JP2019082497A - Coloring composition for color filter - Google Patents

Abstract

To provide a coloring composition for a color filter which can achieve high coloring power and high contrast ratio.SOLUTION: The coloring composition for a color filter contains isoindoline pigment and a by-product. The by-product is a chemical compound represented by a general formula (1), which is contained 5 mass% or less with respect to the sum of the isoindoline pigment and the chemical compound represented by the general formula (1).SELECTED DRAWING: None

Description

  The present invention relates to a coloring composition for color filters used in the manufacture of color filters used in color liquid crystal display devices, solid-state imaging devices and the like, and a color filter formed using the same.

  In the liquid crystal display device, a liquid crystal layer sandwiched between two polarizing plates controls the degree of polarization of light passing through the first polarizing plate to control the amount of light passing through the second polarizing plate. Is a display device that performs display, and the type using a twisted nematic (TN) liquid crystal is mainstream. As another typical liquid crystal display system, an in-plane switching (IPS) system in which a pair of electrodes are provided on a substrate on one side and an electric field is applied in a direction parallel to the substrate, negative dielectric anisotropy Vertical alignment (VA) system for vertically aligning nematic liquid crystal with a liquid crystal, and Optically Convensend bend (OCB) system for optically compensating by making optical axes of uniaxial retardation films orthogonal to each other Etc., and each is put to practical use.

  The liquid crystal display device enables color display by providing a color filter between two polarizing plates, and in recent years it has been used in televisions and personal computer monitors, etc., so that a high contrast ratio to the color filter is realized. It is rising.

  A color filter is a transparent substrate such as glass on which two or more fine band (stripe) filter segments of different hues are arranged in parallel or crossing, or a fine filter segment arrayed in a fixed length and width direction It consists of what was arranged in. The filter segments are as fine as several microns to several hundred microns, and are arranged regularly in a predetermined arrangement for each hue.

  The quality items required for the color filter include the contrast ratio. When a color filter with a low contrast ratio is used, the degree of polarization controlled by the liquid crystal is disturbed, and when light must be blocked (OFF state) when light leaks or light must be transmitted (ON) In the state, the transmitted light is attenuated, resulting in a blurred screen. Therefore, in order to realize a high quality liquid crystal display device, it is essential to increase the contrast ratio.

In the production of such a color filter, the dispersibility of the pigment in the coloring composition is important, and when a color filter is produced using a coloring composition having a low dispersibility, the cause of the poor hue, the decrease in contrast ratio, etc. Become. In addition, even when a coloring composition having fluorescence emission characteristics is used, it causes similarly a hue failure, a decrease in contrast ratio, and the like. With regard to the dispersibility, it is described in Patent Document 1 that the higher the amount of by-products contained in the pigment, the better the dispersibility, but on the other hand, it is confirmed that the coloring power is adversely affected. There is.
Therefore, it has been an issue to improve the dispersibility and suppress the fluorescence characteristics while the content of the by-product is small.

JP-A-63-161061

As described above, demands for physical properties of a coloring composition used for producing a color filter, such as dispersion stability, storage stability, coloring power, coating uniformity when forming a filter segment, are increasing. With pigments conventionally used, it has become difficult to meet the requirements due to the low tinting strength due to by-products and the low contrast ratio due to fluorescence. In particular, in recent years, a liquid crystal display device is applied to a television monitor application, and a high density color filter containing a large amount of pigment is required to make a panel.
Therefore, the present invention is a coloring composition for color filters which is excellent in dispersion stability and can provide high coloring strength and high contrast ratio even when containing high concentration of pigment, and using the same to form filter segments. , The purpose is to provide a color filter with a high contrast ratio.

（式中、Ｘは、Ｏ、またはＮＨを表す。Ｒ₁〜Ｒ₄はそれぞれ独立に、水素原子、置換基を有してもよいアルキル基、置換基を有してもよいアリール基、置換基を有してもよい脂環基、置換基を有してもよいアラルキル基、置換基を有してもよい複素環基、置換基を有してもよいアルコキシ基、置換基を有してもよいアリールオキシ基、置換基を有してもよいアルキルチオ基、置換基を有してもよいアリールチオ基、置換基を有してもよいアルキルアミノ基、置換基を有してもよいジアルキルアミノ基、置換基を有してもよいアリールアミノ基、置換基を有してもよいジアリールアミノ基、ハロゲン原子、ニトロ基、スルホ基、カルボキシル基、ホルミル基、置換基を有してもよいフタルイミドメチル基、または置換基を有してもよいスルホンアミド基を表す。） An isoindoline-based pigment composition (A) containing an isoindoline pigment and a by-product, a metal complex compound (B), a dye derivative, and a coloring composition for a color filter containing a binder resin, wherein the by-product is The coloring composition for a color filter, which is a compound represented by the following general formula (1) and is contained in an amount of 5% by mass or less based on the total of the isoindoline pigment and the compound represented by the general formula (1) .
General formula (1)

