WO2018151044A1 - 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 colored composition, a color filter substrate using the same, and a display device.

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

For green pixels, various combinations of pigments have been studied, but it is common to combine a green color material having a metal phthalocyanine skeleton and a yellow color material. With regard to such technology, for example, a green colorant selected from the group consisting of Pigment Green 7, Pigment Green 36, and Pigment Green 58, and a yellow colorant selected from the group consisting of Pigment Yellow 129, Pigment Yellow 138, and Pigment Yellow 150 There is known a green colorant composition containing azobenzene (see, for example, Patent Document 1).

On the other hand, when phthalocyanine is irradiated with light in an oxygen-blocked state, it is known that the light transmittance of a green pixel formed of phthalocyanine is reduced due to a change in absorption spectrum (for example, Non-Patent Document 1). reference). That is, when a liquid crystal display device having a green pixel formed of phthalocyanine is irradiated with light in an oxygen-blocked state, the light transmittance of the green pixel is lowered and the brightness of the liquid crystal display device is darkened.

JP 2014-41341 A

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

When a green color material having a metal phthalocyanine skeleton as described in Patent Document 1 and a specific yellow color material are combined, when light is irradiated in an oxygen-blocked state, the light transmittance is significantly reduced and the display performance is changed. There was a problem to do. In view of such a situation, the present invention provides a colored composition having high color purity and light transmittance and capable of suppressing a decrease in light transmittance due to light irradiation, and a color filter substrate and a display device using the colored composition. The purpose is to provide.

The present invention relates to a green color material having a metal phthalocyanine skeleton, C.I. I. Pigment yellow 138 and / or C.I. I. A coloring composition containing a yellow colorant including CI Pigment Yellow 185, wherein the green colorant has a metal phthalocyanine skeleton; I. Pigment yellow 138 and C.I. I. It is a coloring composition whose total content with pigment yellow 185 is 2 mass% or more and 16 mass% or less in 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 colored pixels that have high color purity and light transmittance and suppress a decrease in light transmittance due to light irradiation.

The coloring composition of the present invention comprises a green color material having a metal phthalocyanine skeleton, C.I. I. Pigment yellow 138 and / or C.I. I. Contains yellow colorant including CI Pigment Yellow 185. A green color material having a metal phthalocyanine skeleton; I. Pigment yellow 138 and / or C.I. I. By including a yellow color material including Pigment Yellow 185, color purity and light transmittance can be improved. Here, “color purity can be improved” means that in the CIE 1931 color system, the distance from the light source (for example, in the case of the C light source, coordinates x = 0.310, y = 0.316) is more The ability to express distant colors. In addition, since the light transmittance of the coloring composition varies greatly depending on its chromaticity, the phrase “can improve the light transmittance” here means that the light transmittance can be increased when the chromaticity coordinates are the same. That means. On the other hand, as described above, when a green color material having a metal phthalocyanine skeleton is irradiated with light in an oxygen-blocked state, there is a problem that the light transmittance is significantly reduced and the display performance is changed. The present invention relates to C.I. I. Pigment yellow 138 and / or C.I. I. Pigment Yellow 185, a green color material having a metal phthalocyanine skeleton, and C.I. I. Pigment yellow 138 and C.I. I. By making the total content with Pigment Yellow 185 2% by mass or more and 16% by mass or less in the solid content, it is possible to improve the color purity and the light transmittance and to suppress the light transmittance decrease due to light irradiation. Is found.

The green color material having a metal phthalocyanine skeleton is C.I. from the viewpoint of further improving the light transmittance. I. Pigment green 58, C.I. I. Pigment Green 59 is preferable. C. I. Pigment green 58 and C.I. I. The total content of 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, C.I. I. Pigment green 58 or C.I. I. It is preferable to use CI Pigment Green 59 alone. Further, from the viewpoint of further improving the light transmittance retention, C.I. I. Pigment Green 58 is more preferable. From the viewpoint of further improving the light transmittance retention, C.I. I. The content of 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 is C.I. I. Pigment yellow 138 and / or C.I. I. Pigment Yellow 185 may be contained, and other color materials may be further contained. From the viewpoint of further improving light transmittance and light transmittance retention, C.I. I. Pigment Yellow 185 is more preferable. From the viewpoint of improving the light transmittance, C.I. I. Pigment yellow 138 and C.I. I. The total content of Pigment Yellow 185 is preferably 60% by mass or more, more preferably 80% by mass or more, and still more preferably 90% by mass or more in the yellow color material. Furthermore, C.I. I. The content of Pigment Yellow 185 is preferably 60% by mass or more, more preferably 80% by mass or more, and still more preferably 90% by mass or more in the yellow color material. From the viewpoint of improving the light transmittance, C.I. I. Pigment Yellow 185 is preferably used alone.

From the viewpoint of improving the transmittance, C.I. I. Pigment Yellow 185 is preferably contained, but in general, C.I. I. When the content of Pigment Yellow 185 is 50% by mass or more and 90% by mass or less, light transmittance tends to be reduced by light irradiation. As described later, the present invention relates to a green color material having a metal phthalocyanine skeleton, C.I. I. Pigment yellow 138 and C.I. I. By setting the total content of CI Pigment Yellow 185 within a specific range, it is possible to suppress a decrease in transmittance due to light irradiation, and thus C.I. I. When the content of Pigment Yellow 185 is 50% by mass or more and 90% by mass or less, a higher effect is achieved.

C. I. Pigment yellow 138 and C.I. I. Examples of yellow color materials other than Pigment Yellow 185 include organic pigments, inorganic pigments, dyes, and the like. I. Pigment Yellow (hereinafter “PY”) 12, PY13, PY17, PY20, PY24, PY83, PY86, PY93, PY95, PY109, PY110, PY117, PY125, PY129, PY137, PY139, PY147, PY148, PY150, YY153P , PY166, PY168 (all numbers are color index numbers). Two or more of these may be contained. From the viewpoint of color purity, light transmittance, and contrast, PY129, PY139, and PY150 are preferable, and PY150 is more preferable.

The coloring composition of the present invention includes a green color material having a metal phthalocyanine skeleton, C.I. I. Pigment yellow 138 and C.I. I. The total content of CI Pigment Yellow 185 is 2% by mass or more and 16% by mass or less in the solid content. A green color material having a metal phthalocyanine skeleton, C.I. I. Pigment yellow 138 and C.I. I. When the total content of Pigment Yellow 185 is less than 2% by mass in the solid content, the color purity is lowered. The total content thereof is preferably 3% by mass or more, and more preferably 5% by mass or more. On the other hand, a green color material having a metal phthalocyanine skeleton, C.I. I. Pigment yellow 138 and C.I. I. When the total content of Pigment Yellow 185 exceeds 16% by mass in the solid content, the light transmittance is lowered by light irradiation, and the light transmittance retention is lowered.

