CN110268021B - Coloring composition, color filter substrate using the same and display device - Google Patents

Abstract

The present invention is to provide a coloring 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 using the coloring composition, and the present invention is a coloring composition comprising: a green colorant having a metal phthalocyanine skeleton and a yellow colorant containing c.i. pigment yellow 138 and/or c.i. pigment yellow 185, wherein the total content of the green colorant having a metal phthalocyanine skeleton and c.i. pigment yellow 138 and c.i. pigment yellow 185 is 2 mass% or more and 16 mass% or less in solid content.

Description

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

Technical Field

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

Background

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

In the green pixel, various combinations of pigments have been studied, but a green colorant (color material) having a metal phthalocyanine skeleton is generally combined with a yellow colorant. With regard to such a technique, for example, a green colorant composition containing a colorant (colorant) of green color selected from pigment green 7, pigment green 36 and pigment green 58 and a colorant of yellow color selected from pigment yellow 129, pigment yellow 138 and pigment yellow 150 is known (for example, refer to patent document 1).

On the other hand, it is known that if light is irradiated to phthalocyanine in a state where oxygen is blocked, the absorption spectrum changes, and the light transmittance of green pixels formed of phthalocyanine decreases (for example, see non-patent document 1). That is, if light is irradiated to a liquid crystal display device having green pixels formed of phthalocyanine in a state where oxygen is blocked, the light transmittance of the green pixels is lowered, and the brightness of the liquid crystal display device becomes dark.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open No. 2014-41341

Non-patent document

Non-patent document 1: journal of Photopolymer Science and Technology, Volume7, Number1(1994) p.151-158

Disclosure of Invention

Problems to be solved by the invention

When a green colorant having a metal phthalocyanine skeleton as described in patent document 1 is combined with a specific yellow colorant, there is a problem that if light is irradiated in a state where oxygen is blocked, light transmittance is greatly reduced and display performance is changed. In view of such circumstances, an object of the present invention is to provide a color composition having high color purity and high 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 same.

Means for solving the problems

The present invention is a coloring composition containing: a green colorant having a metal phthalocyanine skeleton and a yellow colorant containing c.i. pigment yellow 138 and/or c.i. pigment yellow 185, wherein the total content of the green colorant having a metal phthalocyanine skeleton and c.i. pigment yellow 138 and c.i. pigment yellow 185 is 2 mass% or more and 16 mass% or less in solid content.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the colored composition of the present invention, a color filter substrate and a display device having colored pixels with high color purity and high light transmittance and in which a decrease in light transmittance due to light irradiation is suppressed can be provided.

Detailed Description

The coloring composition of the present invention contains: a green colorant having a metal phthalocyanine skeleton, and a yellow colorant comprising c.i. pigment yellow 138 and/or c.i. pigment yellow 185. By containing: a green colorant having a metal phthalocyanine skeleton and a yellow colorant containing c.i. pigment yellow 138 and/or c.i. pigment yellow 185 can improve color purity and light transmittance. The phrase "capable of improving color purity" as used herein means that a color having a longer distance from a light source (for example, in the case of a C light source, the coordinate x is 0.310 and the coordinate y is 0.316) can be expressed in the CIE 1931 color system. Here, "capable of improving the light transmittance" means that the light transmittance is improved when chromaticity coordinates are the same, because the light transmittance of the coloring composition greatly changes depending on the chromaticity. On the other hand, as described above, there is a problem that if a green colorant having a metal phthalocyanine skeleton is irradiated with light in a state of being blocked from oxygen, the light transmittance is greatly reduced, and the display performance is changed. The present inventors have found that when c.i. pigment yellow 138 and/or c.i. pigment yellow 185 are contained as a yellow colorant, the total content of the green colorant having a metal phthalocyanine skeleton and c.i. pigment yellow 138 and c.i. pigment yellow 185 in the solid content is 2 mass% or more and 16 mass% or less, whereby the color purity and the light transmittance can be improved and the decrease in the light transmittance due to light irradiation can be suppressed.

The green colorant having a metal phthalocyanine skeleton is preferably c.i. pigment green 58 or c.i. pigment green 59, from the viewpoint of further improving the light transmittance. The total content of the c.i. pigment green 58 and the c.i. pigment green 59 is preferably 80% by mass or more, and more preferably 90% by mass or more in the green colorant. 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 alone as the green colorant. Further, from the viewpoint of further improving the light transmittance retention ratio, c.i. pigment green 58 is more preferable. The content of the c.i. pigment green 58 in the green colorant is preferably 80 mass% or more, and more preferably 90 mass% or more, from the viewpoint of further improving the light transmittance retention.

The yellow colorant contains c.i. pigment yellow 138 and/or c.i. pigment yellow 185, and may further contain other colorants. From the viewpoint of further improving the light transmittance and the light transmittance retention ratio, c.i. pigment yellow 185 is more preferable. The total content of the c.i. pigment yellow 138 and the c.i. pigment yellow 185 in the yellow colorant is preferably 60 mass% or more, more preferably 80 mass% or more, and still more preferably 90 mass% or more, from the viewpoint of improving the light transmittance. Further, the content of the c.i. pigment yellow 185 in the yellow colorant 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 improving the light transmittance, c.i. pigment yellow 185 alone is preferably used as the yellow colorant.

From the viewpoint of improving the transmittance, c.i. pigment yellow 185 is preferably contained as the yellow colorant, but generally, if the content of c.i. pigment yellow 185 in the colorant is 50 mass% or more and 90 mass% or less, the light transmittance tends to be easily lowered by light irradiation. In the present invention, as described later, since the decrease in transmittance due to light irradiation can be suppressed by setting the total content of the green colorant having a metal phthalocyanine skeleton, the c.i. pigment yellow 138 and the c.i. pigment yellow 185 to a specific range, a higher effect is exhibited when the content of the c.i. pigment yellow 185 in the colorant whose light transmittance is likely to decrease is 50 mass% or more and 90 mass% or less.

Examples of yellow colorants other than c.i. pigment yellow 138 and c.i. pigment yellow 185 include organic pigments, inorganic pigments, dyes, and the like, and examples thereof include c.i. pigment yellow (hereinafter, "PY") 12, PY13, PY17, PY20, PY24, PY83, PY86, PY93, PY95, PY109, PY110, PY117, PY125, PY129, PY137, PY139, PY147, PY148, PY150, PY153, PY154, PY166, and PY168 (all of the above numbers are color index nos.). More than 2 of these colorants may be contained. From the viewpoints 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 is characterized in that the total content of the green colorant having a metal phthalocyanine skeleton, the c.i. pigment yellow 138 and the c.i. pigment yellow 185 is 2 mass% or more and 16 mass% or less in solid content. If the total content of the green colorant having a metal phthalocyanine skeleton, the c.i. pigment yellow 138 and the c.i. pigment yellow 185 is less than 2 mass% in the solid content, the color purity is lowered. The total content thereof is preferably 3% by mass or more, more preferably 5% by mass or more. On the other hand, if the total content of the green colorant having a metal phthalocyanine skeleton, the c.i. pigment yellow 138 and the c.i. pigment yellow 185 exceeds 16 mass% in the solid content, the light transmittance decreases by light irradiation, and the light transmittance retention decreases.

From the viewpoint of further improving the color purity, the total content of the green colorant having a metal phthalocyanine skeleton, the c.i. pigment yellow 138 and the c.i. pigment yellow 185 in the colorant is preferably 60 mass% or more, more preferably 80 mass% or more, and still more preferably 90 mass% or more.

The green colorant having a metal phthalocyanine skeleton preferably contains c.i. pigment green 58 or c.i. pigment green 59 from the viewpoint of further improving the light transmittance, and the total content of c.i. pigment green 58, c.i. pigment green 59, c.i. pigment yellow 138 and c.i. pigment yellow 185 in the colorant is preferably 60 mass% or more, more preferably 80 mass% or more, and still more preferably 90 mass% or more from the viewpoint of further improving the color purity.

The total content of the colorants including c.i. pigment green 58, c.i. pigment green 59, c.i. pigment yellow 138, and c.i. pigment yellow 185 in the solid content is preferably 2 mass% or more and 16 mass% or less.

Further, from the viewpoint of further improving the color purity, the total content of the c.i. pigment green 58 and the c.i. pigment yellow 185 in the colorant is preferably 60 mass% or more, more preferably 80 mass% or more, and still more preferably 90 mass% or more.

