and so on. Two or more of these may be used.

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

From the viewpoint of the strength of the cured film, the weight average molecular weight of the binder resin is preferably 3,000 or more, and more preferably 9,000 or more. 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, and more preferably 100,000 or less. Here, the weight average molecular weight of a binder resin means the standard polystyrene conversion value measured by colloidal permeation chromatography.

From the viewpoint of suppressing uneven 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 in the solid content. On the other hand, from the viewpoint of pattern formability, the content of the binder resin is preferably 60% by mass or less in the solid content, and more preferably 50% by mass or less.

The coloring material contained in the coloring composition of the present invention can be subjected to mass analysis by laser Raman spectrometry (Ar + laser (457.9nm)), or by using a MALDI mass analyzer or a time-of-flight secondary ion mass analyzer. For identification.

The content of the color material in the coloring composition can be quantified by mass analysis using a MALDI mass analysis device or a time-of-flight secondary ion mass spectrometer, and the mass of the obtained color material and other components can be determined. The content is the ratio (mass%) of the solid content in the coloring composition. When the blending ratio of the raw materials of the coloring composition is known, the proportion of the solid content in the coloring composition can be determined from the blending amount of the coloring material and the blending amount of other components. (quality%).

The coloring composition of the present invention may also contain a dispersant such as a color material and a pigment derivative. Examples of the dispersant include low-molecular dispersants such as intermediates and derivatives of pigments, and high-molecular dispersants. Examples of the pigment derivative include an alkylamine modifier, a carboxylic acid derivative, and a sulfonic acid derivative of a pigment skeleton that promotes moderate wetting or stabilization of the pigment. The sulfonic acid derivative of a pigment skeleton which has a remarkable effect on stabilization of a fine pigment is preferable.

Examples of the polymer dispersant include polyester, polyalkylamine, polyallylamine, polyimide, polyamine, polyurethane, polyacrylate, polyimide, and polyfluorene. Imines or their copolymers, etc. It may contain two or more of these. Among these polymer dispersants, a solid content-based amine value of 5 to 200 mgKOH / g and an acid value of 1 to 100 mgKOH / g are preferred. Among them, a polymer dispersant having a basic group is preferable, and the storage stability of the pigment dispersion liquid and the coloring composition can be improved. Examples of commercially available polymer dispersants having a basic group include "Solsperse" (registered trademark) (manufactured by Avecia), "EFKA" (registered trademark) (manufactured by EFKA), and "AJISPER" ( (Registered trademark) (made by Ajinomoto Fine-Techno), "BYK" (registered trademark) (made by BYK). It may contain two or more of these. Among them, “Solsperse” (registered trademark) 24000 (manufactured by Avecia), “EFKA” (registered trademark) 4300, 4330 (manufactured by EFKA company), 4340 (manufactured by EFKA company), and “AJISPER” (registered trademark) PB821 are preferred. , PB822 (manufactured by Ajinomoto Fine-Techno), "BYK" (registered trademark) 161 to 163, 2000, 2001, 6919, 21116 (by BYK).

When the colored composition of the present invention contains a polymer dispersant and / or a binder resin, the total content thereof is preferably 10% by mass of the solid content from the viewpoint of suppressing uneven film thickness during film formation. The above is more preferably 20% by mass or more, and even more preferably 30% by mass or more. On the other hand, from the viewpoint of pattern formability, the total content of the polymer dispersant and the binder resin is preferably 60% by mass or less, and more preferably 50% by mass of the solid content of the color material excluding the coloring composition. %the following.

The coloring composition of the present invention preferably contains a photopolymerization initiator and can improve the sensitivity during pattern formation. Here, the photopolymerization initiator refers to a compound that is decomposed and / or reacted by light (including ultraviolet rays or electron beams) and generates a radical. Examples of the photopolymerization initiator include oxime ester compounds, benzophenone compounds, acetophenone compounds, thioxanthone compounds, anthraquinone compounds, imidazole compounds, and benzothiazole compounds. Benzo Azole compounds, carbazole compounds, three Compounds, phosphorus compounds, titanocene compounds, and the like.

More specifically, examples of the oxime ester compound include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzidine oxime), and Acetophenone, 1- [9-ethyl-6- (2-methylbenzylidene) -9H-carbazol-3-yl]-, 1- (O-acetamoxime), biacetophenone , 1- [9-ethyl-6- (2-methyl-4-tetrahydrofurylmethoxybenzyl) -9H-carbazol-3-yl]-, 1- (O-acetamoxime) , Biacetophenone, 1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolyl) methoxybenzoyl Fluorenyl} -9H-carbazol-3-yl]-, 1- (O-acetamoxime), 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzene Formamoxime)], "ADEKA ARKLS" (registered trademark) N-1919, NCI-930 (made by ADEKA (stock)), "IRGACURE" (registered trademark) OXE01, OXE02 (BASF (stock)) and so on.

Examples of the benzophenone-based compound include benzophenone, N, N'-tetraethyl-4,4'-diaminobenzophenone, and 4-methoxy-4'-dione. Methylaminobenzophenone and the like.

Examples of the acetophenone-based compound include 2,2-diethoxyacetophenone, benzoin, benzoin methyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, α-Hydroxyisobutyl ketone, 1-hydroxycyclohexyl phenone, 2-methyl-1- [4- (methylthio) phenyl] -2- Phenyl-1-propane, 2-benzyl-2-dimethylamino-1- (4- Phenylphenyl) -butanone, 2- (dimethylamino) -2-[(4-tolyl) methyl] -1- [4- (4- Phenyl) phenyl] -1-butanone, 2-methyl-1- [4- (methylthio) phenyl] -2- Phenylpropan-1-one, "IRGACURE" (registered trademark) 369, 379, 907 (manufactured by BASF).

Examples of the anthraquinone-based compound include tertiary butyl anthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-2-methylanthraquinone, and 2-ethylanthraquinone. , 1,4-naphthoquinone, 9,10-phenanthrenequinone, 1,2-benzoanthraquinone, 1,4-dimethylanthraquinone, 2-phenylanthraquinone, and the like.

Examples of the imidazole-based compound include 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer.

Examples of the benzothiazole-based compound include 2-mercaptobenzothiazole and the like.

As benzo Examples of the azole-based compound include 2-mercaptobenzo Azole and so on.

As three Examples of the compounds are 4- (p-methoxyphenyl) -2,6-di- (trichloromethyl) -s-tri Wait.

It may contain two or more of these. According to the present invention, the green color material having a metal phthalocyanin skeleton and the total content of Pigment Yellow 138 and CI Pigment Yellow 185 are pattern forming sensitivities and pattern processing in a colored composition having a solid content of 2% to 16% by mass Among these, 2-methyl-1- [4- (methylthio) phenyl] -2- is preferred among these. Phenylpropane-1-one, more preferably 2-methyl-1- [4- (methylthio) phenyl] -2- A sensitizer to be described later was used in addition to phosphonopropan-1-one.