Green color material having a metal phthalocyanine skeleton, C.I. I. Pigment yellow 138 and C.I. I. From the viewpoint of further improving the color purity, the total content of CI Pigment Yellow 185 is preferably 60% by mass or more, more preferably 80% by mass or more, and further preferably 90% by mass or more.

From the viewpoint of further improving the light transmittance, the green color material having a metal phthalocyanine skeleton is C.I. I. Pigment green 58 or C.I. I. Pigment Green 59 is preferably included, and C.I. I. Pigment green 58, C.I. I. Pigment green 59, C.I. I. Pigment yellow 138 and C.I. I. From the viewpoint of further improving the color purity, the total content of CI Pigment Yellow 185 is preferably 60% by mass or more, more preferably 80% by mass or more, and further preferably 90% by mass or more.

Also, C.I. I. Pigment green 58, C.I. I. Pigment green 59, C.I. I. Pigment yellow 138 and C.I. I. The total content of the coloring material including Pigment Yellow 185 is preferably 2% by mass or more and 16% by mass or less in the solid content.

Furthermore, C.I. I. Pigment green 58 and C.I. I. From the viewpoint of further improving the color purity, the total content of CI Pigment Yellow 185 is preferably 60% by mass or more, more preferably 80% by mass or more, and further preferably 90% by mass or more.

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

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

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

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

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

Examples of purple pigments include C.I. I. Pigment violet (hereinafter referred to as “PV”) 19, PV23, PV29, PV30, PV32, PV37, PV40, PV50, etc. (all numbers are color index No.).

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

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

In order to increase resistance to heat, light, acid, alkali or organic solvent, the basic dye is preferably a salt-forming compound composed of organic acid such as organic sulfonic acid or organic carboxylic acid or perchloric acid, and tobias acid etc. More preferred is a salt-forming compound comprising naphthalenesulfonic acid or perchloric acid. Similarly, a salt-forming compound composed of a quaternary ammonium salt, a primary to tertiary amine, or a sulfonamide is preferable as the acid dye and the direct dye in order to increase resistance to heat, light, acid, alkali, organic solvent, or the like.

The colored composition of the present invention preferably contains a radical polymerizable compound. By containing a radically polymerizable compound, patterning properties can be imparted. The radically polymerizable compound in the present invention is preferably a compound having an unsaturated hydrocarbon group. Examples of the unsaturated hydrocarbon group include a (meth) acryloyl group, a vinyl group, and a maleimide group. You may have 2 or more types of these.

Examples of the radical polymerizable compound include dipentaerythritol penta (meth) acrylate, tetratrimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and penta (meth) acryloyloxy. Dipentaerythritol monosuccinate, modified ethylene oxide or propylene oxide such as dipentaerythritol hexa (meth) acrylate, styrene derivative, polyfunctional maleimide compound, poly (meth) acrylate carbamate, 1,6-hexane adipic acid Diol (meth) acrylic acid ester, phthalic anhydride propylene oxide (meth) acrylic acid ester, trimellitic acid diethylene glycol (meth) Crylic acid ester, rosin-modified epoxy di (meth) acrylate, oligomer such as alkyd-modified (meth) acrylate, bifunctional (meth) acrylate such as tripropylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate , Trimethylolpropane tri (meth) acrylate, triacryl formal, bisphenoxyethanol full orange acrylate, dicyclopentanedienyl diacrylate, alkyl modified products thereof, alkyl ether modified products and alkyl ester modified products. Two or more of these may be contained.

Among these, from the viewpoint of solubility and patterning properties, a compound having a (meth) acryloyl group is preferable, and a polyfunctional compound having three or more (meth) acryloyl groups is preferable. By using a polyfunctional compound having three or more (meth) acryloyl groups, it is possible to form a sufficiently cured film having excellent heat resistance. Moreover, the compound which has a carboxyl group from a viewpoint of alkali developability is preferable. A compound having three or more (meth) acryloyl groups and a carboxyl group is more preferable. Examples of such a compound include penta (meth) acryloyloxydipentaerythritol monosuccinate.

The content of the radically polymerizable compound in the colored composition of the present invention is preferably 40% by mass or more in the solid content from the viewpoint of patterning properties. On the other hand, from the viewpoint of suppressing film thickness unevenness during film formation and suppressing deformation of the pattern due to flow during firing, the content of the radical polymerizable compound is preferably 90% by mass or less, preferably 70% by mass in the solid content. The following is more preferable, and 60% by mass or less is more preferable. Further, from the viewpoint of patterning properties, the content of the radical polymerizable compound having three or more (meth) acryloyl groups and a carboxyl group is preferably 50% by mass or more and 100% by mass or less in the radical polymerizable compound, and 60% by mass. % To 100% by mass is more preferable.

The colored composition of the present invention further comprises 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, an organic acid, and an organic amino compound. Further, it may contain a curing agent and the like.

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

Examples of the binder resin include acrylic resin, epoxy resin, polyimide resin, urethane resin, urea resin, polyvinyl alcohol resin, melamine resin, polyamide resin, polyamideimide resin, polyester resin, and polyolefin resin. Two or more of these may be contained. 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, vinyl acetic acid, and acid anhydrides thereof. Two or more of these may be used.

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

The acrylic resin preferably has an ethylenically unsaturated group in the side chain, and can improve sensitivity. Examples of the ethylenically unsaturated group include a vinyl group, an allyl group, an acrylic group, and a methacryl group. Examples of the acrylic resin having an ethylenically unsaturated group in 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, and more preferably 100,000 or less. Here, the weight average molecular weight of the binder resin refers to a standard polystyrene equivalent value measured by gel permeation chromatography.

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

The colorant contained in the colored composition of the present invention should be identified by laser Raman spectroscopy (Ar + laser (457.9 nm)), mass spectrometry using a MALDI mass spectrometer or a time-of-flight secondary ion mass spectrometer. Can do.

Further, the content of the coloring material in the coloring composition can be quantified by mass spectrometry using a MALDI mass spectrometer or a time-of-flight secondary ion mass spectrometer. The mass of the obtained coloring material and other components The ratio (mass%) which occupies in solid content in a coloring composition can be calculated | required from content of. In addition, when the blending ratio of the raw material of the coloring composition is known, the ratio (mass%) in the solid content in the coloring composition is obtained from the blending amount of the coloring material and the blending amount of other components. Can do.