The coloring composition of the present invention may contain a green colorant other than the green colorant having a metal phthalocyanine skeleton. Examples of the green colorant other than the green colorant having a metal phthalocyanine skeleton include organic pigments, inorganic pigments, dyes, and the like, and examples thereof include c.i. pigment green (hereinafter, "PG") PG1, PG2, PG4, PG8, PG10, PG13, PG14, PG15, PG17, PG18, PG19, PG26, PG38, PG39, PG45, PG48, PG50, PG51, PG54, and PG55 (the above numbers are all color index nos.). More than 2 of these colorants may be contained.

The coloring composition of the present invention may contain a colorant other than the above-mentioned green colorant and yellow colorant. The colorant includes an organic pigment, an inorganic pigment, a dye, and the like, and 2 or more of these colorants may be contained. Among them, organic pigments and dyes are preferable from the viewpoint of further improving the transmittance.

Examples of the red pigment include c.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, and PR 254.

Examples of orange pigments include c.i. pigment orange (hereinafter, "PO") 13, PO31, PO36, PO38, PO40, PO42, PO43, PO51, PO55, PO59, PO61, PO64, PO65, and PO 71.

Examples of the blue pigment include c.i. pigment blue (hereinafter, "PB") 15, PB 15: 3. PB 15: 4. PB 15: 6. PB21, PB22, PB60, PB64, and the like.

Examples of the violet pigment include c.i. pigment violet (hereinafter referred to as "PV") 19, PV23, PV29, PV30, PV32, PV37, PV40, and PV50 (the above numbers are all color index nos.).

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

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

In order to improve the resistance to heat, light, acid, alkali, organic solvent, or the like, the basic dye is preferably a salt-forming compound containing an organic acid such as an organic sulfonic acid or an organic carboxylic acid, or perchloric acid, and more preferably a salt-forming compound containing naphthalenesulfonic acid such as tobias acid, or perchloric acid. Similarly, in order to improve resistance to heat, light, acid, alkali, organic solvents, or the like, a salt-forming compound containing a quaternary ammonium salt, primary to tertiary amines, or sulfonamide is preferable as the acid dye and the direct dye.

The coloring composition of the present invention preferably contains a radical polymerizable compound. By containing a radical polymerizable compound, pattern formability can be imparted. The radical 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. There may be more than 2 of these groups.

Examples of the radical polymerizable compound include ethylene oxide-modified or propylene oxide-modified products such as dipentaerythritol penta (meth) acrylate, tetra (trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, penta (meth) acryloxydipentaerythritol monosuccinate, dipentaerythritol hexa (meth) acrylate, styrene derivatives, polyfunctional maleimide compounds, poly (meth) acrylate urethane, adipic acid 1, 6-hexanediol (meth) acrylate, phthalic anhydride propylene oxide (meth) acrylate, trimellitic acid diethylene glycol (meth) acrylate, rosin-modified epoxy di (meth) acrylate, alkyd-modified (meth) acrylate, tripropylene glycol di (meth) acrylate, and mixtures thereof, 2-functional (meth) acrylates such as 1, 6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, 1,3, 5-triacryloylhexahydro-1, 3, 5-triazine, bisphenoxyethanol fluorene diacrylate, dicyclopentadienyl diacrylate, alkyl-modified products thereof, alkyl ether-modified products thereof, and alkyl ester-modified products thereof. More than 2 of these compounds may be contained.

Among them, from the viewpoint of solubility and pattern formability, a compound having a (meth) acryloyl group is preferable, and a polyfunctional compound having 3 or more (meth) acryloyl groups is preferable. By using a polyfunctional compound having 3 or more (meth) acryloyl groups, a film having excellent heat resistance and sufficient curing properties can be formed. In addition, from the viewpoint of alkali developability, a compound having a carboxyl group is preferable. More preferably a compound having 3 or more (meth) acryloyl groups and carboxyl groups. Such a compound includes penta (meth) acryloyloxyditolpentaerythritol monosuccinate.

The content of the radical polymerizable compound in the coloring composition of the present invention is preferably 40 mass% or more in the solid content from the viewpoint of pattern formability. On the other hand, from the viewpoint of suppressing film thickness unevenness during film formation and suppressing pattern deformation due to flow during firing, the content of the radical polymerizable compound in the solid content is preferably 90% by mass or less, 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 the radical polymerizable compound having 3 or more (meth) acryloyl groups and carboxyl groups in the radical polymerizable compound is preferably 50% by mass or more and 100% by mass or less, and 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, an organic acid, an organic amino compound, a curing agent, and the like.

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

Examples of the binder resin include acrylic resins, epoxy resins, polyimide resins, urethane resins, urea resins, polyvinyl alcohol resins, melamine resins, polyamide resins, polyamideimide resins, polyester resins, polyolefin resins, and the like. More than 2 of these resins 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. More than 2 of these carboxylic acids may be used.

Examples of the ethylenically unsaturated compound include unsaturated carboxylic acid alkyl esters such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, etc., aromatic vinyl compounds such as styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, and a-methylstyrene, unsaturated carboxylic acid aminoalkyl esters such as aminoethyl acrylate, etc., unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate, glycidyl methacrylate, etc., carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, etc., vinyl acetate, etc., vinyl propionate, etc., and the like, Vinyl cyanide compounds such as acrylonitrile, methacrylonitrile and α -chloroacrylonitrile, aliphatic conjugated dienes such as 1, 3-butadiene and isoprene, and macromonomers such as polystyrene, polymethyl acrylate, polymethyl methacrylate, polybutyl acrylate, polybutyl methacrylate and polyorganosiloxane having a (meth) acryloyl group at a terminal. More than 2 of these compounds 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 acryloyl group, and a methacryloyl group. Examples of the acrylic resin having an ethylenically unsaturated group in a side chain include "サイクロマー" (registered trademark) P (ダイセル chemical industry co., ltd.), and an alkali-soluble cardo resin.

The weight average molecular weight of the binder resin is preferably 3,000 or more, and more preferably 9,000 or more, from the viewpoint of the strength of the cured film. On the other hand, the weight average molecular weight of the binder resin is preferably 200,000 or less, more preferably 100,000 or less, from the viewpoint of stability of the coloring composition. Here, the weight average molecular weight of the binder resin means a value converted to standard polystyrene measured by gel permeation chromatography.

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

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

The content of the colorant in the coloring composition can be quantified by mass spectrometry using a MALDI mass spectrometer or a time-of-flight secondary ion mass spectrometer, and the ratio (% by mass) of the colorant to the solid content in the coloring composition can be determined from the mass of the colorant and the contents of the other components. When the blending ratio of the raw materials of the coloring composition is known, the ratio (% by mass) of the solid content in the coloring composition can be determined from the blending amount of the coloring agent and the blending amount of the other components.

The coloring composition of the present invention may contain a dispersant such as a pigment derivative together with the colorant. Examples of the dispersant include low-molecular dispersants such as intermediates and derivatives of pigments, and high-molecular dispersants. Examples of the pigment derivative include alkylamine modified products, carboxylic acid derivatives, sulfonic acid derivatives, and the like, which contribute to the pigment skeleton and contribute to the appropriate wetting and stabilization of the pigment. The sulfonic acid derivative of the pigment skeleton having a remarkable effect of stabilizing the fine pigment is preferable.

Examples of the polymer dispersant include polyesters, polyalkylamines, polyallylamines, polyimides, polyamides, polyurethanes, polyacrylates, polyimides, polyamideimides, and copolymers thereof. These polymeric dispersants may be contained in 2 or more kinds. Among these polymeric dispersants, those having an amine value of 5 to 200mgKOH/g in terms of solid content and an acid value of 1 to 100mgKOH/g are preferred. Among these, 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 "ソルスパース" (registered trademark) (manufactured by アビシア), "EFKA" (registered trademark) (manufactured by エフカ), "アジスパー" (registered trademark) (manufactured by kaffuran ファインテクノ (ltd)), and "BYK" (registered trademark) (manufactured by ビックケミー). The polymer dispersant may be contained in 2 or more kinds. Among them, "ソルスパース" (registered trademark) 24000 (manufactured by アビシア), "EFKA" (registered trademark) 4300, 4330 (manufactured by エフカ), 4340 (manufactured by エフカ), "アジスパー" (registered trademark) PB821, PB822 (manufactured by kakoku ファインテクノ), and "BYK" (registered trademark) 161 to 163, 2000, 2001,6919, 21116 (manufactured by ビックケミー) are preferable.