From the viewpoints of sensitivity, pattern formability, and processability, the content of the photopolymerization initiator is preferably 1% by mass or more, and more preferably 2% by mass or more, of the solid content of the color material of the coloring composition. More preferably, it is 5 mass% or more. On the other hand, from the viewpoints of sensitivity, pattern formability, processability, and heat resistance, the content of the photopolymerization initiator is preferably 30% by mass or less in the solid content of the color material excluding the coloring composition, and more preferably The content is 20% by mass or less, and more preferably 15% by mass or less.

The coloring composition of the present invention can contain both a photopolymerization initiator and a chain transfer agent, and can further improve the sensitivity. Examples of the chain transfer agent include thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, and N- (2-mercaptopropionate). Fluorenyl) glycine, 2-mercaptonicotinic acid, 3- [N- (2-mercaptoethyl) aminomethylamidino] propanoic acid, 3- [N- (2-mercaptoethyl) amino] propane 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-pyridyl alcohol, 2-mercaptobenzothiazole, thioglycolic acid, trimethylolpropane ginseng (3-mercaptopropionate), 1,3,5-ginseng (3-mercaptobutoxyethyl) -1,3 , 5-three -2,4,6 (1H, 3H, 5H) -trione), pentaerythritol (3-mercaptopropionate), 1,4-bis (3-mercaptobutoxy) butane, "Karenz" ( (Registered trademark) MT PE-1 (manufactured by Showa Denko), "Karenz" (registered trademark) MT NR-1 (manufactured by Showa Denko), "Karenz" (registered trademark) MT BD-1 (Showa Denko (Product), isothiol compounds, disulfide compounds obtained by oxidizing the mercapto compounds, iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid, and other iodine Chemical compound. It may contain two or more of these.

The coloring composition of the present invention may further contain a sensitizer, and the sensitivity may be further improved. Examples of the sensitizer include a thioxanthone-based sensitizer, and an aromatic or aliphatic tertiary amine. Examples of the thioxanthone-based sensitizer include thioxanthone, 2-chlorothioxanthone, and 2,4-diethylthio -9-one, "KAYACURE" (registered trademark) DETX-S (made by Nippon Kayaku Co., Ltd.), and the like. It may contain two or more of these.

The coloring composition of the present invention may further contain an organic solvent. Examples of the organic solvent include diethylene glycol monobutyl ether acetate, benzyl acetate, ethyl benzoate, methyl benzoate, diethyl malonate, 2-ethylhexyl acetate, 2-butoxyethyl acetate, ethylene glycol monobutyl ether acetate, diethyl oxalate, ethyl acetate, cyclohexyl acetate, 3-methoxy-butyl acetate, methyl acetate, Ethyl-3-ethoxypropionate, 2-ethylbutyl acetate, isoamyl 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, methylcarbitol, ethylcarbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol tertiary butyl ether, Dipropylene glycol monomethyl ether, ethyl acetate, butyl acetate, isoamyl acetate butanol, 3-methyl-2-butanol, 3-methyl-3-methoxybutanol, cyclopentanone, cyclohexane Ketones, xylene, ethylbenzene, solvent naphtha, etc. It may contain two or more of these.

The coloring composition of the present invention may further contain a polymerization inhibitor and improve stability. Polymerization inhibitors generally show the effect of inhibiting or stopping polymerization caused by free radicals generated by heat, light, and radical initiators. Generally speaking, they are used for anti-gelling or polymerization of thermosetting resins. Polymerization stop at the time of manufacturing. 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, catechol, tertiary butyl catechol and the like. It may contain two or more of these. 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. From the viewpoint of the balance between stability and photosensitivity, 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, and can improve the adhesion of the coating film of the coloring composition to the substrate. Examples of the adhesion improving agent include ethylene trimethoxysilane, ethylene triethoxysilane, ethylene ginseng (2-methoxyethoxy) silane, and N- (2-amineethyl) -3-aminepropyl Methylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropane Silane coupling agents such as trimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane. It may contain two or more of these.

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 surface of the coating film. Examples of the surfactant include anionic surfactants such as ammonium lauryl sulfate and polyoxyethylene alkyl ether triethanolamine; cationic surfactants such as stearylamine acetate and lauryl trimethylammonium chloride; and lauryl Amphoteric surfactants such as methyl dimethylamine oxide, lauryl carboxymethyl hydroxyethyl imidazolium betaine, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, sorbitan monostearate, etc. Ionic surfactants, fluorine-based surfactants, or silicon-based surfactants. It may contain two or more of these. From the viewpoint of in-plane uniformity of the coating film, the content of the surfactant is preferably 0.001 to 10% by mass in the coloring composition.

The coloring composition of the present invention can be suitably used for a reflection type display device described later.

The coloring composition of the present invention can be, for example, a green coloring material having a metal phthalocyanin skeleton, CI Pigment Yellow 138 and / or CI Pigment Yellow 185, and other coloring materials, adhesive resins, and organic solvents as needed. 2. Disperse other ingredients, prepare pigment dispersion, and mix with other ingredients as needed. Examples of the dispersing machine include a sand mill, a ball mill, a bead mill, a three-roll mill, and a mill. Among these, a bead mill having excellent dispersion efficiency is preferred. Examples of the dispersed beads include zirconia beads, alumina beads, and glass beads. Among these, zirconia beads are preferred. When a pigment is contained as a coloring material, it is preferable to add a solvent or the like to the pigment powder in advance, and use a disperser to refine the secondary particles (the particle diameter is about 1 to 50 μm).

Next, the color filter substrate of the present invention will be described. The color filter substrate of the present invention has a pixel including the coloring composition of the present invention on the substrate. That is, the pixels include a light-cured material or a heat-cured material of the coloring composition of the present invention. It may also have other pixels such as red or blue. Furthermore, it is preferable to have a black matrix, a photosensitive spacer, an overcoat layer, or an alignment film, a polarizing plate, a retardation plate, an anti-reflection film, a transparent electrode, a diffusion plate, and the like.

Examples of the substrate include soda glass, alkali-free glass, borosilicate glass, quartz glass, aluminoborosilicate glass, aluminosilicate glass, alkali aluminosilicate glass, and soda lime whose surface is coated with silica. Inorganic glass plates such as glass, or films or sheets of organic plastics. A black matrix may also be formed on these substrates. When the display device provided with the color filter substrate of the present invention is a reflective display device, the substrate may be opaque.

The organic plastic film or sheet may be a self-supporting film, for example, a film formed by coating or the like on a substrate such as a glass substrate.