The coloring composition of the present invention may contain a dispersing agent such as a pigment derivative together with the coloring material. Examples of the dispersant include low molecular dispersants such as pigment intermediates and derivatives, and polymer dispersants. Examples of the pigment derivative include a modified alkylamine of a pigment skeleton, a carboxylic acid derivative, and a sulfonic acid derivative that contribute to appropriate wetting and stabilization of the pigment. A sulfonic acid derivative having a pigment skeleton having a remarkable effect on the stabilization of the fine pigment is preferred.

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

When the coloring composition of the present invention contains a polymer dispersant and / or a binder resin, the total content thereof is 10% by mass or more in solid content from the viewpoint of suppressing film thickness unevenness during film formation. Preferably, 20 mass% or more is more preferable, and 30 mass% or more is further more preferable. 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, and more preferably 50% by mass or less in the solid content excluding the coloring material of the coloring composition.

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

More specifically, examples of the oxime ester compound include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), ethanone, and 1- [9-ethyl. -6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxy) Benzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3) -Dioxolanyl) methoxybenzoyl} -9H-carbazol-3-yl]-, 1- (O-acetyloxime), 1,2-octanedione, 1- [4- (phenylthio) -2 (O-benzoyloxime)], “Adeka Arcles” (registered trademark) N-1919, NCI-930 (manufactured by ADEKA Corporation), “IRGACURE” (trademark registered) OXE01, OXE02 (manufactured by BASF Corporation), etc. Is mentioned.

Examples of the benzophenone compounds include benzophenone, N, N′-tetraethyl-4,4′-diaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, and the like.

Examples of acetophenone compounds include 2,2-diethoxyacetophenone, benzoin, benzoin methyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, α-hydroxyisobutylphenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [ 4- (methylthio) phenyl] -2-morpholino-1-propane, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (dimethylamino) -2-[(4- Methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, “IRGACURE "(Registered trademark) 369, 379, 907 (BA Made F (Ltd.)), and the like.

Examples of the anthraquinone compounds include t-butylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-2-methylanthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone, 9,10-phenol Nantraquinone, 1,2-benzoanthraquinone, 1,4-dimethylanthraquinone, 2-phenylanthraquinone and the like can be mentioned.

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

Examples of the benzothiazole compound include 2-mercaptobenzothiazole.

Examples of the benzoxazole-based compound include 2-mercaptobenzoxazole.

Examples of the triazine compound include 4- (p-methoxyphenyl) -2,6-di- (trichloromethyl) -s-triazine.

Two or more of these may be contained. Among these, the green color material having a metal phthalocyanine skeleton of the present invention, Pigment Yellow 138, and C.I. I. 2-methyl-1- [4- (methylthio) phenyl] from the viewpoint of patterning sensitivity and pattern workability in a colored composition having a total content of CI Pigment Yellow 185 of 2% by mass to 16% by mass in the solid content -2-Morpholinopropan-1-one is preferred, and in addition to 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, a sensitizer described later may be used in combination. Is more preferable.

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

The colored composition of the present invention may contain a chain transfer agent in combination with the photopolymerization initiator, and can further improve sensitivity. Examples of the chain transfer agent 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, merca Tophenol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercapto-3-pyridinol, 2-mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropane tris (3-mercaptopropionate), 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione), pentaerythritol tetrakis (3-mercaptopropionate), 1,4-bis (3-mercaptobutyryloxy) butane, “Karenz” (registered trademark) MT PE-1 (manufactured by Showa Denko KK), “Karenz” (registered trademark) MT NR-1 (manufactured by Showa Denko KK), Mercapto compounds such as “Karenz” (registered trademark) MT BD-1 (manufactured by Showa Denko KK), the merca Disulfide compounds obtained by oxidizing bets compound, iodoacetic acid, iodopropionic acid, 2-iodo ethanol, 2-iodo-ethanesulfonic acid, iodinated alkyl compounds such as 3-iodo propane sulfonic acid. Two or more of these may be contained.

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

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

The colored composition of the present invention may further contain a polymerization inhibitor and can improve the stability. The polymerization inhibitor generally exhibits an action of inhibiting or stopping polymerization due to radicals generated by heat, light, radical initiators, etc., and generally prevents gelation of thermosetting resins or at the time of polymer production. Used to stop polymerization. Examples of the polymerization inhibitor include hydroquinone, tert-butylhydroquinone, 2,5-bis (1,1,3,3-tetramethylbutyl) hydroquinone, 2,5-bis (1,1-dimethylbutyl) hydroquinone, Catechol, tert-butylcatechol and the like can be mentioned. Two or more of these may be contained. From the viewpoint of the balance between stability and photosensitive characteristics, the content of the polymerization inhibitor is preferably 0.0001% by mass or more, and more preferably 0.005% by mass or more in the solid content. Further, from the viewpoint of the balance between stability and photosensitive properties, the content of the polymerization inhibitor is preferably 1% by mass or less, more preferably 0.5% by mass or less in the solid content.

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

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

The colored composition of the present invention can be preferably used for a reflective display device described later.

The coloring composition of the present invention includes, for example, a green color material having a metal phthalocyanine skeleton, C.I. I. Pigment yellow 138 and / or C.I. I. Pigment Yellow 185 and other colorant, binder resin, organic solvent, and other components as needed may be dispersed to prepare a pigment dispersion, and further blended with other components as necessary. . Examples of the disperser include a sand mill, a ball mill, a bead mill, a three roll mill, and an attritor. Among these, a bead mill excellent in dispersion efficiency is preferable. Examples of the dispersed beads include zirconia beads, alumina beads, and glass beads. Among these, zirconia beads are preferable. 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 make secondary particles (particle diameter of about 1 to 50 μm) finer by a disperser.

Next, the color filter substrate of the present invention will be described. The color filter substrate of the present invention has a pixel made of the colored composition of the present invention on the substrate. That is, a pixel consists of the photocured material or thermosetting material of the coloring composition of this invention. You may have other pixels, such as red and blue. Further, it preferably has a black matrix, a photospacer, and an overcoat layer, and may have an alignment film, a polarizing plate, a retardation plate, an antireflection film, a transparent electrode, a diffusion plate, and the like.

Examples of the substrate 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 whose surface is coated with silica. And organic plastic films and sheets. A black matrix may be formed on these substrates. Note that when the display device including 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, or may be a film formed by coating or the like on a substrate such as a glass substrate.