When the coloring composition of the present invention contains a polymer dispersant and/or a binder resin, the total content thereof 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 at the time of film formation. On the other hand, the total content of the polymeric dispersant and the binder resin in the solid content of the coloring composition excluding the colorant is preferably 60% by mass or less, and more preferably 50% by mass or less, from the viewpoint of pattern formability.

The coloring composition of the present invention preferably contains a photopolymerization initiator, and can improve sensitivity in pattern formation. The photopolymerization initiator is a compound that generates radicals by decomposition and/or reaction with light (including ultraviolet rays or electron beams). Examples of the photopolymerization initiator include oxime ester compounds, benzophenone compounds, acetophenone compounds, thioxanthone compounds, anthraquinone compounds, imidazole compounds, benzothiazole compounds, and benzophenones

Azole compounds, carbazole compounds, triazine 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-benzoyloxime), ethanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -,1- (O-acetyloxime), ethanone, 1- [ 9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9H-carbazol-3-yl ] -1- (O-acetyloxime), ethanone, 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) ], "アデカアークルズ" (trade mark registration) N-1919, NCI-930 (manufactured by ADEKA), "IRGACURE" (trade mark registration) OXE01, OXE02 (manufactured by BASF, Ltd.), and the like.

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

Examples of the acetophenone-based compound include 2, 2-diethoxyacetophenone, benzoin methyl ether, benzoin isobutyl ether, benzildimethylketal,. alpha. -hydroxyisobutylphenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholino-1-propane, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholino) phenyl ] -1-butanone, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one, and mixtures thereof, "IRGACURE" (trademark registration) 369, 379, 907 (manufactured by BASF corporation), and the like.

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

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

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

As benzene

As the azole compound, for example, 2-mercaptobenzo

Oxazoles, and the like.

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

More than 2 of these compounds may be contained. Among them, from the viewpoint of pattern formation sensitivity and pattern processability in the coloring composition containing the green colorant having a metal phthalocyanine skeleton of the present invention, the total content of the pigment yellow 138 and the c.i. pigment yellow 185 in the solid content is 2 mass% or more and 16 mass% or less, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one is preferable, and a sensitizer described later is preferably used in combination with the colorant other than 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one.

The content of the photopolymerization initiator in the solid components other than the colorant in the coloring composition is preferably 1% by mass or more, more preferably 2% by mass or more, and further preferably 5% by mass or more, from the viewpoints of sensitivity, pattern formability, and processability. On the other hand, the content of the photopolymerization initiator in the solid components other than the colorant in the coloring composition is preferably 30% by mass or less, more preferably 20% by mass or less, and further preferably 15% by mass or less, from the viewpoints of sensitivity, pattern formability, processability, and heat resistance.

The colored composition of the present invention may further contain a chain transfer agent together with the photopolymerization initiator, and the sensitivity may be further improved. Examples of the chain transfer agent include thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-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, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, and the like, Mercapto compounds such as mercaptophenol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercapto-3-pyridinol, 2-mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropane tris (3-mercaptopropionate), 1,3, 5-tris (3-mercaptobutyloxyethyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione), pentaerythritol tetrakis (3-mercaptopropionate), 1, 4-bis (3-mercaptobutyryloxy) butane, "カレンズ" (registered trademark) MT PE-1 (manufactured by Showa electrician Co., Ltd), "カレンズ" (registered trademark) MT NR-1 (manufactured by Showa electrician Co., Ltd), "カレンズ" (registered trademark) MT BD-1 (manufactured by Showa electrician Co., Ltd.), and the like, An iodinated alkyl compound such as a disulfide compound obtained by oxidizing the mercapto compound, iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, or 3-iodopropanesulfonic acid. More than 2 of these compounds may be contained.

The coloring composition of the present invention may further contain a sensitizer, and the sensitivity can be further improved. Examples of the sensitizer include a thioxanthone-based sensitizer and an aromatic or aliphatic tertiary amine. Examples of the thioxanthone-based sensitizer include thioxanthone, 2-chlorothioxanthone, 2, 4-diethylthioxanth-9-one, and "KAYACURE" (registered trademark) DETX-S (manufactured by japan chemical corporation). More than 2 of these sensitizers may be contained.

The coloring composition of the present invention may further contain an organic solvent. Examples of the organic solvent include diethylene glycol monobutyl ether acetate, benzyl acetate, ethyl benzoate, methyl benzoate, diethyl malonate, 2-ethylhexyl acetate, 2-butoxyethyl acetate, ethylene glycol monobutyl ether acetate, diethyl oxalate, ethyl acetoacetate, cyclohexyl acetate, 3-methoxybutyl acetate, methyl acetoacetate, ethyl-3-ethoxypropionate, 2-ethylbutyl acetate, isoamyl propionate, propylene glycol monomethyl ether propionate, amyl 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 tert-butyl ether, dipropylene glycol monomethyl ether, methyl ether, ethyl carbitol, propylene glycol monoethyl ether, propylene glycol methyl ether, propylene glycol tert-butyl ether, dipropylene glycol monomethyl ether, methyl ether, ethyl carbitol, propylene glycol methyl ether, ethyl ether, ethyl acetate, butyl acetate, isoamyl acetate butanol, 3-methyl-2-butanol, 3-methyl-3-methoxybutanol, cyclopentanone, cyclohexanone, xylene, ethylbenzene, solvent naphtha, and the like. More than 2 of these solvents may be contained.

The coloring composition of the present invention may further contain a polymerization inhibitor, and stability can be improved. The polymerization inhibitor generally exhibits an action of inhibiting or stopping polymerization by radicals generated by heat, light, radical initiator, and the like, and is generally used for preventing gelation of a thermosetting resin, stopping polymerization at the time of producing a polymer, and the like. Examples of the polymerization inhibitor include hydroquinone, t-butylhydroquinone, 2, 5-bis (1,1,3, 3-tetramethylbutyl) hydroquinone, 2, 5-bis (1, 1-dimethylbutyl) hydroquinone, catechol, t-butylcatechol, and the like. More than 2 kinds of polymerization inhibitors may be contained. From the viewpoint of balance between stability and photosensitive characteristics, the content of the polymerization inhibitor in the solid content is preferably 0.0001% by mass or more, and more preferably 0.005% by mass or more. From the viewpoint of the balance between stability and photosensitive characteristics, the content of the polymerization inhibitor in the solid content is preferably 1% by mass or less, and more preferably 0.5% by mass or less.

The coloring composition of the present invention may further contain an adhesion improving agent, and the adhesion of the coating film of the coloring composition to the substrate can be improved. Examples of the adhesion improving agent include, for example, silane coupling agents such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane. These adhesion improving agents may be contained in 2 or more kinds.

The coloring composition of the present invention may further contain a surfactant, and the coatability of the coloring composition and the uniformity of the coating film surface can be improved. Examples of the surfactant include anionic surfactants such as ammonium lauryl sulfate and triethanolamine polyoxyethylene alkyl ether sulfate, cationic surfactants such as stearylamine acetate and lauryl trimethylammonium chloride, lauryl dimethyl amine oxide, and lauryl carboxymethyl hydroxyethyl imidazole

Amphoteric surfactants such as betaine, nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether and sorbitan monostearate, fluorine-based surfactants, and silicon-based surfactants. More than 2 of these surfactants may be contained. FromThe content of the surfactant in the coloring composition is preferably 0.001 to 10% by mass 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 can be obtained, for example, by preparing a pigment dispersion by dispersing a green colorant having a metal phthalocyanine skeleton, c.i. pigment yellow 138 and/or c.i. pigment yellow 185, and if necessary, other colorants, binder resins, organic solvents, and other components, and further adding other components if necessary. Examples of the dispersing machine include a sand mill, a ball mill, a bead mill, a three-roll mill, and an attritor. Among them, a bead mill having excellent dispersion efficiency is preferable. Examples of the dispersed beads include zirconia beads, alumina beads, and glass beads. Among them, zirconia beads are preferable. When a pigment is contained as the colorant, it is preferable to add a solvent or the like to a pigment powder in advance and to finely divide secondary particles (having a particle diameter of about 1 to 50 μm) by a dispersing machine.