(Wherein, X represents O or NH. R _{1 to} R ₄ each independently represent a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent) An alicyclic group which may have a group, an aralkyl group which may have a substituent, a heterocyclic group which may have a substituent, an alkoxy group which may have a substituent, and a substituent Aryloxy group, alkylthio group which may have a substituent, arylthio group which may have a substituent, alkylamino group which may have a substituent, dialkyl which may have a substituent Amino group, arylamino group which may have a substituent, diarylamino group which may have a substituent, halogen atom, nitro group, sulfo group, carboxyl group, formyl group, which may have a substituent A phthalimidomethyl group or sulfo optionally having a substituent An amide group.)

  The present invention relates to the coloring composition for color filter as described above, wherein the mass ratio of the compound represented by the general formula (1) to the dye derivative is in the range of 0.05 to 0.6.

  From the group consisting of vanadium (V), chromium (Cr), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), and molybdenum (Mo) as the central metal of the metal complex compound (B) The present invention relates to the above-mentioned coloring composition for color filters, which is at least one selected.

  The mass ratio (organic color material / metal complex compound (B)) of the organic color material comprising the isoindoline based pigment composition (A) and the dye derivative to the metal complex compound (B) is 0.005 to 1.0 The present invention relates to the above-mentioned coloring composition for color filter characterized in that

  The present invention relates to the colored composition for color filter as described above, wherein the isoindoline based pigment composition (A) is a CI Pigment Yellow 185 pigment.

  The present invention also relates to the coloring composition for color filters, which further comprises a photopolymerizable monomer and / or a photopolymerization initiator.

  The present invention relates to a color filter comprising a filter segment formed of the above-mentioned coloring composition for color filter on a substrate.

The coloring composition for color filters of the present invention is a paint formed by using the coloring composition by controlling the content of the compound represented by the above general formula (1) which is a by-product at the time of pigment synthesis. The film has high coloring power and high contrast ratio by the addition of the metal complex compound (B).
And, by using the coloring composition for color filter of the present invention, it is possible to manufacture a color filter having a high coloring power filter segment.

First, the coloring composition for color filters of this invention is demonstrated.
The coloring composition for color filters of the present invention is an isoindoline-based pigment composition containing at least a binder resin, a metal complex compound (B), a dye derivative, an isoindoline pigment and a compound represented by the above general formula (1). And (A).
Among the compounds represented by the above general formula (1), compounds wherein X in the formula is NH are cyanoacetic acid amidomethyl and 1,3-diiminoisoindoline compounds at a pH of 8 to 11 and a temperature of 10 to 100 ° C. It can synthesize | combine by making it react below.
Further, among the compounds represented by the general formula (1), a compound in which X is O in the formula can be obtained by heating a compound in which X is NH, for example, in an aqueous solution of acetic acid.

Here, when R _{1 to} R ₄ in the general formula (1) is exemplified, examples of the halogen atom in R _{1 to} R ₄ in the general formula (1) include fluorine, chlorine, bromine, iodine and the like.
As the alkyl group which may have a substituent, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, neopentyl group, n-hexyl group, n-octyl group, stearyl Group, 2-ethylhexyl group, trichloromethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, 2,2-dibromoethyl group, 2,2,3,3-tetrafluoropropyl group, 2- There are ethoxyethyl group, 2-butoxyethyl group, 2-nitropropyl group and the like.
Examples of the aryl group which may have a substituent include phenyl group, naphthyl group, anthranyl group, p-methylphenyl group, p-nitrophenyl group, p-methoxyphenyl group, 2,4-dichlorophenyl group, pentafluorophenyl Group, 2-aminophenyl group, 2-methyl-4-chlorophenyl group, 4-hydroxy-1-naphthyl group, 6-methyl-2-naphthyl group, 4,5,8-trichloro-2-naphthyl group, anthraquinonyl group And 2-amino anthraquinolyl group.