In the case of such a coating film, it can be peeled off by appropriately adjusting the adhesion between the substrate and the film with a laser or the like. Examples of the material of the organic plastic include polyester such as polypropylene, polyethylene, polystyrene, and polyethylene terephthalate (PET), polyphenylene sulfide (PPS), polyimide, polyamide, polyamideimide, polyethersulfone, polytetrafluoroethylene (PTFE), and the like. Fluorine-containing polymers, polyether ether ketone, polyphenylene ether, polyarylate, polysulfone and the like can be mentioned. Among these, from the viewpoint of heat resistance, process compatibility, mechanical strength, dimensional stability, and chemical resistance, when the organic plastic is used as the substrate, the substrate is preferably polyimide. When an organic plastic is used as the substrate, the substrate is preferably a film having a thickness of 5 μm or more, and more preferably 10 μm or more from the viewpoint of the strength of the substrate. On the other hand, from the viewpoint of flexibility, the substrate is preferably a film having a thickness of 100 μm or less.

There is no restriction | limiting in particular in a polyimide, Generally, the polyimide represented by following General formula (1) can be used. This can be obtained, for example, by imide ring closure (imidation reaction) of a polyimide precursor represented by the following general formula (2). It does not specifically limit as a method of imidation reaction, Thermal imidation and chemical imidation are mentioned. Among these, thermal imidization is preferable from the viewpoint of heat resistance of the polyimide film and transparency in the visible light region.

In general formulas (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 or a monovalent organic group having 1 to 10 carbon atoms.

R ¹ in the general formulas (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 aromatic acid dianhydrides, alicyclic acid dianhydrides, and aliphatic acid dianhydrides.

Examples of aromatic dianhydrides include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-terphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-oxyphthale Acid dianhydride, 2,3,3 ′, 4′-oxyphthalic dianhydride, 2,3,2 ′, 3′-oxyphthalic dianhydride, diphenylsulfone-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, -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) benzene dianhydride, bis (1,3-dioxo-1,3-dihydroisobenzfuran- 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, 0-perylenetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 2,2-bis (4- (3,4-dicarboxybenzoyloxy) phenyl ) Hexafluoropropane dianhydride, 1,6-difluoropromellitic dianhydride, 1-trifluoromethylpyromellitic dianhydride, 1,6-ditrifluoromethylpyromellitic 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] hexafluoropropane dianhydride, or an aromatic group such as an alkyl group, an alkoxy group, Examples thereof include, but are not limited to, acid dianhydride compounds substituted with a halogen atom or the like.

Examples of the alicyclic acid dianhydride include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,2,3,4- Cyclopentanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4- Cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cycloheptanetetracarboxylic dianhydride, 2,3 , 4,5-tetrahydrofurantetracarboxylic dianhydride, 3,4-dicarboxy-1-cyclohexylsuccinic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 3,4-dicarbo Ci-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride, bicyclo [4, 3,0] nonane-2,4,7,9-tetracarboxylic dianhydride, bicyclo [4,4,0] decane-2,4,7,9-tetracarboxylic dianhydride, bicyclo [4, 4,0] decane-2,4,8,10-tetracarboxylic dianhydride, tricyclo [6,3,0,0 <2,6>] undecane-3,5,9,11-tetracarboxylic dianhydride Anhydride, bicyclo [2,2,2] octane-2,3,5,6-tetracarboxylic dianhydride, bicyclo [2,2,2] oct-7-ene-2,3,5,6- Tetracarboxylic dianhydride, bicyclo [2,2,1] heptanetetracarboxylic dianhydride, Cyclo [2,2,1] heptane-5-carboxymethyl-2,3,6-tricarboxylic dianhydride, 7-oxabicyclo [2,2,1] heptane-2,4,6,8-tetracarboxylic Acid dianhydride, octahydronaphthalene-1,2,6,7-tetracarboxylic dianhydride, tetradecahydroanthracene-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-dicarboxylicsan anhydride, “Licacid” (registered trademark) BT-100 (above, trade name, manufactured by Shin Nippon Rika Co., Ltd.) and derivatives thereof, or these Examples of the alicyclic ring include, but are not limited to, acid dianhydride compounds substituted with an alkyl group, an alkoxy group, a halogen atom, or the like.

Examples of the aliphatic 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.

Of these, pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4, from the viewpoint of being commercially available and easy to obtain, and reactivity. 4′-oxyphthalic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 2,2′-bis [(dicarboxyphenoxy) phenyl] propane dianhydride, 2 , 3,6,7-Naphthalenetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3 ′, 4,4′-dicyclohexanetetracarboxylic dianhydride 1,2,3,4-cyclobutanetetracarboxylic dianhydride is preferably used.

Further, from the viewpoint of heat resistance and prevention of coloring during firing, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3,4′′4′-oxyphthalic dianhydride, 2,2 It is more preferable to use bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride or 2,2′-bis [(dicarboxyphenoxy) phenyl] propane dianhydride.

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

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

Examples of aromatic diamine compounds include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenyl sulfone, 4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfide, 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'- Chlorobenzidine, 2,2'3,3'-tetrachlorobenzidine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis (4-aminophenoxyphenyl) sulfone, Bis (3-aminophenoxyphenyl) sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 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-aminobenzamido) -4-hydroxyphenyl] hexafluoropropane, or these Place an alkyl group, alkoxy group, halogen atom, etc. They include diamine compounds, but is not limited thereto.

Examples of the alicyclic diamine compound include cyclobutane diamine, isophorone diamine, bicyclo [2,2,1] heptane bismethylamine, tricyclo [3,3,1,13,7] decane-1,3-diamine, 1,2 -Cyclohexyl diamine, 1,3-cyclohexyl diamine, 1,4-cyclohexyl diamine, trans-1,4-diaminocyclohexane, 4,4'-diaminodicyclohexyl methane, 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'-diaminodicyclohexyl ether, 3,3'-dimethyl-4,4'-diaminodicyclohexyl 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′-diaminodicyclohexyl 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-di Til-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 a diamine compound in which these alicyclic rings are substituted with an alkyl group, an alkoxy group, a halogen atom, or the like, is not limited thereto.

Aliphatic diamine compounds include ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, and 1,8-diaminooctane. Alkylene diamines such as 1,9-diaminononane and 1,10-diaminodecane, ethylene glycol diamines such as bis (aminomethyl) ether, bis (2-aminoethyl) ether, bis (3-aminopropyl) ether, And siloxanes such as 1,3-bis (3-aminopropyl) tetramethyldisiloxane, 1,3-bis (4-aminobutyl) tetramethyldisiloxane, α, ω-bis (3-aminopropyl) polydimethylsiloxane Although diamine is mentioned, 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.

X ¹ and X ^{2 in the} general formulas (1) and (2) each independently represent a hydrogen atom or 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 a methyl group, an ethyl group, and a butyl group. 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.