In the case of this coating film, the adhesion between the substrate and the film can be adjusted to a suitable level by using a laser or the like, and peeling can be performed. Examples of the material of the organic plastic include polyester such as polypropylene, polyethylene, polystyrene, and polyethylene terephthalate (PET), polyphenylene sulfide (PPS), polyimide, and poly Fluorine polymers such as fluorene, polyfluorene, imine, polyether fluorene, polytetrafluoroethylene (PTFE), polyether ether ketone, polyphenylene ether, polyaromatic ester, polyfluorene, and the like. Among these, from the viewpoints of heat resistance, process suitability, mechanical strength, dimensional stability, and chemical resistance, when an organic plastic is used as a substrate, it is preferable that the substrate is polyimide. When an organic plastic is used as the substrate, 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.

Polyimide is not particularly limited, and in general, a polyimide represented by the following general formula (1) can be used. The aforementioned can be obtained, for example, by subjecting a polyfluorene imine precursor represented by the following general formula (2) to ring closure (fluorine imidization) of fluorene. The method of the amidine imidization reaction is not particularly limited, and examples thereof include thermal amidine imidation and chemical amidine imidization. Among these, from the viewpoints of heat resistance of the polyfluorene imide film and transparency in the visible light region, thermal fluorimidization is preferred.

In the general formulae (1) and (2), R ¹ represents a tetravalent organic group, and R ² represents a divalent organic group. X ¹ and X ² each independently represent a hydrogen atom and a monovalent organic group having 1 to 10 carbon atoms.

R ¹ in the general formulae (1) and (2) represents a tetravalent organic group, and is an acid dianhydride and a derivative residue thereof.

The acid dianhydride is not particularly limited, and examples thereof include an aromatic acid dianhydride, an alicyclic acid dianhydride, and an aliphatic acid dianhydride.

Examples of the aromatic acid dianhydride include pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,3,3', 4'-biphenyltetracarboxylic acid Dianhydride, 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-bitriphenyltetracarboxylic dianhydride, 3,3 ', 4,4'- Oxyphthalic acid dianhydride, 2,3,3 ', 4'-oxyphthalic acid dianhydride, 2,3,2', 3'-oxyphthalic acid dianhydride, diphenylphosphonium-3 , 3 ', 4,4'-tetracarboxylic dianhydride, benzophenone-3,3', 4,4'-tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl ) Propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,1-bis ( 2,3-dicarboxyphenyl) ethane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, 1,4- (3 , 4-dicarboxyphenoxy) phthalic anhydride, bis (1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylic acid) 1,4-phenylene-2, 2-bis (4- (4-aminophenoxy) phenyl) propane, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-fluorenetetracarboxylic dianhydride, 2 , 2-bis (3,4-dicarboxyphenyl) hexa Propane dianhydride, 2,2-bis (4- (3,4-dicarboxybenzyloxy) phenyl) hexafluoropropane dianhydride, 1,6-difluoro pyromellitic dianhydride, 1-tris Fluoromethyl pyromellitic dianhydride, 1,6-ditrifluoromethyl pyromellitic dianhydride, 2,2'-bis (trifluoromethyl) -4,4'-bis (3,4- Dicarboxyphenoxy) biphenyl dianhydride, 2,2'-bis [(dicarboxyphenoxy) phenyl] propane dianhydride, 2,2'-bis [(dicarboxyphenoxy) phenyl] hexa Fluoropropane dianhydride or an acid dianhydride compound in which such an aromatic ring is substituted by an alkyl group, an alkoxy group, a halogen atom, or the like is not limited thereto.

Examples of the alicyclic acid dianhydride include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,2,3 1,4-Cyclopentanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1 , 2,3,4-cyclobutane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclo Heptane tetracarboxylic dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 3,4-dicarboxy-1-cyclohexyl succinic dianhydride, 2,3,5-tricarboxycyclopentyl Acetic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic dianhydride, bicyclic [3,3,0] octane-2,4,6,8-tetra Carboxylic dianhydride, bicyclic [4,3,0] nonane-2,4,7,9-tetracarboxylic dianhydride, bicyclic [4,4,0] decane-2,4,7,9-tetra Carboxylic dianhydride, bicyclic [4,4,0] decane-2,4,8,10-tetracarboxylic dianhydride, tricyclic [6,3,0,0 <2,6>] undecane- 3,5,9,11-tetracarboxylic dianhydride, bicyclic [2,2,2] octane-2,3,5,6-tetracarboxylic dianhydride, bicyclic [2,2,2] oct-7 -Ene-2,3,5,6-tetracarboxylic dianhydride, bicyclic [2,2,1] heptane tetracarboxylic dianhydride, bicyclic [2,2,1] heptane-5-carboxymethyl- 2,3,6-tricarboxylic dianhydride, 7-oxabicyclo [2,2,1] heptane-2,4,6,8-tetracarboxylic dianhydride, octahydronaphthalene-1,2,6 , 7-tetracarboxylic dianhydride, tetrahydroanthracene-1,2,8,9-tetracarboxylic dianhydride, 3,3 ', 4,4'-dicyclohexanetetracarboxylic dianhydride, 3,3 ', 4,4'-oxydicyclohexanetetracarboxylic dianhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene- 1,2-dicarboxylic anhydride, and "RIKACID" (registered trademark) BT-100 (the above are the trade names, manufactured by Nippon Rika Co., Ltd.) and their derivatives, or are alkyl, alkoxy, The alicyclic acid dianhydride compounds which substitute halogen atoms and the like are not limited to these.

Examples of the aliphatic acid dianhydride include 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-pentanetetracarboxylic dianhydride, and derivatives thereof. It is not limited to these.

These aromatic acid dianhydrides, alicyclic acid dianhydrides, or aliphatic acid dianhydrides can be used alone or in combination of two or more kinds.

From the viewpoint of being commercially available and easily available, and the viewpoint of reactivity, it is preferable to use pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic acid di among these. Anhydride, 3,3 ', 4,4'-oxyphthalic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 2,2'-bis [(di Carboxyphenoxy) phenyl] propane dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3 ', 4 , 4'-dicyclohexane tetracarboxylic dianhydride, 1,2,3,4-cyclobutane tetracarboxylic dianhydride.

Furthermore, from the viewpoints of heat resistance and prevention of coloring during firing, it is more preferable to use 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 3,3,4', 4'- Oxyphthalic acid dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 2,2'-bis [(dicarboxyphenoxy) phenyl] propane dianhydride.

R ² in the general formulae (1) and (2) represents a divalent organic group, and is a diamine or a derivative residue thereof.

The diamine is not particularly limited, and examples thereof include an aromatic diamine compound, an alicyclic diamine compound, and an aliphatic diamine compound.