The alicyclic group which may have a substituent includes cyclopentyl group, 2,5-dimethylcyclopentyl group, cyclohexyl group, 4-tert-butylcyclohexyl group, adamantyl group and the like.
As the aralkyl group which may have a substituent, benzyl group, 4-methylbenzyl group, 4-tert-butylbenzyl group, 4-methoxybenzyl group, 4-nitrobenzyl group, 2,4-dichlorobenzyl group, etc. There is.
As a heterocyclic group which may have a substituent, pyridinyl group, 3-methyl pyridinyl group, pyrazinyl group, pipedinyl group, N-methyl pipedinyl group, pyranyl group, morpholinyl group, n-methyl pyrrolinyl group, acridinyl group etc. is there.
The alkoxy group which may have a substituent is, for example, methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, isobutyloxy group, tert-butyloxy group, neopentyloxy group, n-hexyloxy group , N-octyloxy group, stearyloxy group, 2-ethylhexyloxy group, trichloromethoxy group, trifluoromethoxy group, 2,2,2-trifluoroethoxy group, 2,2,3,3-tetrafluoropropyloxy group And 2-ethoxyethoxy, 2-butoxyethoxy, 2-nitropropoxy and the like.

The aryloxy group which may have a substituent includes phenoxy group, naphthoxy group, anthranyloxy group, p-methyl phenoxy group, p-nitro phenoxy group, p-methoxy phenoxy group, 2,4-dichloro phenoxy group, There are pentafluorophenoxy group, 2-methyl-4-chlorophenoxy group and the like.
As the alkylthio group which may have a substituent, methylthio group, ethylthio group, propylthio group, isopropylthio group, n-butylthio group, isobutylo group, tert-butylthio group, neopentylthio group, n-hexylthio group, n- There is an octylthio group.
Examples of the arylthio group which may have a substituent include phenylthio group, naphthylthio group, p-methylphenylthio group, p-nitrophenylthio group, p-methoxyphenylthio group and the like.

The alkylamino group which may have a substituent includes a methylamino group, an ethylamino group and the like.
Examples of the dialkylamino group which may have a substituent include dimethylamino group, dimethylamino group, diisopropyl group, cyclohexylamino group and the like.
The arylamino group which may have a substituent includes phenylamino, p-nitrophenylamino and 4-methylphenylamino.
Examples of the diarylamino group which may have a substituent include diphenylamino group and di (4-methoxyphenyl) amino group.
Examples of the phthalimidomethyl group which may have a substituent include 4-nitrophthalimidomethyl group and tetrachlorophthalimidomethyl group.
R _{1 to} R ₄ are not limited to these.

In the following, ¹ H-NMR and LC / MS measurements were performed on the pigment composition to determine by-product concentrations, as defined in the present invention, to identify pigments and by-products. In addition, DMF was added to the pigment composition, applied to an ultrasonic bath, and passed through a filter having a pore size of 1 μm or less. Thereafter, the pigment and by-products were quantified by LC / MS measurement. The by-product concentration in the pigment composition was defined by the by-product concentration in the pigment composition = (mass of by-product) / (mass of pigment composition). Here, (mass of pigment composition) = (mass of pigment) + (mass of by-product).

<Isoindoline-based pigment composition (A)>
The isoindoline pigment composition (A) contains an isoindoline pigment and a compound represented by the above general formula (1) which is a by-product at the time of pigment synthesis. The by-products in the present specification include unreacted pigment intermediates in addition to the by-products at the time of pigment synthesis.
The isoindoline pigment is a pigment having a structure as a structure in which two hydrogens combined with carbon constituting the five-membered ring of isoindoline are substituted by carbon.
In the isoindoline-based pigment composition (A) of the present invention, the method for lowering the concentration of by-products in the pigment composition is not particularly limited. I. It is preferable to prepare Pigment Yellow 185 by washing with a solvent in order to obtain a pigment having a lower impurity concentration. The solvent for washing used in the present invention can be freely selected as long as the solvent does not dissolve the pigment composition itself but dissolves the by-product.