Since the polyimide used for the substrate is required to have heat resistance and high transparency in the visible light region, it is effective to use an alicyclic monomer component for the acid dianhydride or diamine component in order to further increase the transparency. . The alicyclic monomer may be used for both the acid dianhydride and the diamine component, or may be used for one side. Furthermore, you may use together with an aromatic monomer.

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

Further, from the viewpoint of reducing the linear expansion coefficient of polyimide, R ² in the general formulas (1) and (2) is 1 selected from structures represented by the following general formulas (9) to (12) Preferably, the structure represented by the following general formulas (9) to (12) in R ¹ in the general formulas (1) and (2) is preferably 50 mol% or more, and more Preferably it is 80 mol% or more and 100 mol% is more preferable. Among them, high solubility, from the viewpoint of decreasing the linear expansion coefficient of the general formula (1), it is preferably the following general formula as R ² in (2) (10). Further, from the viewpoint of increasing the transmittance of polyimide, R ² in the general formulas (1) and (2) is preferably the following general formula (9) or (10).

In addition, from the viewpoints of increasing the transmittance of polyimide, facilitating laser peeling, and reducing the linear expansion coefficient, R ² in the general formulas (1) and (2) is represented by the following general formula (13) or (14) It is preferable that 1 or more types selected from the structure represented by these are included. In addition, the oxazole ring of General formula (14) produces | generates by dehydration ring closure from the structure represented by General formula (13). Further, from the viewpoint of processability of pixels formed on polyimide, the structure represented by the following general formula (13) or (14) in R ² in the general formulas (1) and (2) is 30 mol% or less. It is preferable that it is 20 mol% or less.

The polymerization reaction method for obtaining the polyimide and the polyimide precursor is not particularly limited as long as the target polyimide and polyimide precursor can be produced, and a known method can be used. As a specific reaction method, a predetermined amount of all the diamine component and solvent are charged and dissolved in a reactor, and then a predetermined amount of acid dianhydride component is charged and stirred at room temperature to 80 ° C. for 0.5 to 30 hours. The method of doing is mentioned. Known acid dianhydrides and diamines used for the synthesis of the polyimide precursor can be used, and those described above are preferred. Polyimide precursors such as polyamic acid, polyamic acid ester, and polyamic acid silyl ester can be synthesized by a reaction between a diamine compound and an acid dianhydride or a derivative thereof. Examples of the derivatives include tetracarboxylic acids of the acid dianhydrides, mono-, di-, tri-, or tetra-esters of the tetracarboxylic acids, acid chlorides, and the like, and specifically include methyl groups, ethyl groups, and n-propyl. And a structure esterified with a group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group and the like.

In order to adjust the molecular weight to a preferable range, both ends of the polyimide and the polyimide precursor may be sealed with a terminal sealing agent. Examples of the terminal blocking agent that reacts with the acid dianhydride include monoamines and monohydric alcohols. Examples of the terminal blocking agent that reacts with the diamine compound include acid anhydrides, monocarboxylic acids, monoacid chloride compounds, monoactive ester compounds, dicarbonates, and vinyl ethers. Moreover, various organic groups can be introduce | transduced as a terminal group by making terminal blocker react.

The introduction ratio of the acid anhydride group terminal sealing agent is preferably in the range of 0.1 to 60 mol%, particularly preferably 5 to 50 mol%, relative to the acid dianhydride component. In addition, the introduction ratio of the amino group terminal blocking agent is preferably in the range of 0.1 to 100 mol%, particularly preferably 5 to 90 mol%, relative to the diamine component. A plurality of different end groups may be introduced by reacting a plurality of end-capping agents.

Pixels include colored pixels such as red and blue and transparent pixels. Examples of the material constituting the pixel include the colored composition of the present invention, and a colored photosensitive composition containing a binder resin such as an acrylic resin and 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 further 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 prevents a decrease in contrast and color purity due to light leakage between pixels, and is preferably disposed between pixels or in a frame portion. Examples of the material constituting the black matrix include a photosensitive composition containing a binder resin such as an acrylic resin and a polyimide resin and a radical polymerizable compound, a non-photosensitive resin composition colored in black, and the like. The film thickness of the black matrix is preferably 0.5 μm or more and more preferably 1.0 μm or more from the viewpoint of light shielding properties. On the other hand, from the viewpoint of workability, 2.0 μm or less is preferable, and 1.5 μm or less is more preferable.

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

The overcoat layer suppresses the permeation of impurities from the pixels of the color filter substrate or flattens the steps due to the pixels of the color filter substrate. Examples of the material constituting the overcoat layer include epoxy resins, acrylic epoxy resins, acrylic resins, siloxane resins, polyimide resins, and photosensitive or non-photosensitive materials that are commercially available as planarization materials. The film thickness of the overcoat layer is preferably 0.5 μm or more, more preferably 1.0 μm or more, from the viewpoint of workability. On the other hand, from the viewpoint of flatness of the color filter substrate, 5.0 μm or less is preferable, and 3.0 μm or less is more preferable.

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

Examples of the method for producing a color filter substrate include a method of patterning pixels made of a resin composition on a substrate. Hereinafter, the production method will be described by taking as an example a color filter substrate having pixels made of the colored composition of the present invention having photosensitivity. The color composition of the present invention is applied onto a substrate, patterned by selective exposure and development using a photomask, and baked to form pixels and obtain a color filter substrate.

Examples of the method for applying the colored composition of the present invention on 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, and a substrate immersed in the colored composition. The method, the method of spraying a coloring composition on a board | substrate, etc. are mentioned. Then, the board | substrate which apply | coated the coloring composition is dried, and the coating film of a coloring composition is formed on a board | substrate. Examples of the drying method include air drying, heat drying, and vacuum drying. Two or more of these may be combined. For example, it is preferable to dry under reduced pressure and then heat dry. The heat drying temperature is preferably 80 to 130 ° C., and the hot drying apparatus 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 colored composition on a substrate on which a black matrix has been previously formed.

Next, a photomask is placed on the coating film of the colored composition, and selective exposure is performed. Examples of the exposure machine include a proximity exposure machine, a mirror projection exposure machine, a lens scan exposure machine, and a stepper. From the viewpoint of accuracy, a lens scanning exposure machine is preferable. Examples of the light source used for 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 alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, ethylamine, and n-propylamine. Examples include primary amines, secondary amines such as diethylamine and di-n-propylamine, tertiary amines such as triethylamine and methyldiethylamine, and organic alkalis such as tetramethylammonium hydroxide. Examples of the alkaline developer include 0.02 to 1% by mass of potassium hydroxide or tetramethylammonium hydroxide. Examples of the developing method include a method of immersing the exposed coating film in an alkali developer for 20 to 300 seconds.