Next, the color filter substrate of the present invention will be explained. The color filter substrate of the present invention has pixels formed of the colored composition of the present invention on a substrate. That is, the pixel is formed of a photo-cured product or a thermosetting product of the coloring composition of the present invention. There may be other pixels of red, blue, etc. Further, the liquid crystal display device preferably has a black matrix, a photo spacer (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 a plate of inorganic glass such as soda glass, alkali-free glass, borosilicate glass, quartz glass, aluminoborosilicate glass, aluminosilicate glass, alkali aluminosilicate glass, soda lime glass having a silica-coated surface, and a film or sheet of organic plastic. Black matrices may be formed on these substrates. In the case where the display device including the color filter substrate of the present invention is a reflective display device, the substrate may be opaque.

The film or sheet of the organic plastic may be a free-standing film, or may be a film formed by coating or the like on a substrate such as a glass substrate.

In the case of such a coating film, the adhesion between the substrate and the film can be appropriately adjusted by laser or the like to be peeled. Examples of the material of the organic plastic include polyesters such as polypropylene, polyethylene, polystyrene, and polyethylene terephthalate (PET), fluoropolymers such as polyphenylene sulfide (PPS), polyimide, polyamide, polyamideimide, polyethersulfone, and Polytetrafluoroethylene (PTFE), polyetheretherketone, polyphenylene oxide, polyarylate, and polysulfone. Among them, in the case of using an organic plastic as the substrate, polyimide is preferable from the viewpoint of heat resistance, process suitability, mechanical strength, dimensional stability, and chemical resistance. In the case of using an organic plastic as the substrate, the substrate is preferably a film having a thickness of 5 μm or more, 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.

The polyimide is not particularly limited, and in general, a polyimide represented by the following general formula (1) can be used. The polyimide precursor is obtained by, for example, subjecting a polyimide precursor represented by the following general formula (2) to imide ring closure (imidization). The method of the imidization reaction is not particularly limited, and thermal imidization and chemical imidization may be mentioned. Among them, thermal imidization is preferable from the viewpoint of heat resistance and transparency in the visible light region of the polyimide film.

In the general formulae (1) and (2), R¹Represents a 4-valent organic group, R²Represents a 2-valent organic group. X¹And X²Each independently represents a hydrogen atom or a 1-valent organic group having 1 to 10 carbon atoms.

As R in the general formulae (1) and (2)¹And represents a 4-valent organic group, and is a residue of acid dianhydride or a derivative 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 dianhydride, 2 ', 3, 3' -biphenyltetracarboxylic dianhydride, 3,3 ', 4, 4' -terphenyltetracarboxylic dianhydride, 3,3 ', 4, 4' -oxybenzenedicarboxylic acid dianhydride (3,3 ', 4, 4' -oxyphthalic dianhydride), 2,3,3 ', 4' -oxybenzenedicarboxylic acid dianhydride, 2,3, 2 ', 3' -oxybenzenedicarboxylic acid dianhydride, diphenylsulfone-3, 3 ', 4, 4' -tetracarboxylic dianhydride, benzophenone-3, 3 ', 4, 4' -tetracarboxylic dianhydride, 2-bis (3, 4-dicarboxyphenyl) propane dianhydride, 2-bis (2, 3-dicarboxyphenyl) propane dianhydride, 1-bis (3, 4-dicarboxyphenyl) ethane dianhydride, 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-dihydroisobenzofuran-5-carboxylic acid) 1, 4-phenylene-2, 2-bis (4- (4-aminophenoxy) phenyl) propane, 1,2,5, 6-naphthalene tetracarboxylic dianhydride, 2,3,6, 7-naphthalene tetracarboxylic dianhydride, 9-bis (3, 4-dicarboxyphenyl) fluorene dianhydride, 2,3,5, 6-pyridinetetracarboxylic dianhydride, 3,4,9, 10-perylenetetracarboxylic dianhydride, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride, 2-bis (4- (3, 4-dicarboxybenzoyloxy) phenyl) hexafluoropropane dianhydride, 1, 6-difluoropyromellitic dianhydride, 1-trifluoromethylpyromellitic dianhydride, 1, 6-bis (trifluoromethyl) pyromellitic dianhydride, 2 '-bis (trifluoromethyl) -4, 4' -bis (3, 4-dicarboxyphenoxy) biphenyl dianhydride, 2 '-bis [ (dicarboxyphenoxy) phenyl ] propane dianhydride, 2' -bis [ (dicarboxyphenoxy) phenyl ] hexafluoropropane dianhydride, or with an alkyl group, an alkoxy group, An acid dianhydride compound in which an aromatic ring is substituted with a halogen atom or the like, but the acid dianhydride compound 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, 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-tetrahydrofuranetetracarboxylic dianhydride, 3, 4-dicarboxyl-1-cyclohexylsuccinic dianhydride, 2,3, 5-tricarboxycyclopentylacetic acid dianhydride, 3, 4-dicarboxyl-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, 4,8, 10-tetracarboxylic dianhydride, tricyclo [6,3,0,0 > 2,6 > ] undecane-3, 5,9, 11-tetracarboxylic dianhydride, bicyclo [2,2,2] octane-2, 3,5, 6-tetracarboxylic dianhydride, bicyclo [2,2,2] octan-7-ene-2, 3,5, 6-tetracarboxylic dianhydride, bicyclo [2,2,1] heptane tetracarboxylic dianhydride, heptanes dianhydride, bicyclo [2,2,1] heptane tetracarboxylic dianhydride, and bicyclo [4,4, 6, 8-tetracarboxylic dianhydride, Bicyclo [2,2,1] heptane-5-carboxymethyl-2, 3, 6-tricarboxylic acid dianhydride, 7-oxabicyclo [2,2,1] heptane-2, 4,6, 8-tetracarboxylic acid dianhydride, octahydronaphthalene-1, 2,6, 7-tetracarboxylic acid dianhydride, decatetrahydroanthracene-1, 2,8, 9-tetracarboxylic acid dianhydride, 3 ', 4, 4' -dicyclohexyl-tetracarboxylic acid dianhydride, 3 ', 4, 4' -oxydicyclohexane-tetracarboxylic acid dianhydride, 5- (2, 5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1, 2-dicarboxylic anhydride, and "リカシッド" (registered trademark) BT-100 (see above, trade name, new japanese physicochemical (strain)), and derivatives thereof, Or an acid dianhydride compound in which these alicyclic rings are substituted with an alkyl group, an alkoxy group, a halogen atom, or the like, but is not limited thereto.

Examples of the aliphatic acid dianhydride include, but are not limited to, 1,2,3, 4-butane tetracarboxylic dianhydride, 1,2,3, 4-pentane tetracarboxylic dianhydride, and derivatives thereof.

These aromatic acid dianhydrides, alicyclic acid dianhydrides, or aliphatic acid dianhydrides may be used singly or in combination of 2 or more.

Among them, pyromellitic dianhydride, 3 ', 4,4 ' -biphenyltetracarboxylic dianhydride, 3 ', 4,4 ' -oxybenzoic acid dianhydride, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride, 2 ' -bis [ (dicarboxyphenoxy) phenyl ] propane dianhydride, 2,3,6, 7-naphthalenetetracarboxylic dianhydride, 1,2,4, 5-cyclohexanetetracarboxylic dianhydride, 3 ', 4,4 ' -bicyclohexane tetracarboxylic dianhydride, and 1,2,3, 4-cyclobutanetetracarboxylic dianhydride are preferably used from the viewpoint of being commercially available and easy to handle, and from the viewpoint of reactivity.