Specific examples of the washing solvent include alcohols, ether alcohols, ethers, ketones, carboxylic acid amides, carboxylic acid esters, and mixtures thereof. The individual examples are:
Aliphatic and araliphatic monohydric or polyhydric alcohols having up to 10 carbon atoms, such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butanol, amyl alcohol, isoamyl alcohol, Hexanol, isohexanol, heptanol, octanol, 2-ethylhexanol, ethylene glycol, 1,2-propylene glycol, and 1,3-propylene glycol, cyclohexanol, methylcyclohexanol, benzyl alcohol, and 2-phenylethanol;
Mono-C 2 -C 3 -alkylene glycol mono-C 1 -C 4 -alkyl ethers, and di-C 2 -C 3 -alkylene glycol mono-C 1 -C 4 -alkyl ethers, such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol Monobutyl ether, and diethylene glycol monomethyl ether, and diethylene glycol monoethyl ether;
Acyclic and cyclic aliphatic ethers having up to 10 carbon atoms, such as dipropyl ether, diisopropyl ether, dibutyl ether, dibutyl ether, diisobutyl ether, tetrahydrofuran, dioxane, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether;
Acyclic and cyclic aliphatic and araliphatic ketones having up to 10 carbon atoms, such as acetone, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, diethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone Ketones, cyclopentanone, cyclohexanone, methylcyclohexanone, acetophenone and propiophenone;
Amides, and C1 -C4 alkyl amides of aliphatic carboxylic acids having up to 4 carbon atoms, such as formamide, N, N-dimethylformamide, and N, N-diethylformamide, N, N-dimethylacetamide, and N , N-diethylacetamide, N, N-dimethylpropionic acid amide, and N, N-diethylpropionic acid amide, and N-methylpyrrolidone;
Esters of aromatic carboxylic acids having a maximum of 12 carbon atoms in total, such as dimethyl phthalate and diethyl phthalate.

  In this case, preferably, after pigment washing, a solvent which can be easily removed during post-treatment is used.

Particularly preferred solvents are methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butanol, amyl alcohol, isoamyl alcohol, hexanol, isohexanol, heptanol, octanol, 2-ethylhexanol, ethylene glycol, 1,2-propylene Glycols and alcohols such as 1,3-propylene glycol, cyclohexanol, methylcyclohexanol, benzyl alcohol and 2-phenylethanol, dipropyl ether, diisopropyl ether, dibutyl ether, diisobutyl ether, tetrahydrofuran, dioxane, diethylene glycol dimethyl ether, and Acyclic and cyclic such as diethylene glycol diethyl ether Aliphatic ethers, acetone, methyl ethyl ketone, methyl propyl ketone, ketones such as methyl butyl ketone, diethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone, acetophenone, and propiophenone.
These solvents are preferable because they have high solubility of impurities other than pigments and can be easily removed by post-treatment.

  The above washing may be performed once or twice or more as needed.

  The isoindoline-based pigment composition in the present invention is added to the washing with the above-mentioned solvent in order to lower the concentration of by-products in the pigment composition, and further water, dilute acetic acid solution, dilute sulfuric acid solution, dilute phosphoric acid solution, dilute hydrochloric acid The solution may be washed. This can further reduce the concentration of by-products in the pigment composition.

  The coloring composition for color filters of the present invention may further contain a coloring agent other than the isoindoline-based pigment composition (A).

<Colorant>
As a coloring agent which can be used for the coloring composition for color filters of this invention, it can select arbitrarily from conventionally well-known various pigments and dyes. The following are representative pigments and dyes that can be used in the present invention.

  Examples of red pigments that can be used in the present invention include C.I. I. Pigment red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 57: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 221, 224, 242, 246, 254, 264, 270, 272, 273, 274, 276, 277, 278, 279, 280, 281, 2 2,283,284,285,286,287 or diketopyrrolopyrrole pigment described in JP-T 2011-523433 discloses the like, but not particularly limited thereto. Further, red dyes such as xanthene dyes, azo dyes, disazo dyes, anthraquinone dyes, and dipyrromethene dyes can also be used. Specifically, C.I. I. Salt-forming compounds of xanthene acid dyes such as Acid Red 52, 87, 92, 289, 338 and the like can be mentioned.

  Orange pigments that can be used in the present invention are, for example, C.I. I. Pigment orange 38, 43, 71, or 73, but not limited thereto.

  Examples of yellow pigments that can be used in the present invention include C.I. I. Pigment yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, 220, 221, or the quinophthalone-based pigments described in Japanese Patent No. 4993026, etc. There may be mentioned, but not particularly limited thereto. In addition, yellow dyes such as quinoline type, azo type, methine type, coumarin type and isoindoline type can also be used.

  Green pigments that can be used in the present invention are, for example, C.I. I. Pigment greens 7, 10, 36, 37, 58, JP 2008-19383 A, JP 2007-320986 A, JP 2004 70342 A, WO 2015/118720 pamphlet, etc. Examples thereof include, but are not particularly limited to, pigments, and the like. Further, blue-green dyes such as triarylmethanes, phthalocyanines and squaryliums can also be used.