Thereafter, the obtained coating film pattern is heated to obtain a color filter substrate on which pixels are patterned. The heat treatment may be performed in any of air, nitrogen atmosphere, and vacuum. The heating temperature is preferably 150 to 350 ° C, more preferably 180 to 250 ° C. The heating time is preferably 5 minutes to 5 hours. As the heat treatment apparatus, a hot air oven or a hot plate is preferable. The heat treatment may be performed continuously or stepwise.

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

In addition, when the color composition containing the green color material and the yellow color material and the ratio of the yellow color material in the color material is high, the light transmittance retention of the color pixel is low, so the color filter substrate of the present invention Is a color filter substrate having a red pixel, a green pixel, a blue pixel, and a fourth color pixel, wherein the fourth color pixel is made of a photocured product or a thermally cured product of the colored composition of the present invention. Is preferred. Further, from the viewpoint of improving color purity and increasing light transmittance retention, the light absorption rate at 480 nm of the color pixel of the fourth color is 50% or more and the light absorption rate at 650 nm is 10% or more and 90% or less. It is preferable that

The light absorptance of a color pixel here refers to the proportion of light that is prevented from passing when a certain wavelength of light passes through the color pixel. For example, the microscopic spectrophotometer LCF-100MA manufactured by Otsuka Electronics Co., Ltd. Can be measured. The light absorptance of the fourth color pixel on the color filter substrate is the light absorptance of the region where no color pixel is formed on the color filter substrate and the region of the fourth color pixel on the color filter substrate. It can be calculated from the light absorption rate.

In order to obtain such a fourth color pixel, the color pixel is C.I. I. Pigment green 58, C.I. I. Pigment Yellow 185, and C.I. I. The content of Pigment Yellow 185 is preferably 50% by mass, and the content of the coloring material in the solid content is preferably 5% by mass or more.

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 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 and a diffusion plate. The display device refers to a device that displays an image by visually recognizing a part of the screen. Examples of the display element include a liquid crystal element, an organic EL element, an inorganic EL element, a display element using MEMS, a display element using quantum dots, 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 electronic paper. In a transmissive liquid crystal display, the brightness of the display can be easily improved by increasing the intensity of the backlight light source, whereas in a reflective liquid crystal display that mainly uses ambient light, the light of the color filter. Since the transmittance is one of the factors that determine the brightness of display, the color filter substrate of the present invention is preferably used for a reflective display device such as a transflective liquid crystal display or a reflective liquid crystal display. Examples of the reflective display device include devices that display with outdoor light or indoor light, such as wearable terminals, digital signage, digital signage, and electronic shelf labels. In the case of a reflective display device, it has a reflective layer made of a metal such as silver or aluminum inside, and light incident from the front surface of the display device is reflected by the reflective layer and transmitted twice through the color filter substrate. By doing so, while the color purity can be further increased, the light transmittance tends to decrease. Even in such a reflective display device, a green color material having a metal phthalocyanine skeleton and C.I. I. Pigment yellow 138 and C.I. I. By setting the total content of Pigment Yellow 185 to 2% by mass or more and 16% by mass or less in the solid content, a display device having excellent display characteristics can be obtained. The reflective layer only needs to reflect light in the visible light region, and may have a layered structure made of a metal such as silver or aluminum, or a multilayer structure made of transparent resins having different refractive indexes. As the reflective layer, a layer made of a metal in which a metal such as silver or aluminum is formed by sputtering or vapor deposition is preferable from the viewpoint of reflectivity.

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 through a liquid crystal alignment film provided on the substrates and a spacer for maintaining a cell gap. Note that a TFT liquid crystal display device or a TFD liquid crystal display device can be manufactured by providing a thin film transistor (TFT) element or a thin film diode (TFD) element, a scanning line, a signal line, or the like over an array substrate. Next, after injecting liquid crystal from the injection port provided in the seal portion, the injection port is sealed. Furthermore, a liquid crystal display device is completed by attaching a backlight and mounting an IC driver or the like. As the backlight, a two-wavelength LED, a three-wavelength LED, a CCFL, or the like can be used. However, a three-wavelength LED is preferable because the color reproduction range of the liquid crystal display device can be expanded and the power consumption can be reduced. .

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples. First, the evaluation method in an Example and a comparative example is demonstrated.

<Evaluation of chromaticity and light transmittance>
On the glass substrate, the colored compositions obtained in Examples 1 to 13 and Comparative Examples 1 to 8 were applied, followed by drying at 90 ° C. for 10 minutes. The obtained colored composition coating film is exposed to i-line 200 mJ / cm ² through a negative photomask, and then developed with a 0.3 mass% tetramethylammonium hydroxide aqueous solution at 23 ° C. As a result, a desired pattern was formed. Subsequently, heat treatment was performed at 230 ° C. for 30 minutes to obtain a film having a film thickness of 1.7 μm. However, only in Example 13, the film thickness was set to 2.5 μm. With respect to this film, chromaticity x, y and light transmittance Y were measured with a C light source using a microspectrophotometer LCF-100MA manufactured by Otsuka Electronics Co., Ltd.

<Evaluation of light absorption rate>
On the glass substrate, the colored compositions obtained in Examples 1 to 13 and Comparative Examples 1 to 8 were applied, followed by drying at 90 ° C. for 10 minutes. The obtained colored composition coating film is exposed to i-line 200 mJ / cm ² through a negative photomask, and then developed with a 0.3 mass% tetramethylammonium hydroxide aqueous solution at 23 ° C. As a result, a desired pattern was formed. Subsequently, heat treatment was performed at 230 ° C. for 30 minutes to obtain a film having a film thickness of 1.7 μm. However, only in Example 13, the film thickness was set to 2.5 μm. The film was measured for optical absorptance at 480 nm and 650 nm using a microspectrophotometer LCF-100MA manufactured by Otsuka Electronics Co., Ltd.

<Evaluation of light transmittance retention by light irradiation>
The colored compositions obtained in Examples 1 to 13 and Comparative Examples 1 to 8 were applied on a glass substrate on which a black matrix was formed, and then heat-dried at 90 ° C. for 10 minutes. The obtained colored composition coating film is exposed to i-line 200 mJ / cm ² through a negative photomask, and then developed with a 0.3 mass% tetramethylammonium hydroxide aqueous solution at 23 ° C. As a result, a desired pattern was formed. Subsequently, a heat treatment was performed at 230 ° C. for 30 minutes to obtain a color filter substrate having a green pixel thickness of 1.7 μm. However, only in Example 13, the film thickness was set to 2.5 μm. For the green pixel of this color filter substrate, the Y value was measured with a C light source using a microspectrophotometer LCF-100MA manufactured by Otsuka Electronics Co., Ltd., and the obtained value was designated as Y0.