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

As R in the general formulae (1) and (2)²And represents a 2-valent organic group, which is a residue of a diamine or a derivative 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 ' -diaminodiphenyl ether, 3,4 ' -diaminodiphenyl methane, 4 ' -diaminodiphenyl methane, 3 ' -diaminodiphenyl sulfone, 3,4 ' -diaminodiphenyl sulfone, 4 ' -diaminodiphenyl sulfone, 3,4 ' -diaminodiphenyl sulfide, 4 ' -diaminodiphenyl sulfide, 1, 4-bis (4-aminophenoxy) benzene, benzidine, 2 ' -bis (trifluoromethyl) benzidine, 3 ' -bis (trifluoromethyl) benzidine, 2 ' -dimethylbenzidine, 3 ' -dimethylbenzidine, 2 ' 3,3 ' -tetramethylbenzidine, 3,4 ' -diaminodiphenyl sulfide, 1,4 ' -bis (4-aminophenoxy) benzene, and the like, 2,2 ' -dichlorobenzidine, 3 ' -dichlorobenzidine, 2 ', 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-bis (4-aminophenyl) fluorene, 2 ' -bis [3- (3-aminobenzamide) -4-hydroxyphenyl ] hexafluoropropane, or a diamine compound having an aromatic ring thereof substituted with an alkyl group, an alkoxy group, a halogen atom or the like, but is not limited thereto.

Examples of the alicyclic diamine compound include cyclobutanediamine, isophoronediamine, bicyclo [2,2,1] heptanedimethylamine, tricyclo [3,3,1,13,7] decane-1, 3-diamine, 1, 2-cyclohexyldiamine, 1, 3-cyclohexyldiamine, 1, 4-cyclohexyldiamine, trans-1, 4-diaminocyclohexane, 4 ' -diaminodicyclohexylmethane, 3 ' -dimethyl-4, 4 ' -diaminodicyclohexylmethane, 3 ' -diethyl-4, 4 ' -diaminodicyclohexylmethane, 3 ', 5,5 ' -tetramethyl-4, 4 ' -diaminodicyclohexylmethane, 3 ', 5,5 ' -tetraethyl-4, 4 ' -diaminodicyclohexylmethane, dimethylcyclohexylmethane, dimethylcyclohexyl, 3, 5-diethyl-3 ', 5 ' -dimethyl-4, 4 ' -diaminodicyclohexylmethane, 4 ' -diaminodicyclohexylether, 3 ' -dimethyl-4, 4 ' -diaminodicyclohexylether, 3 ' -diethyl-4, 4 ' -diaminodicyclohexylether, 3 ', 5,5 ' -tetramethyl-4, 4 ' -diaminodicyclohexylether, 3 ', 5,5 ' -tetraethyl-4, 4 ' -diaminodicyclohexylether, 3, 5-diethyl-3 ', 5 ' -dimethyl-4, 4 ' -diaminodicyclohexylether, 2-bis (4-aminocyclohexyl) propane, 2-bis (3-methyl-4-aminocyclohexyl) propane, 4 ' -diaminodicyclohexyl ether, 2,4 ' -diaminodicyclohexyl ether, and mixtures thereof, 2, 2-bis (3-ethyl-4-aminocyclohexyl) propane, 2-bis (3, 5-dimethyl-4-aminocyclohexyl) propane, 2-bis (3, 5-diethyl-4-aminocyclohexyl) propane, 2- (3, 5-diethyl-3 ', 5 ' -dimethyl-4, 4 ' -diaminodicyclohexyl) propane, or a diamine compound in which an alicyclic ring thereof is substituted with an alkyl group, an alkoxy group, a halogen atom, or the like, but the present invention is not limited thereto.

Examples of the aliphatic diamine compound include, but are not limited to, alkylenediamines such as ethylenediamine, 1, 3-diaminopropane, 1, 4-diaminobutane, 1, 5-diaminopentane, 1, 6-diaminohexane, 1, 7-diaminoheptane, 1, 8-diaminooctane, 1, 9-diaminononane, and 1, 10-diaminodecane, ethylenediamines such as bis (aminomethyl) ether, bis (2-aminoethyl) ether, and bis (3-aminopropyl) ether, and siloxane diamines such as 1, 3-bis (3-aminopropyl) tetramethyldisiloxane, 1, 3-bis (4-aminobutyl) tetramethyldisiloxane, and α, ω -bis (3-aminopropyl) polydimethylsiloxane.

These aromatic diamine, alicyclic diamine, or aliphatic diamine may be used alone or in combination of 2 or more.

As X in the general formulae (1) and (2)¹And X²Each independently represents a hydrogen atom or a 1-valent organic group having 1 to 10 carbon atoms. Examples of the 1-valent organic group having 1 to 10 carbon atoms include a saturated hydrocarbon group, an unsaturated hydrocarbon group, an aromatic group, and the like. 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, and a biphenyl groupPhenyl, phenylethynyl, and the like. The saturated hydrocarbon group may be further substituted with a halogen atom. Examples of the aromatic group include a phenyl group and the like. The aromatic group may be further substituted with a saturated hydrocarbon group, an unsaturated hydrocarbon group, or a halogen atom.

Since polyimide used for the substrate is required to have high 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 improve the transparency. The alicyclic monomer may be used for both the acid dianhydride and the diamine component, or may be used for either component. Further, it may be used in combination with an aromatic monomer.

In order to maintain the transparency of the polyimide at a higher level, R in the general formulae (1) and (2)¹Preferably 1 or more selected from the group consisting of the structures represented by the following general formulae (3) to (8), and R in the general formulae (1) and (2)¹The amount of the structure represented by the following general formulae (3) to (8) is preferably 50 mol% or more, more preferably 80 mol% or more, and still more preferably 100 mol%. Among them, R in the general formulae (1) and (2) is R in view of lowering the linear expansion coefficient¹The following general formulae (3), (5) and (6) are preferred.

In addition, R in the general formulae (1) and (2) is R from the viewpoint of lowering the linear expansion coefficient of polyimide²Preferably 1 or more selected from the group consisting of the structures represented by the following general formulae (9) to (12), and R in the general formulae (1) and (2)¹The amount of the structure represented by the following general formulae (9) to (12) is preferably 50 mol% or more, more preferably 80 mol% or more, and still more preferably 100 mol%. Among them, R in the general formulae (1) and (2) is R from the viewpoint of high solubility and low linear expansion coefficient²The following general formula (10) is preferable. In addition, R in the general formulae (1) and (2) is R from the viewpoint of increasing the transmittance of polyimide²The following general formula (9) or (10) is preferable.

In addition, R in the general formulae (1) and (2) is R from the viewpoint of high transmittance of polyimide, easy laser lift-off, and low linear expansion coefficient²Preferably, the resin composition contains 1 or more selected from the group consisting of the structures represented by the following general formulae (13) and (14). In addition, of the general formula (14)

The azole ring is formed by dehydration ring closure of the structure represented by the general formula (13). In addition, from the viewpoint of processability of a pixel formed on polyimide, R in the general formulae (1) and (2)²The amount of the structure represented by the following general formula (13) or (14) in (a) is preferably 30 mol% or less, and more preferably 20 mol% or less.

The method for obtaining the polymerization reaction of the polyimide and the polyimide precursor is not particularly limited as long as the target polyimide and the polyimide precursor can be produced, and a known method can be used. Specific examples of the reaction method include a method in which a predetermined amount of all of the diamine component and the solvent are charged into a reactor and dissolved, and then a predetermined amount of the acid dianhydride component is added and stirred at room temperature to 80 ℃ for 0.5 to 30 hours. The acid dianhydride and diamine used for the synthesis of the polyimide precursor may be known ones, and are preferably those described above. Polyimide precursors such as polyamic acids, polyamic acid esters, and polyamic acid silyl esters can be synthesized by reacting a diamine compound with an acid dianhydride or a derivative thereof. Examples of the derivative include tetracarboxylic acid of the acid dianhydride, a monoester of the tetracarboxylic acid, a diester of the tetracarboxylic acid, a triester of the tetracarboxylic acid, a tetraester of the tetracarboxylic acid, and an acid chloride, and specifically include structures esterified with a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, and the like.

In order to adjust the molecular weight to a preferred range, the polyimide and the polyimide precursor may be sealed at both ends by a capping agent. Examples of the end-capping agent to be reacted with the acid dianhydride include monoamines and monoalcohols. Examples of the end-capping agent to be reacted with the diamine compound include acid anhydrides, monocarboxylic acids, monoacid chloride compounds, mono-active ester compounds, dicarbonates, vinyl ethers, and the like. Further, by reacting the end-capping agent, various organic groups can be introduced as end groups.