  Blue pigments that can be used in the present invention are, for example, C.I. I. Pigment blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, JP-A-2004-333817, Although the aluminum phthalocyanine pigment etc. which are described in the patent 4893859 grade | etc., Are mentioned, it is not limited in particular in these.

  Purple pigments which can be used in the present invention are, for example, C.I. I. Pigment violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 25, 29, 31, 32, Examples thereof include 37, 39, 42, 44, 47, 49, 50 and the like, but not limited thereto.

The coloring composition for a color filter of the present invention includes metal oxides such as titanium dioxide, iron oxide, antimony pentoxide, zinc oxide and silica, cadmium sulfide, calcium carbonate, barium carbonate, barium sulfate, clay, talc, yellow lead And inorganic pigments such as carbon black can also be used. The inorganic pigment is used in combination with an organic pigment in order to ensure good coatability, sensitivity, developability, etc. while maintaining a balance between chroma and lightness.
The coloring agent used in the present invention contains the above-mentioned pigment, but in addition to that, it can also contain a dye within the range not to reduce the heat resistance due to the toning.

  The preferable content of the colorant in the total non-volatile components of the coloring composition according to the present invention is 10 to 90% by mass, more preferably 15 to 85% by mass from the viewpoint of sufficient color reproducibility and stability. And most preferably 20 to 80% by mass.

  In the coloring composition for color filters of the present invention, the compound represented by the general formula (1) is 5% by mass or less based on 100% by mass in total of the isoindoline pigment and the compound represented by the general formula (1) The content is preferably 0.1 to 5% by mass, more preferably 3% by mass or less, and further 100% in total of the isoindoline pigment and the compound represented by the general formula (1) from the viewpoint of coloring power. It is more preferable to contain in the ratio of 0.5-1.5 mass% with respect to%. When the content of the compound represented by the general formula (1) is less than the above range, the dispersion stabilization effect of the pigment is not sufficiently exhibited, and conversely, if it is more than the above range, the hue of the filter segment is unfavorably undesirable. There is a possibility of change, and also a problem in terms of manufacturing cost.

<Metal Complex Compound (B)>
The metal complex compound used in the present invention has fluorescence quenching ability, and the effect of increasing the contrast ratio of the coloring composition is obtained by using it together with the isoindoline-based pigment composition (A) having fluorescence emission ability. is there.

  The metal complex compound used in the present invention is preferably a complex compound with a transition metal atom. As a transition metal which comprises a transition metal ion, scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni) , Copper (Cu), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag) , Lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy) , Holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), hafnium (Hf), tantalum (Ta), tungsten (W), rhenium (Re), osmium (Os) , I Examples include lithium (Ir), platinum (Pt), gold (Au), and the like.

  Preferred examples of the transition metal include those in which the transition metal belongs to the first series (that is, the fourth period), that is, scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), iron (Fe), Cobalt (Co), nickel (Ni), copper (Cu), and molybdenum (Mo) in which the transition metal belongs to the second series (that is, the fifth period). Among these, more preferable examples are vanadium (V), chromium (Cr), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), molybdenum (Mo), and particularly preferable Are chromium (Cr) and cobalt (Co).

  The molecular weight of one ligand in the metal complex compound is preferably 20 or more and less than 300. When the molecular weight is 300 or more, the molecular weight increases, and the effect of improving the contrast ratio is reduced.

  As a ligand in a metal complex compound, all general ligands can be used and both a monodentate ligand and a polydentate ligand can be used suitably. Specific examples of the above-mentioned ligand include fluoro, chloro, bromo, iodo, hydroxo, aqua, tetrahydrofuran, ethylene glycol dimethyl ether, acetonitrile, benzonitrile, oxo, peroxo, carbonyl, carbonato, oxalato, acetato, ethanolato, 1-butanethiolato , Thiophenolato, 2,2'-thiobis (4-t-octyl) phenolate, acetylacetonato, 2,2,6,6-tetramethyl-3,5-heptanedionato, trifluoroacetylacetonato, hexafluoroacetylacetoate Nato, ethylacetoacetonato, thiocyanato, isothiocyanato, diethyl dithiocarbamate, di-n-butyl dithiocarbamate, cyano, amine, dimethylamine, diethylamine, tetraethyl ammonium , Piperidine, N-methylaniline, pyridine, 2-phenylpyridine, ethylenediamine, N, N, N ', N'-tetramethylethylenediamine, 1,2-diaminocyclohexane, 2,2'-bipyridine, 1,10-phenanthroline Ethylenediaminetetraacetate, 1,4,8,11-tetraazacyclotetradecane, tris (2-aminoethyl) amine, sulfato, nitro, nitrite, phosphato, diisopropyl dithiophosphate, diethyl dithiophosphate, triethyl phosphine, tributyl phosphine, Tricyclohexyl phosphine, dimethyl phenyl phosphine, triphenyl phosphine, diphenyl phosphine, tricyclohexyl phosphine, cyclopentadiene, pentamethyl cyclopentadiene, Kurookuten, 1,5-cyclooctadiene, bicyclo [2.2.1] hepta-2,5-diene, benzene, naphthalene, allyl and the like.