An array substrate was prepared by forming TFT elements, transparent electrodes, etc. on alkali-free glass. A polyimide alignment film was formed on each of the produced color filter substrate and array substrate, and rubbed. A sealant kneaded with microrods was printed on the array substrate, and a bead spacer having a thickness of 6 μm was sprayed, and then the array substrate and the color filter substrate were bonded together. After injecting nematic liquid crystal (“Rixon” JC-5007LA manufactured by Chisso Co., Ltd.) from the injection port provided in the seal portion, a polarizing film is bonded to both surfaces of the liquid crystal cell so that the polarization axis is vertical. I got a panel. A white LED backlight composed of a blue LED and a YAG phosphor was attached to this liquid crystal panel, and a TAB module, a printed board, etc. were mounted to produce a liquid crystal display device. A white LED backlight with a luminous intensity of 10,000 cd / m ² was used. This liquid crystal display device was put into a constant temperature and high humidity bath at 60 ° C. and 60% for 100 hours with the backlight turned on. Thereafter, the panel was disassembled, and the Y value of the green pixel was measured with a C light source using a microspectrophotometer LCF-100MA manufactured by Otsuka Electronics Co., Ltd., and the obtained Y value was defined as Y1. Y1 / Y0 was calculated and used as the light transmittance retention.

Production Example 1 (Preparation of dispersion (A1))
C. I. 150 g of Pigment Yellow 185 (BASF "Paliotol (registered trademark) Yellow D1155)," BYK "(registered trademark) LPN6919 (manufactured by BYK Chemie, polymer dispersant solution (60 mass% propylene glycol monomethyl ether solution)), 125 g Cyclomer (registered trademark) ACA250 (manufactured by Daicel Chemical Industries, Ltd., 45 g of 45% by mass dipropylene glycol monomethyl ether solution) and 625 g of propylene glycol monomethyl ether (PMA) were mixed to prepare a slurry. The beaker containing the slurry was connected with a dyno mill and a tube, and zirconia beads having a diameter of 0.5 mm were used as media, and a dispersion treatment was performed at a peripheral speed of 14 m / s for 8 hours. I. Pigment Yellow 185 dispersion (A1) was prepared.

Production Example 2 (Preparation of Dispersion (A2))
C. I. Pigment Yellow 185 instead of C.I. I. Pigment Green 58 (“FASTGEN” (registered trademark) Green A110, manufactured by DIC Corporation) 150 g was used in the same manner as in Production Example 1, except that C.I. I. Pigment Green 58 dispersion (A2) was prepared.

Production Example 3 (Preparation of dispersion (A3))
C. I. Pigment Yellow 185 instead of C.I. I. C.I. Pigment Yellow 138 ("LIONOGEN" (registered trademark) YELLOW1010 manufactured by Toyo Ink Co., Ltd.) 150 g was used in the same manner as in Production Example 1 except that C.I. I. Pigment Yellow 138 Dispersion (A3) was prepared.

Production Example 4 (Synthesis of binder resin solution (B1))
In a 500 mL three-necked flask, 33 g (0.3 mol) of methyl methacrylate, 33 g (0.3 mol) of styrene, 34 g (0.4 mol) of methacrylic acid, 3 g of 2,2′-azobis (2-methylbutyronitrile) (0 0.02 mol) and 150 g of propylene glycol monomethyl ether acetate (PGMEA) were stirred, stirred at 90 ° C. for 2 hours, then the internal temperature was raised to 100 ° C., and further stirred for 1 hour to obtain a reaction solution. To the obtained reaction solution, 33 g (0.2 mol) of glycidyl methacrylate, 1.2 g (0.009 mol) of dimethylbenzylamine and 0.2 g (0.002 mol) of p-methoxyphenol were added at 90 ° C. After stirring for a period of time, 50 g of PGMEA was added to obtain a binder resin solution (B1) having a solid concentration of 40% by mass. When the acid value of the binder resin was measured for a 0.1 mol / L potassium hydroxide / ethanol solution using an automatic potentiometric measuring device AT-610 manufactured by Kyoto Electronics Industry Co., Ltd., the acid value was 80.0 (mgKOH / g). Moreover, when the weight average molecular weight of polystyrene conversion was computed using the GPC apparatus, the weight average molecular weight was 22,000.

Example 1
In a 50 mL plastic bottle, 0.99 g of dispersion A1 obtained in Production Example 1, 3.95 g of dispersion A2 obtained in Production Example 2, 3.27 g of binder resin solution B1 obtained in Production Example 4, penta ( (Meth) acryloyloxydipentaerythritol monosuccinate (C1) 2.30 g, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (D1) 0.31 g, 2 , 4-Diethylthioxanthen-9-one (D2) 0.15 g and dipropylene glycol methyl ether acetate (hereinafter referred to as DPMA) 19.03 g were added and stirred for 3 hours to prepare a colored composition (E1). . About the obtained coloring composition, when the light transmittance retention was evaluated by the said method, Y1 / Y0 was 0.980. Further, chromaticity was x = 0.309, y = 0.594, and 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 and Comparative Examples 1 to 8
A colored composition (E2 to E21) was prepared in the same manner as in Example 1 except that the dispersion liquid, binder resin solution, radical polymerizable compound, photopolymerization initiator, and organic solvent were changed in kind and charge ratio as shown in Table 1. ) Tables 2 and 3 summarize the results evaluated by the above method using the obtained colored composition.

Example 14
In a 100 mL four-necked flask under a dry nitrogen stream, 3.34 g (17.0 mmol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 4.64 g of 2,2′-bis (trifluoromethyl) benzidine ( 14.5 mmol), 1.55-g (2.56 mmol) of 2,2-bis [3- (3-aminobenzamido) -4-hydroxyphenyl] hexafluoropropane, and 50 g of N-methyl-2-pyrrolidone were added at 60 ° C. And stirred with heating. After 8 hours, it was cooled to obtain a varnish.

Next, the varnish obtained on a glass substrate was spin-coated, and a prebaking treatment at 140 ° C. for 4 minutes was performed to form a film having a thickness of 10 μm. Thereafter, the prebaked film was heated to 300 ° C. at 3.5 ° C./min under a nitrogen stream (oxygen concentration 20 ppm or less) using an inert oven (INH-21CD manufactured by Koyo Thermo System Co., Ltd.), and held for 30 minutes. The polyimide film was formed by cooling to 50 ° C. at 5 ° C./min.