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

Examples of the pixel include a colored pixel such as red or blue and a transparent pixel. 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 or a polyimide resin and a radical polymerizable compound. 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, from the viewpoint of improving color purity. 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 a substance that prevents a decrease in contrast and color purity due to light leakage between pixels, and is preferably disposed between pixels and in a frame portion. Examples of the material constituting the black matrix include a photosensitive composition containing a binder resin such as an acrylic resin or a polyimide resin and a radical polymerizable compound, a black-colored non-photosensitive resin composition, and the like. From the viewpoint of light-shielding properties, the 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, more preferably 1.5 μm or less.

The photo spacers are formed by providing a predetermined gap between the photo spacers and the opposing substrate, and the gap can be filled with a liquid crystal compound or the like, so that the step of disposing the spacers can be omitted in the production of the liquid crystal display device. Preferably, the fixing member is fixed to a specific position of the color filter substrate so as to be in contact with 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 photo spacer include a cylindrical shape, a prismatic shape, a truncated conical shape, and a truncated pyramidal 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 transmission of impurities from pixels of the color filter substrate or planarizes level differences caused by the pixels of the color filter substrate. Examples of the material constituting the overcoat layer include epoxy resin, acrylic resin, silicone resin, polyimide resin, and photosensitive or non-photosensitive materials commercially available as planarization materials. From the viewpoint of processability, the film thickness of the overcoat layer is preferably 0.5 μm or more, and more preferably 1.0 μm or more. On the other hand, from the viewpoint of flatness of the color filter substrate, it is preferably 5.0 μm or less, and more preferably 3.0 μm or less.

Examples of 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).

As a method for manufacturing a color filter substrate, for example, a method for patterning pixels formed of a resin composition on a substrate is given. The manufacturing method will be described below by taking a color filter substrate having pixels formed from the photosensitive colored composition of the present invention as an example. The color filter substrate can be obtained by coating the color composition of the present invention on a substrate, patterning by selective exposure using a photomask and development, and firing to form pixels.

Examples of the method for applying the coloring 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 the coloring composition, a method of spraying the coloring composition onto a substrate, and the like. Next, the substrate coated with the coloring composition is dried, thereby forming a coating film of the coloring composition on the substrate. Examples of the drying method include air drying, heat drying, and vacuum drying. These may be combined with 2 or more kinds, and for example, it is preferable to dry under reduced pressure and then heat dry. The heating and drying temperature is preferably 80-130 ℃, and the heating and drying device is preferably a hot blast stove or an electric hot plate. In the case of a color filter substrate having a black matrix, it is preferable to form a coating film of a coloring composition on a substrate on which a black matrix is formed in advance.

Next, a photomask was placed on the coating film of the coloring composition, and selective exposure was 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 scanner 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.

Then, the unexposed portion is removed by development with an alkaline developer, and a coating film pattern is formed. Examples of the basic substance used in the alkaline developer include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, primary amines such as ethylamine and n-propylamine, secondary amines such as diethylamine and di-n-propylamine, tertiary amines such as triethylamine and methyldiethylamine, and organic bases such as tetramethylammonium hydroxide. Examples of the alkaline developer include 0.02 to 1 mass% of potassium hydroxide, tetramethylammonium hydroxide, and the like. Examples of the developing method include a method in which the coating film after exposure is immersed in an alkaline developer for 20 to 300 seconds.

Then, by subjecting the resultant coating film pattern to heat treatment, a color filter substrate in which pixels are patterned is obtained. The heat treatment may be performed in any of air, a nitrogen atmosphere, and a vacuum. The heating temperature is preferably 150 to 350 ℃, and more preferably 180 to 250 ℃. The heating time is preferably 5 minutes to 5 hours. The heating device is preferably a hot-blast stove or an electric hot plate. The heat treatment may be performed continuously or stepwise.

The pixels of 3 to 6 colors included in the color filter substrate are formed in sequence by the above method. The order of formation of each color is not particularly limited, and when a pixel including a dye is formed, it is preferable to form the pixel including the dye after formation of other pixels from the viewpoint of further suppressing color shift of the colorant.

Further, in the case of a coloring composition containing a green coloring agent and a yellow coloring agent, and the ratio of the yellow coloring agent in the coloring agent is high, the light transmittance retention ratio of the color pixel becomes low, and therefore, the color filter substrate of the present invention is preferably a color filter substrate having a red pixel, a green pixel, a blue pixel, and a color pixel of the 4 th color, and the color pixel of the 4 th color is formed by a photo-cured product or a thermosetting product of the coloring composition of the present invention. In addition, from the viewpoint of improving color purity and improving light transmittance retention, it is preferable that the light absorption rate of the color pixel of the 4 th color at 480nm is 50% or more and the light absorption rate at 650nm is 10% or more and 90% or less.

The light absorption of a color pixel herein means a ratio of light which is prevented from passing through the color pixel when light of a certain wavelength passes through the color pixel, and can be measured, for example, by an Otsuka type micro spectrometer LCF-100 MA. Further, the light absorptance of the color pixel of the 4 th color on the color filter substrate can be calculated from the light absorptance of the area where the color pixel is not formed on the color filter substrate and the light absorptance of the area of the color pixel of the 4 th color on the color filter substrate.

In order to obtain such a color pixel of the 4 th color, the color pixel includes c.i. pigment green 58 and c.i. pigment yellow 185, the content of the c.i. pigment yellow 185 in the colorant is preferably 50 mass%, and the content of the colorant in the solid content is preferably 5 mass% or more.

The color filter substrate of the present invention may be a component of a display device such as a liquid crystal display, an organic EL display, and electronic paper. That is, the display device of the present invention includes the color filter substrate of the present invention and a display element. Further, the display device may have various kinds of films such as a light source such as an external light source, a luminance improving film, and a diffusion plate. The display device is a device that displays an image by making a part of a screen visible. Examples of the display element include a liquid crystal element, an organic EL element, an inorganic EL element, a display element using MEMS, a display element using quantum dots, an electronic ink, an electronic powder fluid, and an electrophoretic element. Examples of the display device include a transmissive liquid crystal display, a semi-transmissive liquid crystal display, a reflective liquid crystal display, an organic EL display, an inorganic EL display, a quantum dot display, and electronic paper. In contrast to a transmissive liquid crystal display in which the intensity of a backlight light source is increased to easily improve the brightness of display, a reflective liquid crystal display in which ambient light is mainly used has one of factors that determine the brightness of display, and therefore 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 light from outside or inside, such as wearable terminals, electronic signboards, digital billboards, and electronic shelf labels. In the case of a reflective display device, a reflective layer made of metal such as silver or aluminum is provided inside the reflective display device, and light incident from the front surface of the display device is reflected by the reflective layer and passes through the color filter substrate 2 times, whereby the color purity can be further improved, while the light transmittance tends to be easily lowered. Even in such a reflective display device, a display device having excellent display characteristics can be obtained by setting the total content of the green colorant having a metal phthalocyanine skeleton and the c.i. pigment yellow 138 and the c.i. pigment yellow 185 to 2 mass% or more and 16 mass% or less in the solid content. The reflective layer may have a layered structure formed of a metal such as silver or aluminum, or may have a multilayer structure formed of transparent resins having different refractive indices, as long as it reflects light in the visible light region. The reflective layer is preferably a layer made of a metal such as silver or aluminum formed by sputtering, vapor deposition, or the like, from the viewpoint of reflectance.

As an example of the method for manufacturing a display device of the present invention, a method for manufacturing a liquid crystal display device is described below. The color filter substrate and the array substrate are bonded to each other in a manner facing each other via a spacer for holding a liquid crystal alignment film and a cell gap provided on the substrates. In addition, a Thin Film Transistor (TFT) element, a Thin Film Diode (TFD) element, a scanning line, a signal line, or the like is provided on the array substrate, so that a TFT liquid crystal display device or a TFD liquid crystal display device can be manufactured. Next, after injecting liquid crystal from an injection port provided in the sealing portion, the injection port is sealed. Further, a backlight, an IC driver, and the like are mounted, and thus the liquid crystal display device is completed. In addition, as the backlight, a 2-wavelength LED, a 3-wavelength LED, a CCFL, or the like may be used, but a 3-wavelength LED is preferable in terms of that the color reproduction range of the liquid crystal display device can be expanded and the power consumption can be reduced.

Examples

The present invention will be described below with reference to examples, but the present invention is not limited to these examples. First, the evaluation methods in examples and comparative examples will be described.