  Preferred examples of the above-mentioned ligand include fluoro, chloro, bromo, iodo, hydroxo, aqua, tetrahydrofuran, ethylene glycol dimethyl ether, acetonitrile, oxo, peroxo, carbonyl, carbonato, oxalato, acetato, ethanolato, 1-butanethiolato, acetylaceto Nato, 2,2,6,6-tetramethyl-3,5-heptanedionato, trifluoroacetylacetonato, hexafluoroacetylacetonato, ethylacetoacetonato, thiocyanato, isothiocyanato, diethyldithiocarbamate, di-n-butyldithiote Carbamate, cyano, amine, dimethylamine, diethylamine, tetraethylammonium, ethylenediamine, N, N, N ', N'-tetramethylethylenediamine, 1,2 -Diaminocyclohexane, ethylenediaminetetraacetate, 1,4,8,11-tetraazacyclotetradecane, tris (2-aminoethyl) amine, sulfato, nitro, nitrite, phosphato, diisopropyl dithiophosphate, diethyl dithiophosphate, triethyl phosphine, Tributyl phosphine, tricyclohexyl phosphine, cyclooctene, 1,5-cyclooctadiene, bicyclo [2.2.1] hepta-2,5-diene, allyl and the like can be mentioned.

  Further preferable examples of the above-mentioned ligand include acetate, acetylacetonate, hexafluoroacetylacetonate, thiocyanate, diethyl dithiocarbamate and di-n-butyl dithiocarbamate.

Moreover, as a metal complex compound other than the above, the metal complex compound which had the following cation site | parts can be used. The counter anion species is not particularly limited, but is preferably any one selected from Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ ⁻ , PF ₆ ⁻ , BF ₄ ⁻ , SO ₄ ^2- and CF ₂ SO ₃ ⁻ .

As the addition amount of the metal complex compound of the present invention, the mass ratio of the organic color material to the metal complex compound (B) is preferably in the range of 0.005 to 1.0, and more preferably 0.01 to 0. Most preferably, it is in the range of .2. Below 0.005, the fluorescence quenching effect is scarce and the contrast ratio improving effect is scarce. If it is 1.0 or more, the coloring strength may be reduced.
The organic coloring material is defined as containing an isoindoline based pigment composition (A) and a dye derivative.

<Dye derivative>
Moreover, the coloring composition for color filters of this invention contains a pigment derivative.
The dye derivative is a compound represented by the following general formula (2), and includes those having a basic substituent and those having an acidic substituent.
General formula (2)
A-B
A: Organic pigment residue B: Basic substituent or acidic substituent

  In the general formula (2), as the organic pigment constituting the organic pigment residue of A, diketopyrrolopyrrole based pigments, azo based pigments such as azo, disazo and polyazo, copper phthalocyanine, halogenated copper phthalocyanine, metal free phthalocyanine Phthalocyanine based pigments such as aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavanthrone, anthantrone, indanthrone, indanthrone, pyranthrone, anthraquinone based pigments such as biolanthrone, quinacridone based pigments, dioxazine based pigments, perinone based pigments, perylene based pigments, Thioindigo based pigments, isoindoline based pigments, isoindolinone based pigments, quinophthalone based pigments, slen based pigments, metal complex based pigments and the like.

式（４）

式（５）

式（６）

In the general formula (2), examples of the basic substituent of B include the substituents represented by the following formulas (3), (4), (5), and (6), and as the acidic substituent And the substituents shown by Formula (7), Formula (8), and Formula (9) are mentioned.
Formula (3)

Formula (4)

Formula (5)

Formula (6)

式（８）

式（９）

Formula (7)

Formula (8)

Formula (9)

_{X 1, X 2, X 3} : -SO 2 -, - CO -, - represents a or a direct bond - CH _2.
n represents an integer of 1 to 10.
_{R 5, R 6, R7,} R 8: each independently, an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms, optionally substituted A good phenyl group or an optionally substituted heterocyclic ring containing an additional nitrogen, oxygen or sulfur atom, as R ₅ , R 6, R 7, R ₈ together.
R ₉ represents an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms, or an optionally substituted phenyl group.
Each of R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ independently represents a hydrogen atom, an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms or substitution Represents a phenyl group which may be substituted.