Examples of the aromatic diamine compound include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, and 4,4 ' -Diaminodiphenylmethane, 3,3'-diaminodiphenylhydrazone, 3,4'-diaminodiphenylhydrazone, 4,4'-diaminodiphenylhydrazone, 3,4'-di Amino diphenyl sulfide, 4,4'-diamino diphenyl sulfide, 1,4-bis (4-aminophenoxy) benzene, benzidine, 2,2'-bis (trifluoromethyl) ) Benzidine, 3,3'-bis (trifluoromethyl) benzidine, 2,2'-dimethylbenzidine, 3,3'-dimethylbenzidine, 2,2'3,3'- Tetramethylbenzidine, 2,2'-dichlorobenzidine, 3,3'-dichlorobenzidine, 2,2'3,3'-tetrachlorobenzidine, m-phenylenediamine, p-phenylenediamine Amine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis (4-aminophenoxyphenyl) fluorene, bis (3-aminophenoxyphenyl) fluorene, bis [4- (3-Aminophenoxy) phenyl] pyrene, bis (4-aminophenoxy) biphenyl, bis {4- (4-aminophenoxy) phenyl} ether, 1,4-bis (4-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) fluorene, 2,2'-bis [3- (3-aminobenzylamine) -4-hydroxyphenyl ] Hexafluoropropane, or substituted with an alkyl, alkoxy, halogen atom, etc. And other aromatic ring diamine compounds, but are not limited to these.

Examples of the alicyclic diamine compound include cyclobutanediamine, isophoronediamine, bicyclo [2,2,1] heptanedimethylamine, and tricyclo [3,3,1,13,7 ] Decane-1,3-diamine, 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, trans-1,4-diaminocyclohexane Alkanes, 4,4'-diaminodicyclohexylmethane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 3,3'-diethyl-4,4 ' -Diaminodicyclohexylmethane, 3,3 ', 5,5'-tetramethyl-4,4'-diaminodicyclohexylmethane, 3,3', 5,5'-tetraethyl- 4,4'-diaminodicyclohexylmethane, 3,5-diethyl-3 ', 5'-dimethyl-4,4'-diaminodicyclohexylmethane, 4,4'-di Amino dicyclohexyl ether, 3,3'-dimethyl-4,4'-diamino dicyclohexyl ether, 3,3'-diethyl-4,4'-diamino dicyclohexyl ether , 3,3 ', 5,5'-tetramethyl-4,4'-diaminodicyclohexyl ether, 3,3', 5,5'-tetraethyl-4,4'-diamine Dicyclohexyl ether, 3,5-diethyl-3 ', 5'-dimethyl-4,4'-diaminodicyclohexyl ether, 2,2-bis (4-aminocyclohexyl) propane , 2,2-bis (3-methyl-4-aminocyclohexyl) propane, 2,2-bis (3-ethyl-4-aminocyclohexyl) propane , 2,2-bis (3,5-dimethyl-4-aminocyclohexyl) propane, 2,2-bis (3,5-diethyl-4-aminocyclohexyl) propane, 2,2 -(3,5-diethyl-3 ', 5'-dimethyl-4,4'-diaminodicyclohexyl) propane, or substituted with an alkyl, alkoxy, halogen atom, etc. An alicyclic diamine compound is not limited to these.

Examples of the aliphatic diamine compound include ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, and 1,6-diamine Alkane diamines such as hexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, and bis ( Ethylene glycol diamines such as amine methyl) ether, bis (2-aminoethyl) ether, bis (3-aminopropyl) ether, and 1,3-bis (3-aminopropyl) tetramethyldiamine Siloxane diamines such as siloxane, 1,3-bis (4-aminobutyl) tetramethyldisilazane, α, ω-bis (3-aminopropyl) polydimethylsiloxane , But it is not limited to these.

These aromatic diamines, alicyclic diamines, or aliphatic diamines can be used alone or in combination of two or more kinds.

X ¹ and X ² in the general formulae (1) and (2) each independently represent a hydrogen atom and a monovalent organic group having 1 to 10 carbon atoms. Examples of the monovalent organic group having 1 to 10 carbon atoms include a saturated hydrocarbon group, an unsaturated hydrocarbon group, and an aromatic group. Examples of the saturated hydrocarbon group include alkyl groups such as methyl, ethyl, and butyl. Examples of the unsaturated hydrocarbon group include a vinyl group, an ethynyl group, a biphenyl group, and a phenylethynyl group. The saturated hydrocarbon group may be further substituted with a halogen atom. Examples of the aromatic group include a phenyl group. The aromatic group may be further substituted with a saturated hydrocarbon group, an unsaturated hydrocarbon group, or a halogen atom.

The polyfluorene imide used for the substrate requires heat resistance and high transparency in the visible light region. Therefore, in order to further improve transparency, it is effective to use an alicyclic monomer component system for an acid dianhydride or a diamine component. The alicyclic monomer can be used for both the acid dianhydride and the diamine component, and can also be used for the single side. Further, it may be used in combination with an aromatic monomer.

In order to maintain the transparency of polyimide at a higher level, it is preferable that R ¹ in the general formulae (1) and (2) is selected from the following general formulae (3) to (8) It is preferable that one or more of the structures shown in the following general formulae (3) to (8) in R ¹ in the general formulae (1) and (2) are 50 mol% or more, and more It is preferably 80 mol% or more, and even more preferably 100 mol%. Among these, from the viewpoint of reducing the coefficient of linear expansion, R ¹ in the general formulae (1) and (2) is preferably the following general formulae (3), (5), and (6).

From the viewpoint of reducing the coefficient of linear expansion of polyfluoreneimine, R ² in the general formulae (1) and (2) is preferably selected from the following general formulae (9) to (12) One or more of the structures shown is preferably 50 mol% or more in the structure represented by the following general formulae (9) to (12) in R ¹ in the general formulae (1) and (2), It is more preferably 80 mol% or more, and still more preferably 100 mol%. Among them, from the viewpoint of improving solubility and reducing the coefficient of linear expansion, R ² in the general formulae (1) and (2) is preferably the following general formula (10). From the viewpoint of improving the transmittance of polyfluoreneimide, as R ² in the general formulae (1) and (2), the following general formula (9) or (10) is preferred.

In addition, from the viewpoint of increasing the transmittance of polyfluoreneimide, facilitating laser peeling, and reducing the coefficient of linear expansion, it is preferable that R ² in the general formulae (1) and (2) include One or more of the structures represented by the general formula (13) or (14) are described. Furthermore, the general formula (14) The azole ring system is formed by dehydration ring closure of a structure represented by the general formula (13). From the viewpoint of processability of a pixel formed on polyimide, R ² in the general formulae (1) and (2) is represented by the following general formula (13) or (14). The structure shown is preferably 30 mol% or less, and more preferably 20 mol% or less.