< evaluation of chromaticity and light transmittance >

The colored compositions obtained in examples 1 to 13 and comparative examples 1 to 8 were applied to a glass substrate, and then dried by heating at 90 ℃ for 10 minutes. The resultant colored composition coating film was subjected to an i-ray treatment using a negative photomask at 200mJ/cm²After the exposure, the resist was developed with a 0.3 mass% aqueous tetramethylammonium hydroxide solution at 23 ℃ to form a desired pattern. Then, heat treatment was carried out at 230 ℃ for 30 minutes to obtain a film having a thickness of 1.7 μm. However, only example 13 had a film thickness of 2.5 μm. The film was measured using an Otsuka Denshi microscopical analyzer LCF-100MA (Denko Co., Ltd.) under a C light sourceThe chromaticity x, Y and the light transmittance Y are determined.

< evaluation of light absorption >

The colored compositions obtained in examples 1 to 13 and comparative examples 1 to 8 were applied to a glass substrate, and then dried by heating at 90 ℃ for 10 minutes. The resultant colored composition coating film was subjected to i-ray treatment with 200mJ/cm through a negative photomask²After the exposure, the resist was developed with a 0.3 mass% aqueous tetramethylammonium hydroxide solution at 23 ℃ to form a desired pattern. Then, heat treatment was carried out at 230 ℃ for 30 minutes to obtain a film having a thickness of 1.7 μm. However, only example 13 had a film thickness of 2.5 μm. The film was measured for light absorptance at 480nm and 650nm using an Otsuka type micro spectrometer LCF-100 MA.

< evaluation of light transmittance maintenance ratio by light irradiation >

The coloring compositions obtained in examples 1 to 13 and comparative examples 1 to 8 were applied to a glass substrate on which a black matrix was formed, and then dried by heating at 90 ℃ for 10 minutes. The resultant colored composition coating film was subjected to an i-ray treatment using a negative photomask at 200mJ/cm²After the exposure, the resist was developed with a 0.3 mass% aqueous tetramethylammonium hydroxide solution at 23 ℃ to form a desired pattern. Subsequently, heat treatment was performed at 230 ℃ 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. The green pixel of the color filter substrate was measured for the Y value with a C light source using an Otsuka electron micro spectrometer LCF-100MA, and the obtained value was Y0.

The array substrate is fabricated by forming TFT elements, transparent electrodes, and the like on alkali-free glass. Polyimide alignment films were formed on the manufactured color filter substrate and array substrate, respectively, and rubbing treatment was performed thereon. A sealant containing a micro-rod was printed on the array substrate, and a bead spacer having a thickness of 6 μm was scattered, and then the array substrate and the color filter substrate were bonded. Nematic liquid crystal ("リクソン" JC-5007LA, manufactured by チッソ corporation) was injected from an injection port provided in the sealing part, and then the polarizing film was oriented such that the polarizing axis was perpendicular to the polarizing axisThe substrates were bonded to both sides of the liquid crystal cell to obtain a liquid crystal panel. A white LED backlight composed of a blue LED and a YAG phosphor is attached to the liquid crystal panel, and a TAB module, a printed circuit board, and the like are attached to the liquid crystal panel to fabricate a liquid crystal display device. The white LED backlight uses a luminosity of 10000cd/m²The backlight of (1). The liquid crystal display device was put into a 60% constant temperature and high humidity chamber at 60 ℃ for 100 hours in a state where the backlight was turned on. Then, the panel was detached, and the Y value was measured using an Otsuka electron micro spectrometer LCF-100MA for green pixels using a C light source, and the obtained Y value was set to Y1. The light transmittance retention was calculated as Y1/Y0.

Production example 1 (preparation of Dispersion (A1))

A slurry was prepared by mixing 150g of C.I. pigment Yellow 185 ("Paliotol" (registered trademark) Yellow D1155, manufactured by BASF, "125 g of" BYK "(registered trademark) LPN6919 (manufactured by ビックケミー, polymeric dispersant solution (60 mass% propylene glycol monomethyl ether solution)", "サイクロマー" (registered trademark) ACA250(ダイセル chemical Co., Ltd., 45 mass% dipropylene glycol monomethyl ether solution) "100 g, and 625g of propylene glycol monomethyl ether (PMA). The beaker containing the slurry was connected to a dinor mill (dyno-mill) through a tube, and dispersion treatment was performed for 8 hours using zirconia beads having a diameter of 0.5mm as a medium at a peripheral speed of 14m/s to prepare a c.i. pigment yellow 185 dispersion (a 1).

Production example 2 (preparation of Dispersion (A2))

A c.i. pigment Green 58 dispersion (a2) was prepared in the same manner as in production example 1, except that 150g of c.i. pigment Green 58 ("FASTGEN" (registered trademark) Green a110, manufactured by DIC corporation) was used instead of the c.i. pigment yellow 185.

Production example 3 (preparation of Dispersion (A3))

A c.i. pigment YELLOW 138 dispersion (A3) was prepared in the same manner as in production example 1, except that 150g of c.i. pigment YELLOW 138 ("LIONOGEN" (registered trademark) YELLOW1010, manufactured by imperial インキ, ltd.) was used instead of the c.i. pigment YELLOW 185.

Production example 4 (Synthesis of Binder resin solution (B1))

A500 mL three-necked flask was charged with 33g (0.3mol) of methyl methacrylate, 33g (0.3mol) of styrene, 34g (0.4mol) of methacrylic acid, 3g (0.02mol) of 2, 2' -azobis (2-methylbutyronitrile) and 150g of Propylene Glycol Monomethyl Ether Acetate (PGMEA), and the mixture was stirred at 90 ℃ for 2 hours, then the internal temperature was increased to 100 ℃ and further stirred for 1 hour to obtain a reaction solution. To the obtained reaction solution were added 33g (0.2mol) of glycidyl methacrylate, 1.2g (0.009mol) of dimethylbenzylamine and 0.2g (0.002mol) of p-methoxyphenol, and after stirring at 90 ℃ for 4 hours, PGMEA50g was added to obtain a binder resin solution (B1) having a solid content of 40 mass%. The acid value of the binder resin was measured with respect to a 0.1mol/L potassium hydroxide/ethanol solution using an automatic potential difference measuring apparatus AT-610 manufactured by Kyoto electronics industries, Ltd., and was 80.0 (mgKOH/g). Further, the weight average molecular weight was calculated in terms of polystyrene using a GPC device, and as a result, the weight average molecular weight was 22,000.

Example 1

To a50 mL plastic bottle were added 10.99g of the dispersion obtained in production example 1, 23.95g of the dispersion obtained in production example 2, 13.27g of the binder resin solution obtained in production example 4, 2.30g of penta (meth) acryloyloxyditolpentaerythritol monosuccinate (C1), 0.31g of 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one (D1), 0.15g of 2, 4-diethylthioxanthen-9-one (D2), and 19.03g of dipropylene glycol methyl ether acetate (hereinafter, DPMA), and the mixture was stirred for 3 hours to prepare a colored composition (E1). The obtained colored composition was evaluated for light transmittance retention by the above-mentioned method, and Y1/Y0 was 0.980. Further, the chromaticity is 0.309, Y is 0.459, and the light transmittance Y is 78.1. Further, the light absorption at 480nm was 47.8%, and the light absorption at 650nm was 86.1%.

Examples 2 to 13 and comparative examples 1 to 8

A colored composition (E2 to E21) was obtained in the same manner as in example 1, except that the kinds and addition ratios of the dispersion liquid, the binder resin solution, the radical polymerizable compound, the photopolymerization initiator, and the organic solvent were changed to those described in table 1. The obtained coloring compositions were evaluated by the above-described methods, and the results are shown in tables 2 and 3.

[ TABLE 1]

Example 14

In a 100mL four-necked flask, 3.34g (17.0mmol) of 1,2,3, 4-cyclobutanetetracarboxylic dianhydride, 4.64g (14.5mmol) of 2, 2' -bis (trifluoromethyl) benzidine, 1.55g (2.56mmol) of 2, 2-bis [3- (3-aminobenzamide) -4-hydroxyphenyl ] hexafluoropropane and 50g of N-methyl-2-pyrrolidone were charged under a stream of dry nitrogen gas, and the mixture was stirred under heating at 60 ℃. After 8 hours, cool to make a varnish.