_{Y: -NR 14 -Z-NR 15} - or a direct bond.
R ₁₆ , R ₁₇ , R ₁₈ and R ₁₉ each independently represent a hydrogen atom, an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms, or Represents an optionally substituted phenyl group.
Z represents a C1-C36 optionally substituted alkylene group, a C2-36 optionally substituted alkenylene group, or an optionally substituted phenylene group.
R: represents a substituent represented by the formula (10) or a substituent represented by the formula (11).
Q: represents a hydroxyl group, an alkoxyl group, a substituent represented by the formula (10) or a substituent represented by the formula (11).

式（１１）

Formula (10)

Formula (11)

R ₂₀ and R ₂₁ are the same as R ₅ , R 6, R 7 and R ₈ .
R ₂₂ : Same as R ₉
R ₂₃ , R ₂₄ , R ₂₅ and R ₂₆ are the same as R ₁₆ , R ₁₇ , R ₁₈ and R ₁₉ .

M ₁ and M _{2 each represent a} hydrogen atom, a calcium atom, a barium atom, a strontium atom, a manganese atom or an aluminum atom.
i represents the valence of M ₁ and M ₂ .

  Examples of the amine component used to form a substituent represented by Formula (3) to Formula (6) and Formula (10) or Formula (11) include, for example, dimethylamine, diethylamine, N, N-ethylisopropyl Amine, N, N-ethylpropylamine, N, N-methylbutylamine, N, N-methylisobutylamine, N, N-butylethylamine, N, N-tert-butylethylamine, diisopropylamine, dipropylamine, N, N N-sec-butylpropylamine, dibutylamine, di-sec-butylamine, diisobutylamine, N, N-isobutyl-sec-butylamine, diamylamine, diisoamylamine, dihexylamine, di (2-ethylhexyl) amine, dioctylamine , N, N-methyloctadecylamine, didecyl Min, diallylamine, N, N-ethyl-1,2-dimethylpropylamine, N, N-methylhexylamine, dioleylamine, distearylamine, N, N-dimethylaminomethylamine, N, N-dimethylaminoethylamine, N, N-dimethylaminoamylamine, N, N-dimethylaminobutylamine, N, N-diethylaminoethylamine, N, N-diethylaminopropylamine, N, N-diethylaminohexylamine, N, N-diethylaminobutylamine, N, N -Diethylaminopentylamine, N, N-dipropylaminobutylamine, N, N-dibutylaminopropylamine, N, N-dibutylaminoethylamine, N, N-dibutylaminobutylamine, N, N-diisobutylaminopentylamine, N, N Methyl-laurylaminopropylamine, N, N-ethyl-hexylaminoethylamine, N, N-distearylaminoethylamine, N, N-dioleylaminoethylamine, N, N-distearylaminobutylamine, piperidine, 2-pipecoline, 3-pipecoline, 4-pipecoline, 2,4-lupetidine, 2,6-lupetidine, 3,5-lupetidine, 3-piperidinemethanol, pipecolic acid, isonipecotic acid, methyl isonicotinate, ethyl isonicotinate, 2-piperidine ethanol, Pyrrolidine, 3-hydroxypyrrolidine, N-aminoethylpiperidine, N-aminoethyl-4-pipecoline, N-aminoethylmorpholine, N-aminopropylpiperidine, N-aminopropyl-2-pipecoline, N-aminopropyl- 4-pipecoline, N-aminopropyl morpholine, N-methyl piperazine, N-butyl piperazine, N-methyl homopiperazine, 1-cyclopentyl piperazine, 1-amino-4-methyl piperazine, 1-cyclopentyl piperazine and the like.

  The amine component used to form the sulfonic acid amine salt of the formula (9) may be any of primary, secondary, tertiary and quaternary amines. For example, as a primary amine, it has a side chain. Hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, nonadecylamine, An amine such as eicosylamine or an unsaturated amine corresponding to each carbon number can be mentioned.