As a method for the polymerization reaction to obtain polyimide and a polyimide precursor, as long as the intended polyimide and a polyimide precursor can be produced, the method is not particularly limited, and a known method can be used. As a specific reaction method, a method of adding a predetermined amount of all diamine components and a solvent to a reactor and dissolving, adding a predetermined amount of an acid dianhydride component, and stirring at room temperature to 80 ° C for 0.5 to 30 hours may be mentioned. Wait. As the acid dianhydride and diamine used in the synthesis of the polyimide precursor, a known one can be used, and preferably one as described above. In addition, polyimide precursors such as polyamic acid, polyamic acid esters, and polysilicic acid silane esters can be synthesized by reacting a diamine compound with an acid dianhydride or a derivative thereof. Examples of the derivative include tetracarboxylic acids of the acid dianhydride, mono-, di-, tri-, or tetra-esters of the tetracarboxylic acid, acid chlorides, and the like. Specific examples include methyl, ethyl, Esterified structures such as n-propyl, isopropyl, n-butyl, secondary butyl, tertiary butyl, etc.

In order to adjust the molecular weight to a better range, the polyimide and the polyimide precursor may be blocked at both ends by a blocking agent. Examples of the end-capping agent that reacts with an acid dianhydride include monoamines and monovalent alcohols. Examples of the terminal blocking agent that reacts with a diamine compound include acid anhydrides, monocarboxylic acids, monoacid chloride compounds, monoactive ester compounds, dicarbonates, vinyl ethers, and the like. In addition, by reacting the blocking agent, various organic groups can be introduced as terminal groups.

The introduction ratio of the blocking agent at the end of the acid anhydride group is preferably in the range of 0.1 to 60 mole%, and particularly preferably 5 to 50 mole% relative to the acid dianhydride component. The introduction ratio of the amine-terminated blocking agent is preferably in the range of 0.1 to 100 mole%, and particularly preferably 5 to 90 mole% relative to the diamine component. By reacting a plurality of end-capping agents, a plurality of different terminal groups can also be introduced.

Examples of the pixels include red and blue colored pixels and transparent pixels. Examples of the material constituting the pixels include a coloring composition of the present invention, and a coloring photosensitive composition 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 still 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, it is preferably 3.0 μm or less, and more preferably 2.8 μm or less.

The black matrix is for preventing the contrast caused by light leakage between pixels or the decrease in color purity, and is preferably disposed between pixels or a frame edge 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 radical polymerizable compound, and a non-photosensitive resin composition colored in black. From the viewpoint of light-shielding 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.

Since the photosensitive spacer is provided with a certain gap between the opposing plate, and the gap can be filled with a liquid crystal compound or the like, the step of arranging the spacer can be omitted when manufacturing the liquid crystal display device. It is preferably formed at a specific position of the color filter substrate while being in contact with and fixed to the counter substrate when the liquid crystal display device is manufactured. Examples of the material constituting the photosensitive spacer 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 photosensitive spacer include a cylindrical shape, an angular pillar shape, a truncated cone shape, a truncated cone shape, and the like. The diameter of the photosensitive spacer is not particularly specified, but is preferably 2 to 20 μm, and more preferably 3 to 10 μm. The height of the photosensitive spacer is preferably 1 to 10 μm.

The overcoat layer is to suppress the transmission of impurities from the pixels of the color filter substrate, and flatten the step difference caused by the pixels of the color filter substrate. Examples of the material constituting the overcoat layer include epoxy resin, acrylic epoxy resin, acrylic resin, siloxane resin, polyimide resin, and commercially available photosensitive or non-photosensitive materials as flattening materials. Of materials, etc. 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 the material constituting the transparent electrode include metals such as aluminum, chromium, tantalum, titanium, neodymium, and molybdenum, indium tin oxide (ITO), and indium zinc oxide (InZnO).

Examples of a method for manufacturing a color filter substrate include a method of patterning pixels including a resin composition on a substrate. Hereinafter, a manufacturing method will be described using a color filter substrate having a pixel including the coloring composition of the present invention having a photosensitive property as an example. The coloring composition of the present invention is coated on a substrate, patterned by selective exposure and development using a photomask, and pixels are formed by firing to obtain a color filter substrate.

Examples of the method for applying the colored composition of the present invention to a substrate include a spin coater, a bar coater, a blade coater, a roll coater, a die coater, an ink jet printing method, a screen printing method, A method of immersing a substrate in a colored composition, a method of spraying a colored composition on a substrate, and the like. Next, the substrate on which the colored composition is applied is dried to form a coating film of the colored composition on the substrate. Examples of the drying method include air drying, heat drying, and vacuum drying. Two or more of these may be combined, and for example, drying under reduced pressure and then heating and drying are preferred. The heating and drying temperature is preferably 80 to 130 ° C. As the heating and drying device, a hot air oven and a hot plate are preferred. In the case of a color filter substrate having a black matrix, it is preferable to form a coating film of a colored composition on a substrate on which a black matrix is formed in advance.

Next, a photomask is placed on the coating film of the colored composition, and exposure is selectively performed. Examples of the exposure machine include a proximity exposure machine, a mirror projection exposure machine, a lens scanning exposure machine, and a stepper. From the viewpoint of accuracy, a lens scanning exposure machine is preferred. Examples of the light source used in the exposure include an ultrahigh-pressure mercury lamp, a chemical lamp, and a high-pressure mercury lamp.

Thereafter, 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 developer include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium silicate, sodium metasilicate, and ammonia, ethylamine, and Primary amines such as propylamine, secondary amines such as diethylamine and di-n-propylamine, tertiary amines such as triethylamine and methyldiethylamine, and organic bases 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 of immersing a coating film after exposure in an alkali developing solution for 20 to 300 seconds.

Thereafter, the obtained coating film pattern is subjected to a heat treatment to obtain a color filter substrate in which a pixel pattern is formed. Heat treatment can also be performed in any air, nitrogen environment, and vacuum. The heating temperature is preferably 150 to 350 ° C, and more preferably 180 to 250 ° C. The heating time is preferably 5 minutes to 5 hours. As a heat processing apparatus, a hot-air oven and a hot plate are preferable. The heat treatment may be performed continuously or stepwise.

For each pixel of 3 to 6 colors that the color filter substrate has, pixel formation is performed sequentially using the method described above. The formation order of each color is not particularly limited, but when forming a pixel containing a dye, it is preferable to form a pixel containing a dye after the formation of other pixels from the viewpoint of further suppressing the color shift of the color material.