Next, after apply | coating the coloring composition obtained in Example 3, it heat-dried at 90 degreeC for 10 minute (s). The obtained colored composition coating film is exposed to i-line 200 mJ / cm ² through a negative photomask, and then developed with a 0.3 mass% tetramethylammonium hydroxide aqueous solution at 23 ° C. As a result, a 20 μm × 200 μm size pattern and a 15 μm × 150 μm size pattern were formed. Subsequently, heat treatment was performed at 230 ° C. for 30 minutes to obtain a film having a film thickness of 1.7 μm.

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

Example 15
In a 100 mL four-necked flask under a dry nitrogen stream, 2,33,4-cyclobutanetetracarboxylic dianhydride 2.33 g (11.9 mmol), 2,2-bis [3- (3-aminobenzamide) -4 -Hydroxyphenyl] hexafluoropropane (7.19 g, 11.9 mmol) and N-methyl-2-pyrrolidone (50 g) were added, and the mixture was heated and stirred at 60 ° C. After 8 hours, it was cooled to obtain a varnish.

Next, the varnish obtained on a glass substrate was spin-coated, and a prebaking treatment at 140 ° C. for 4 minutes was performed to form a film having a thickness of 10 μm. Thereafter, the prebaked film was heated to 300 ° C. at 3.5 ° C./min under a nitrogen stream (oxygen concentration 20 ppm or less) using an inert oven (INH-21CD manufactured by Koyo Thermo System Co., Ltd.), and held for 30 minutes. The polyimide film was formed by cooling to 50 ° C. at 5 ° C./min.

Next, after apply | coating the coloring composition obtained in Example 3, it heat-dried at 90 degreeC for 10 minute (s). The obtained colored composition coating film is exposed to i-line 200 mJ / cm ² through a negative photomask, and then developed with a 0.3 mass% tetramethylammonium hydroxide aqueous solution at 23 ° C. As a result, a 20 μm × 200 μm size pattern was formed, but a 15 μm × 150 μm size pattern could not be formed. Subsequently, heat treatment was performed at 230 ° C. for 30 minutes to obtain a film having a film thickness of 1.7 μm.

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

Example 16
In a 100 mL four-necked flask under a dry nitrogen stream, 3.62 g (18.4 mmol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 5.38 g of 1,3-bis (4-aminophenyl) benzene ( 18.4 mmol) and 50 g of N-methyl-2-pyrrolidone were added and the mixture was heated and stirred at 60 ° C. After 8 hours, it was cooled to obtain a varnish.

Next, the varnish obtained on a glass substrate was spin-coated, and a prebaking treatment at 140 ° C. for 4 minutes was performed to form a film having a thickness of 10 μm. Thereafter, the prebaked film was heated to 300 ° C. at 3.5 ° C./min under a nitrogen stream (oxygen concentration 20 ppm or less) using an inert oven (INH-21CD manufactured by Koyo Thermo System Co., Ltd.), and held for 30 minutes. The polyimide film was formed by cooling to 50 ° C. at 5 ° C./min.

Next, after apply | coating the coloring composition obtained in Example 3, it heat-dried at 90 degreeC for 10 minute (s). The obtained colored composition coating film is exposed to i-line 200 mJ / cm ² through a negative photomask, and then developed with a 0.3 mass% tetramethylammonium hydroxide aqueous solution at 23 ° C. As a result, a 20 μm × 200 μm size pattern and a 15 μm × 150 μm size pattern were formed. Subsequently, heat treatment was performed at 230 ° C. for 30 minutes to obtain a film having a film thickness of 1.7 μm.

When the obtained substrate with pixels was irradiated with a 308 nm excimer laser (shape: 21 mm × 1.0 mm) from the glass substrate side and a laser peeling test was performed, the irradiation energy was 400 mJ / cm ² from the glass substrate. The floating of the polyimide film was confirmed.

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

Claims (16)

A green color material having a metal phthalocyanine skeleton; I. Pigment yellow 138 and / or C.I. I. A coloring composition containing a yellow colorant including CI Pigment Yellow 185, wherein the green colorant has a metal phthalocyanine skeleton; I. Pigment yellow 138 and C.I. I. The coloring composition whose sum total content with pigment yellow 185 is 2 mass% or more and 16 mass% or less in solid content. A green color material having the metal phthalocyanine skeleton; I. Pigment yellow 138 and C.I. I. The coloring composition according to claim 1, wherein a total content of the yellow color material including Pigment Yellow 185 is 60% by mass or more in the color material. The green color material having the metal phthalocyanine skeleton is C.I. I. Pigment green 58 and / or C.I. I. Pigment Green 59, C.I. I. Pigment green 58 and C.I. I. Pigment green 59, C.I. I. Pigment yellow 138, C.I. I. The coloring composition according to claim 2, wherein the total content of Pigment Yellow 185 is 80% by mass or more in the coloring material. C. I. Pigment green 58, C.I. I. Pigment green 59, C.I. I. Pigment yellow 138 and C.I. I. The coloring composition according to claim 3, wherein the total content of the coloring material including CI Pigment Yellow 185 is 2% by mass or more and 16% by mass or less in the solid content. C. I. The coloring composition according to claim 3 or 4, wherein the content of pigment green 58 is 80% by mass or more in the green color material. C. I. The colored composition according to any one of claims 1 to 5, wherein the content of Pigment Yellow 185 is 60% by mass or more in the yellow color material. C. I. The coloring composition according to any one of claims 1 to 6, wherein the content of Pigment Yellow 185 is 50% by mass or more and 90% by mass or less in the coloring material. The colored composition according to any one of claims 1 to 7, further comprising a radical polymerizable compound, wherein the content of the radical polymerizable compound is 40% by mass or more and 90% by mass or less in the solid content. The radical polymerizable compound contains a radical polymerizable compound having three or more (meth) acryloyloxy groups and a carboxyl group, and has three or more (meth) acryloyloxy groups and a carboxyl group. The colored composition according to claim 8, wherein the content of is not less than 50 mass% and not more than 100 mass% in the radical polymerizable compound. The colored composition according to any one of claims 1 to 9, which is used for a reflective display device. A color filter substrate having at least a substrate and pixels, wherein the pixels are made of a photocured product or a heat cured product of the colored composition according to any one of claims 1 to 10. 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 is the color composition according to any one of claims 1 to 10. A color filter substrate made of a photocured product or a thermoset. 13. The color filter substrate according to claim 12, wherein the light absorption rate at 480 nm of the fourth color pixel is 50% or more and the light absorption rate at 650 nm is 10% or more and 90% or less. The color filter substrate according to claim 11 or 12, wherein the substrate is made of polyimide. A display device comprising at least the color filter substrate according to any one of claims 11 to 14 and a display element. The display device according to claim 15, further comprising a reflective layer.