Subsequently, the varnish thus obtained was spin-coated on a glass substrate, and subjected to a pre-baking treatment at 140 ℃ for 4 minutes to form a film having a thickness of 10 μm. Then, the pre-baked film was heated to 300 ℃ at 3.5 ℃/min under a nitrogen gas flow (oxygen concentration: 20ppm or less) using an inert gas oven (INH-21 CD manufactured by Toyobo サーモシステム Co., Ltd.), was held for 30 minutes, and was cooled to 50 ℃ at 5 ℃/min to form a polyimide film.

Subsequently, the coloring composition obtained in example 3 was applied, and then, heat drying was performed at 90 ℃ for 10 minutes. The resultant colored composition coating film was subjected to an i-ray treatment using a negative photomask at 200mJ/cm²After the exposure, development was carried out with a 0.3 mass% aqueous tetramethylammonium hydroxide solution at 23 ℃ to form a pattern of 20 μm × 200 μm size and a pattern of 15 μm × 150 μm size. Subsequently, heat treatment was carried out at 230 ℃ for 30 minutes to obtain a film having a thickness of 1.7 μm.

The obtained substrate with pixels was irradiated with 308nm excimer laser from the glass substrate sideA laser lift-off test was carried out using light (shape: 21 mm. times.1.0 mm), and the result was that the irradiation energy was 250mJ/cm²In this case, the polyimide film was confirmed to be lifted from the glass substrate.

Example 15

In a 100mL four-necked flask, 2.33g (11.9mmol) of 1,2,3, 4-cyclobutanetetracarboxylic dianhydride, 7.19g (11.9mmol) of 2, 2-bis [3- (3-aminobenzamide) -4-hydroxyphenyl ] hexafluoropropane and 50g of N-methyl-2-pyrrolidone were charged under a stream of dry nitrogen gas, and the mixture was heated and stirred at 60 ℃. After 8 hours, cool to make a varnish.

Subsequently, the varnish thus obtained was spin-coated on a glass substrate, and subjected to a pre-baking treatment at 140 ℃ C.. times.4 minutes to form a film having a thickness of 10 μm. Then, the pre-baked film was heated to 300 ℃ at 3.5 ℃/min under a nitrogen gas flow (oxygen concentration: 20ppm or less) using an inert gas oven (INH-21 CD manufactured by Toyobo サーモシステム Co., Ltd.), was held for 30 minutes, and was cooled to 50 ℃ at 5 ℃/min to form a polyimide film.

Subsequently, the coloring composition obtained in example 3 was applied, and then, heat drying was performed at 90 ℃ for 10 minutes. The resultant colored composition coating film was subjected to an i-ray treatment using a negative photomask at 200mJ/cm²After the exposure, the resist was developed with a 0.3 mass% aqueous tetramethylammonium hydroxide solution at 23 ℃ to form a pattern of 20 μm × 200 μm in size, but a pattern of 15 μm × 150 μm in size could not be formed. Subsequently, heat treatment was carried out at 230 ℃ for 30 minutes to obtain a film having a thickness of 1.7 μm.

The obtained substrate with pixels was irradiated with 308nm excimer laser (shape: 21 mm. times.1.0 mm) from the glass substrate side, and subjected to a laser lift-off test, as a result of which the irradiation energy was 250mJ/cm²In this case, the polyimide film was confirmed to be lifted from the glass substrate.

Example 16

In a 100mL four-necked flask, 3.62g (18.4mmol) of 1,2,3, 4-cyclobutanetetracarboxylic dianhydride, 5.38g (18.4mmol) of 1, 3-bis (4-aminophenyl) benzene, and 50g of N-methyl-2-pyrrolidone were charged under a dry nitrogen gas flow, and the mixture was heated and stirred at 60 ℃. After 8 hours, cool to make a varnish.

Subsequently, the varnish thus obtained was spin-coated on a glass substrate, and subjected to a pre-baking treatment at 140 ℃ C.. times.4 minutes to form a film having a thickness of 10 μm. Then, the pre-baked film was heated to 300 ℃ at 3.5 ℃/min under a nitrogen gas flow (oxygen concentration: 20ppm or less) using an inert gas oven (INH-21 CD manufactured by Toyobo サーモシステム Co., Ltd.), was held for 30 minutes, and was cooled to 50 ℃ at 5 ℃/min to form a polyimide film.

Subsequently, the coloring composition obtained in example 3 was applied, and then, heat drying was performed at 90 ℃ for 10 minutes. The resultant colored composition coating film was subjected to an i-ray treatment using a negative photomask at 200mJ/cm²After the exposure, development was carried out with a 0.3 mass% aqueous tetramethylammonium hydroxide solution at 23 ℃ to form a pattern of 20 μm × 200 μm size and a pattern of 15 μm × 150 μm size. Subsequently, heat treatment was carried out at 230 ℃ for 30 minutes to obtain a film having a thickness of 1.7 μm.

The obtained substrate with pixels was irradiated with 308nm excimer laser (shape: 21 mm. times.1.0 mm) from the glass substrate side, and subjected to a laser lift-off test, as a result of which the irradiation energy was 400mJ/cm²In this case, the polyimide film was confirmed to be lifted from the glass substrate.

Industrial applicability

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

Claims (15)

1. A coloring composition comprising:

a green colorant having a metal phthalocyanine skeleton, and

a yellow colorant comprising c.i. pigment yellow 185, or comprising c.i. pigment yellow 138 and c.i. pigment yellow 185;

the total content of the green colorant having a metal phthalocyanine skeleton, the c.i. pigment yellow 138 and the c.i. pigment yellow 185 is 2 mass% or more and 16 mass% or less in the solid content,

the content of c.i. pigment yellow 185 in the colorant is 50 mass% or more and 90 mass% or less.

2. The coloring composition according to claim 1, wherein a total content of the green colorant having a metal phthalocyanine skeleton and the yellow colorant comprising c.i. pigment yellow 138 and c.i. pigment yellow 185 is 60% by mass or more in the colorant.

3. The coloring composition according to claim 2, wherein the green colorant having a metal phthalocyanine skeleton contains c.i. pigment green 58 and/or c.i. pigment green 59, and the total content of c.i. pigment green 58 and c.i. pigment green 59, c.i. pigment yellow 138, and c.i. pigment yellow 185 in the colorant is 80% by mass or more.

4. The coloring composition according to claim 3, wherein the total content of the colorants comprising C.I. pigment Green 58, C.I. pigment Green 59, C.I. pigment yellow 138 and C.I. pigment yellow 185 is 2 to 16 mass% in solid content.

5. The coloring composition according to claim 3 or 4, wherein the content of C.I. pigment green 58 in the green colorant is 80% by mass or more.

6. The coloring composition according to claim 1 or 2, wherein the content of c.i. pigment yellow 185 in the yellow colorant is 60% by mass or more.

7. The coloring composition according to claim 1 or 2, further comprising a radical polymerizable compound, wherein a content of the radical polymerizable compound in the solid content is 40% by mass or more and 90% by mass or less.

8. The coloring composition according to claim 7, wherein the radical polymerizable compound contains a radical polymerizable compound having a carboxyl group and 3 or more (meth) acryloyloxy groups, and the content of the radical polymerizable compound having a carboxyl group and 3 or more (meth) acryloyloxy groups is 50% by mass or more and 100% by mass or less in the radical polymerizable compound.

9. The colored composition according to claim 1 or 2, which is used for a reflective display device.

10. A color filter substrate comprising at least a substrate and pixels, wherein the pixels are formed from a photo-cured product or a thermally cured product of the coloring composition according to any one of claims 1 to 9.

11. A color filter substrate comprising at least a substrate and a red pixel, a green pixel, a blue pixel and a color pixel of the 4 th color, wherein the color pixel of the 4 th color is formed from a photo-cured product or a thermosetting product of the coloring composition according to any one of claims 1 to 9.

12. The color filter substrate according to claim 11, wherein the color pixel of the 4 th color has a light absorptance at 480nm of 50% or more, and a light absorptance at 650nm of 10% or more and 90% or less.

13. The color filter substrate according to claim 10 or 11, which is formed of polyimide.

14. A display device having at least the color filter substrate according to any one of claims 10 to 13 and a display element.

15. The display device of claim 14, further having a reflective layer.