In addition, when the coloring composition containing a green color material and a yellow color material and the ratio of the yellow color material in the color material is high, from the viewpoint that the light transmittance retention of the color pixels becomes low, The color filter substrate is a color filter substrate having red pixels, green pixels, blue pixels, and a color pixel of a fourth color. It is preferable that the color pixels of the fourth color include the coloring of the present invention. Light-cured or heat-cured composition. From the viewpoint of improving color purity and improving transmittance retention, it is preferable that the light absorption rate of the fourth color pixel at 480 nm is 50% or more, and the light absorption rate at 650 nm is 10 Above 90%.

Here, the light absorbance of a color pixel refers to the proportion of light that hinders the passage of light of a certain wavelength when passing through the color pixel. Determination. In addition, the light absorption rate of the fourth color pixel on the color filter substrate can be determined from the light absorption rate of the area where no color pixel is formed on the color filter substrate and the fourth color pixel on the color filter substrate. The light absorptivity of the color pixel area is calculated.

In order to obtain the color pixels of the fourth color as described above, it is preferable that the color pixels include CI Pigment Green 58 and CI Pigment Yellow 185, and the content of CI Pigment Yellow 185 in the color material is 50% by mass. The content of the color material in the component is preferably 5% by mass or more.

The color filter substrate of the present invention can be a constituent element of a display device such as a liquid crystal display, an organic EL display, or an electronic paper. That is, the display device of the present invention includes 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 enhancement film, or a diffusion plate. A display device refers to a device that recognizes a part of a screen and displays an image. Examples of the display element include a liquid crystal element, an organic EL element, an inorganic EL element, a display element using a MEMS, a display element using a quantum dot, an electronic ink, an electronic powder fluid, and an electrophoretic element. Examples of the display device include a transmissive liquid crystal display, a transflective liquid crystal display, a reflective liquid crystal display, an organic EL display, an inorganic EL display, a quantum dot display, and an electronic paper. In a transmissive liquid crystal display, the brightness of the display can be easily increased by increasing the intensity of the backlight light source. In a reflective liquid crystal display that mainly uses ambient light, the transmittance of the color filter determines the brightness of the display. One of the main reasons is that the color filter substrate of the present invention is preferably used in a reflective display device such as a semi-transmissive liquid crystal display or a reflective liquid crystal display. Examples of the reflective display device include a display device using outdoor light or indoor light, such as a wearable terminal, an electronic sign, a digital signage system, and an electronic shelf label. In the case of a reflective display device, a reflective layer made of a metal such as silver or aluminum is provided inside. The reflective layer reflects light incident from the front of the display device and transmits the color filter substrate twice, which can further improve color purity. On the other hand, the light transmittance tends to decrease. Even in the above-mentioned reflective display device, the total content of the green color material having a metal phthalocyanine skeleton and CI Pigment Yellow 138 and CI Pigment Yellow 185 is set to 2% by mass or more and 16% by mass or less in the solid content. Also, a display device having excellent display characteristics can be obtained. The reflective layer is only required to reflect light in the visible light region, and may be a layered structure made of a metal such as silver or aluminum, or a multilayer structure including transparent resins having different refractive indices. From the viewpoint of reflectance, the reflective layer is preferably a layer containing a metal such as silver or aluminum, which is formed by sputtering or vapor deposition.

As an example of a method for manufacturing a display device of the present invention, a method for manufacturing a liquid crystal display device will be described below. The color filter substrate and the array substrate are bonded to each other with a liquid crystal alignment film and a spacer for maintaining a cell gap interposed therebetween. Furthermore, by providing a thin film transistor (TFT) element or a thin film diode (TFD) element, a scanning circuit or a signal circuit on the array substrate, a TFT liquid crystal display device or a TFD liquid crystal display device can be manufactured. Next, after the liquid crystal is injected through an injection port provided in the sealing portion, the injection port is closed. Furthermore, a liquid crystal display device is completed by installing a backlight and constructing an IC driver. In addition, as the backlight, a 2-wavelength LED, a 3-wavelength LED, a CCFL, or the like can be used, but a 3-wavelength LED is preferred from the viewpoint of expanding the color reproduction range of the liquid crystal display device and suppressing power consumption to a low level.

    [Example]    

Examples are given below to illustrate the present invention, but the present invention is not limited to these examples. First, the evaluation methods in Examples and Comparative Examples will be described.

    <Evaluation of chromaticity and light transmittance>    

After applying the colored composition obtained in Examples 1 to 13 and Comparative Examples 1 to 8 on a glass substrate, the glass substrate was heated and dried at 90 ° C for 10 minutes. The obtained coloring composition coating film was exposed at 200 mJ / cm ² with i-rays through a negative mask, and then developed with a 0.3% by mass tetramethylammonium hydroxide aqueous solution at 23 ° C. to form a desired pattern. Next, a heat treatment was performed at 230 ° C. for 30 minutes to obtain a film having a film thickness of 1.7 μm. However, only Example 13 had a film thickness of 2.5 μm. With respect to this film, chromaticity x, y, and light transmittance Y were measured using a C light source using a micro spectrometer LCF-100MA made by Otsuka Electronics Co., Ltd.

    <Evaluation of light absorption rate>    

After applying the colored composition obtained in Examples 1 to 13 and Comparative Examples 1 to 8 on a glass substrate, the glass substrate was heated and dried at 90 ° C for 10 minutes. The obtained coloring composition coating film was exposed at 200 mJ / cm ² with i-rays through a negative mask, and then developed with a 0.3% by mass tetramethylammonium hydroxide aqueous solution at 23 ° C. to form a desired pattern. Next, a heat treatment was performed at 230 ° C. for 30 minutes to obtain a film having a film thickness of 1.7 μm. However, only Example 13 had a film thickness of 2.5 μm. With respect to this film, the optical absorption coefficients at 480 nm and 650 nm were measured using a micro spectrometer LCF-100MA made by Otsuka Electronics Co., Ltd.

    <Evaluation of transmittance retention by light irradiation>    

The colored substrates obtained in Examples 1 to 13 and Comparative Examples 1 to 8 were coated on a glass substrate forming a black matrix, and then heated and dried at 90 ° C for 10 minutes. The obtained coloring composition coating film was exposed at 200 mJ / cm ² with i-rays through a negative mask, and then developed with a 0.3% by mass tetramethylammonium hydroxide aqueous solution at 23 ° C. to form a desired pattern. Next, a heat treatment was performed at 230 ° C. for 30 minutes to obtain a color filter substrate having a green pixel film thickness of 1.7 μm. However, only Example 13 had a film thickness of 2.5 μm. With respect to the green pixels of the color filter substrate, a Y spectrometer LCF-100MA made by Otsuka Electronics Co., Ltd. was used to measure the Y value with a C light source, and the obtained value was taken as Y0.

A TFT element, a transparent electrode, etc. are formed on an alkali-free glass, and an array substrate is produced. On the produced color filter substrate and the array substrate, a polyimide alignment film is formed respectively, and a rubbing treatment is performed. A micron-column sealant was printed on the array substrate, and a bead spacer having a thickness of 6 μm was dispersed, and then the array substrate and the color filter substrate were bonded. A nematic liquid crystal ("Lixon" JC-5007LA, manufactured by Chisso Corporation) was injected through an injection port provided in the sealing portion, and then the polarizing axis was made vertical, and polarizing films were laminated on both sides of the liquid crystal cell to obtain a liquid crystal panel. A white LED backlight including a blue LED and a YAG phosphor is mounted on the liquid crystal panel, and a TAB module, a printed circuit board, and the like are configured to produce a liquid crystal display device. The white LED backlight uses a luminance of 10000 cd / m ² . The liquid crystal display device was put into a constant-temperature, high-humidity tank at 60 ° C. and 60% for 100 hours with the backlight turned on. Then, the panel was disassembled, and a green pixel was measured with a light source C and a Y spectrometer LCF-100MA made by Otsuka Electronics Co., Ltd., and the obtained Y value was used as Y1. Calculate Y1 / Y0 as the transmittance retention.

    Production Example 1 (Preparation of Dispersion (A1))    

150g of CI Pigment Yellow 185 ("Paliotol" (registered trademark) Yellow D1155, manufactured by BASF), 125 g of "BYK" (registered trademark) LPN6919 (manufactured by BYK, polymer dispersant solution (60% by mass of propylene glycol monomethyl ether solution)) , 100 g of "CYCLOMER" (registered trademark) ACA250 (manufactured by Daicel Chemical Co., Ltd., 45% by weight dipropylene glycol monomethyl ether solution), and 625 g of propylene glycol monomethyl ether (PMA) to prepare a slurry. The beaker to which the slurry was added was connected to a horizontal wet disperser with a tube, and a zirconia bead with a diameter of 0.5 mm was used as a medium to perform a dispersion treatment at a peripheral speed of 14 m / s for 8 hours to prepare a CI Pigment Yellow 185 dispersion (A1).

    Production Example 2 (Preparation of Dispersion (A2))    

150. C.I. Pigment Green 58 ("FASTGEN" (registered trademark) Green A110, manufactured by DIC) was used instead of C.I. Pigment Yellow 185, except that C.I. Pigment Green 58 dispersion (A2) was prepared.

    Production Example 3 (Preparation of Dispersion (A3))    

CI Pigment Yellow 138 ("LIONOGEN" (registered trademark) YELLOW 010) manufactured by Toyo Ink Co., Ltd.) was used instead of CI Pigment Yellow 185 except that 150 g of CI Pigment Yellow 138 was used. .

    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, 34 g (0.4 mol) of methacrylic acid, and 2,2'-azobis (2-methylbutyronitrile) were added. ) 3 g (0.02 mol) and 150 g of propylene glycol monomethyl ether acetate (PGMEA), and after stirring at 90 ° C for 2 hours, the internal temperature was raised to 100 ° C and further stirred for 1 hour to obtain a reaction solution. To the obtained reaction solution, 33 g (0.2 mol) of propylene methacrylate, 1.2 g (0.009 mol) of dimethylaniline and 0.2 g (0.002 mol) of p-methoxyphenol were added, and the mixture was stirred at 90 ° C. After 4 hours, 50 g of 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 using a potential difference automatic measuring device AT-610 manufactured by Kyoto Electronics Industry Co., Ltd. for a 0.1 mol / L potassium hydroxide. Ethanol solution, and the acid value was 80.0 (mgKOH / g). In addition, using a GPC device, the weight average molecular weight in terms of polystyrene was calculated, and the weight average molecular weight was 22,000.

    Example 1    

In a 50 mL plastic bottle, 0.99 g of the dispersion liquid A1 obtained in Production Example 1, 3.95 g of the dispersion liquid A2 obtained in Production Example 2, 3.27 g of the binder resin solution B1 obtained in Production Example 4, and penta (meth) propylene were added. 2.30 g of oxydipentaerythritol monosuccinate (C1), 2-methyl-1- [4- (methylthio) phenyl] -2- Phenylpropan-1-one (D1) 0.31g, 2,4-diethylsulfur 0.15 g of -9-one (D2) and 19.03 g of dipropylene glycol methyl ether acetate (hereinafter referred to as DPMA) were stirred for 3 hours to prepare a colored composition (E1). With respect to the obtained colored composition, the light transmittance retention was evaluated by the aforementioned method, and Y1 / Y0 was 0.980. The chromaticity was x = 0.309, y = 0.459, and the light transmittance Y was 78.1. The light absorption rate at 480 nm was 47.8%, and the light absorption rate at 650 nm was 86.1%.

    Examples 2 to 13, Comparative Examples 1 to 8    

As described in Table 1, the coloring composition was obtained in the same manner as in Example 1 except that the types and addition ratios of the dispersion liquid, the binder resin solution, the radical polymerizable compound, the photopolymerization initiator, and the organic solvent were changed. (E2 ~ E21). Using the obtained coloring composition, the evaluation results by the aforementioned methods are summarized in Tables 2 and 3.

    Example 14    

Under a stream of dry nitrogen, 3.34 g (17.0 mmol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 2,2'-bis (trifluoromethyl) benzidine 4.64 were added to a 100 mL 4-necked flask. g (14.5 mmol), 2,2-bis [3- (3-aminobenzylamine) -4-hydroxyphenyl] hexafluoropropane 1.55 g (2.56 mmol), N-methyl-2-pyrrolidine 50 g of ketone was heated and stirred at 60 ° C. After 8 hours, cool as a varnish.

Next, the obtained varnish was spin-coated on a glass substrate and subjected to a pre-baking treatment at 140 ° C. for 4 minutes to form a film having a film thickness of 10 μm. After that, the pre-baking film was heated to 300 ° C. at 3.5 ° C./min under a nitrogen flow (oxygen concentration of 20 ppm or less) using an oxidation-free oven (INH-21CD manufactured by Koyo Thermo Systems Co., Ltd.) for 30 minutes, and Cool at 5 ° C / min to 50 ° C to form a polyimide film.

Next, the colored composition obtained in Example 3 was applied, and then heated and dried at 90 ° C for 10 minutes. The obtained coloring composition coating film was exposed to 200 mJ / cm ^{2 of} i-rays through a negative mask, and then developed with a 0.3% by mass tetramethylammonium hydroxide aqueous solution at 23 ° C. to form 20 μm × 200 μm. Size pattern and 15 μm × 150 μm size pattern. Next, a heat treatment was performed at 230 ° C. for 30 minutes to obtain a film having a film thickness of 1.7 μm.

The obtained substrate with pixels was irradiated with 308 nm excimer laser (shape: 21 mm × 1.0 mm) from the glass substrate side, and after the laser peel test was performed, the irradiation energy was 250 mJ / cm ² from the glass. The substrate confirmed the curl of the polyimide film.

    Example 15    

Under a stream of dry nitrogen, 2.33 g (11.9 mmol) of 2,2-bis [3- (3-aminobenzyl) was added to a 100 mL 4-necked flask. Amido) -4-hydroxyphenyl] hexafluoropropane 7.19 g (11.9 mmol) and N-methyl-2-pyrrolidone 50 g, and the mixture was heated with stirring at 60 ° C. After 8 hours, cool as a varnish.

Next, the obtained varnish was spin-coated on a glass substrate and subjected to a pre-baking treatment at 140 ° C. for 4 minutes to form a film having a film thickness of 10 μm. After that, the pre-baking film was heated to 300 ° C. at 3.5 ° C./min under a nitrogen flow (oxygen concentration of 20 ppm or less) using an oxidation-free oven (INH-21CD manufactured by Koyo Thermo Systems Co., Ltd.) for 30 minutes, and Cool at 5 ° C / min to 50 ° C to form a polyimide film.

Next, the colored composition obtained in Example 3 was applied, and then heated and dried at 90 ° C for 10 minutes. The obtained coloring composition coating film was exposed to 200 mJ / cm ^{2 of} i-rays through a negative mask, and then developed with a 0.3% by mass tetramethylammonium hydroxide aqueous solution at 23 ° C. to form 20 μm × 200 μm. Size pattern, but a pattern with a size of 15 μm × 150 μm cannot be formed. Next, a heat treatment was performed at 230 ° C. for 30 minutes to obtain a film having a film thickness of 1.7 μm.

The obtained substrate with pixels was irradiated with 308 nm excimer laser (shape: 21 mm × 1.0 mm) from the glass substrate side, and after the laser peel test was performed, the irradiation energy was 250 mJ / cm ² from the glass. The substrate confirmed the curl of the polyimide film.

    Example 16    

Under a stream of dry nitrogen, 3.62 g (18.4 mmol) of 1,3-bis (4-aminophenyl) benzene 5.38 was added to a 100 mL 4-necked flask. g (18.4 mmol) and 50 g of N-methyl-2-pyrrolidone, and heated and stirred at 60 ° C. After 8 hours, cool as a varnish.

Next, the obtained varnish was spin-coated on a glass substrate and subjected to a pre-baking treatment at 140 ° C. for 4 minutes to form a film having a film thickness of 10 μm. After that, the pre-baking film was heated to 300 ° C. at 3.5 ° C./min under a nitrogen flow (oxygen concentration of 20 ppm or less) using an oxidation-free oven (INH-21CD manufactured by Koyo Thermo Systems Co., Ltd.) for 30 minutes, and Cool at 5 ° C / min to 50 ° C to form a polyimide film.

Next, the colored composition obtained in Example 3 was applied, and then heated and dried at 90 ° C for 10 minutes. The obtained coloring composition coating film was exposed to 200 mJ / cm ^{2 of} i-rays through a negative mask, and then developed with a 0.3% by mass tetramethylammonium hydroxide aqueous solution at 23 ° C. to form 20 μm × 200 μm. Size pattern and 15 μm × 150 μm size pattern. Next, a heat treatment was performed at 230 ° C. for 30 minutes to obtain a film having a film thickness of 1.7 μm.

For the obtained substrate with pixels, an excimer laser (shape: 21 mm × 1.0 mm) at 308 nm was irradiated from the glass substrate side, and after performing a laser peel test, the irradiation energy was 400 mJ / cm ² from the glass. The substrate confirmed the curl of the polyimide film.

Industrial availability

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

Claims (16)

    A coloring composition comprising a green coloring material having a metal phthalocyanin skeleton and a yellow coloring material including CI Pigment Yellow 138 and / or CI Pigment Yellow 185, wherein the green coloring material has a metal phthalocyanin skeleton The total content of the material and CI Pigment Yellow 138 and CI Pigment Yellow 185 is 2% by mass or more and 16% by mass or less in the solid content.         The coloring composition according to claim 1, wherein the total content of the green color material having a metal phthalocyanin skeleton and the yellow color material containing C.I. Pigment Yellow 138 and C.I. Pigment Yellow 185 is 60% by mass or more in the color material.         For example, the coloring composition of claim 2, wherein the green coloring material having a metal phthalocyanin skeleton includes CI Pigment Green 58 and / or CI Pigment Green 59, wherein CI Pigment Green 58 and CI Pigment Green 59, CI Pigment Yellow 138, The total content of CI Pigment Yellow 185 is 80% by mass or more in the color material.         For example, the coloring composition of claim 3, which contains C.I. Pigment Green 58, C.I. Pigment Green 59, C.I. Pigment Yellow 138, and C.I. Pigment Yellow 185 in a total content of 2 to 16% by mass of the solid content.         For example, the coloring composition of claim 3 or 4, wherein the content of C.I. Pigment Green 58 is 80% by mass or more in the green color material.         The coloring composition according to any one of claims 1 to 5, wherein the content of C.I. Pigment Yellow 185 is 60% by mass or more in the yellow color material.         The coloring composition according to any one of claims 1 to 6, wherein the content of C.I. Pigment Yellow 185 is 50% by mass or more and 90% by mass or less in the color material.         The colored composition according to any one of claims 1 to 7, further comprising a radical polymerizable compound, and the content of the radical polymerizable compound is 40% by mass or more and 90% by mass or less in the solid content.         The colored composition according to claim 8, wherein the radically polymerizable compound contains a radically polymerizable compound having three or more (meth) acryloxy groups and a carboxyl group, and the (meth) acrylic acid has three or more The content of the radically polymerizable compound of an oxygen group and a carboxyl group is 50% by mass or more and 100% by mass or less of the radically polymerizable compound.         The coloring composition according to any one of claims 1 to 9, which is for a reflective display device.         A color filter substrate is a color filter substrate having at least a substrate and a pixel, the pixel including a light-hardened material or a heat-hardened material of the coloring composition according to any one of claims 1 to 10.         A color filter substrate is a color filter substrate having at least a substrate and a red pixel, a green pixel, a blue pixel, and a fourth color pixel, wherein the fourth color pixel includes The light-hardened material or the heat-hardened material of the colored composition according to any one of claims 1 to 10.         For example, the color filter substrate of claim 12, wherein the light absorption rate of the fourth color pixel at 480 nm is 50% or more, and the light absorption rate at 650 nm is 10% or more and 90% or less.         The color filter substrate of claim 11 or 12, wherein the substrate comprises polyimide.         A display device includes at least a color filter substrate and a display element according to any one of claims 11 to 14.         The display device of claim 15 further has a reflective layer.