As secondary, tertiary and quaternary amines, dioleylamine, distearylamine, dimethyloctylamine, dimethyldecylamine, dimethyllaurylamine, dimethylstearylamine, dilaurylmonomethylamine, trioctylamine, dimethyldidodecylammonium chloride, Dimethyl dioleyl ammonium chloride, dimethyl didecyl ammonium chloride, dimethyl dioctyl ammonium chloride, trimethyl stearyl ammonium chloride, dimethyl distearyl ammonium chloride, trimethyl decyl ammonium chloride, trimethyl hexadecyl ammonium chloride, trimethyl octadecyl ammonium chloride, dimethyl dodecyl tetradecyl ammonium chloride , Dimethyl hexadecyl octadesi Ammonium chloride, and the like.
When any one of R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ in the formula (9) represents a polyoxyalkylene group, examples thereof include a polyoxyethylene group, a polyoxypropylene group and the like.

The mass ratio of the compound represented by the general formula (1) in the present invention to the dye derivative is preferably in the range of 0.05 to 0.6, and if it exceeds 0.6, a decrease in coloring strength may be caused. is there. If it is less than 0.05, the improvement in contrast ratio is poor.
In the present invention, a mixture of a colorant containing an isoindoline pigment, a compound represented by the general formula (1), and a dye derivative is used as an organic colorant.

<Binder resin>
The colorant carrier for dispersing the colorant and the compound represented by the general formula (1) is constituted of a binder resin, a precursor thereof or a mixture thereof. The binder resin is a resin having a transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength range of 400 to 700 nm in the visible light range. The binder resin includes a resin type dispersant, a thermoplastic resin, a thermosetting resin, and a photosensitive resin, and the precursor includes a monomer or an oligomer which is cured by irradiation with radiation to generate a binder resin. These can be used alone or in combination of two or more.

  The resin type dispersant used in the present invention has a colorant affinity site having a property of adsorbing to a colorant, and a site compatible with the colorant carrier, and is adsorbed to the colorant and is adsorbed to the colorant carrier. Works to stabilize the dispersion of Specific examples of the resin type dispersant include polyurethane, polycarboxylic acid ester such as polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid (partial) amine salt, polycarboxylic acid ammonium salt, polycarboxylic acid alkylamine salt , Polysiloxane, long chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, modified products thereof, amide formed by reaction of poly (lower alkyleneimine) with polyester having free carboxyl group, and salts thereof Etc., (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinyl pyrrolidone, etc. Resin, water soluble polymer, polyester, modified poly Acrylate-based, ethylene oxide / propylene oxide addition compound, phosphate ester-based and the like are used, they can be used alone or in admixture of two or more, not necessarily limited thereto.

  As a site | part with high affinity to the dispersion medium of the resin type dispersing agent used for this invention, the at least 1 sort (s) of polymer unit chosen from polyester, a polyether, and a poly (meth) acrylate is preferable.

  For example, as polyesters, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol 1,4-bis (hydroxymethyl) cyclohexan, bisphenol A, hydrogenated bisphenol A, hydroxypivalylhydroxypivalate, trimethylolethane, trimethylolpropane, 2,2,4-trimethyl-1,3-pentanediol, Glycerin or one or more alcohols such as hexanetriol and succinic acid, adipic acid, sebacic acid, azelaic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid ,Guru Conic acid, 1,2,5-hexanetricarboxylic acid, 1,4-cyclohexanehicarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-cyclohexahexaenoic acid A polyester polyol etc. which are obtained by co-condensation with 1 or more types of carboxylic acids, such as a tricarboxylic acid or 2,5,7- naphthalene tricarboxylic acid, etc. are mentioned.

  For example, as polyethers, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexane Diol, 1,4-bis (hydroxymethyl) cyclohexan, bisphenol A, hydrogenated bisphenol A, hydroxypivalylhydroxypivalate, trimethylolethane, trimethylolpropane, 2,2,4-trimethyl-1,3-pentanediol , Glycerin or alcohols such as hexanetriol, ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether Others include modified polyether polyols and the like obtained by ring-opening polymerization of various (cyclic) ether bond-containing compounds such as allyl glycidyl ether.

  For example, as poly (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-Butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, phenyl (Meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, oxetane (meth) acrylate, etc. Alkoxypolyalkylene glycol (meth) acrylates such as xylopolypropylene glycol (meth) acrylate and ethoxy polyethylene glycol (meth) acrylate, (meth) acrylamide, and N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylate ) N-substituted (meth) acrylamides such as acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, acryloyl morpholine, etc., N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl ( Examples thereof include homopolymers and copolymers such as amino group-containing (meth) acrylates such as meta) acrylate and nitriles such as (meth) acrylonitrile. These may be used alone or in combination, or may be in the form of a block polymer, a graft polymer or a random polymer.

  Commercially available resin type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 154, 161, 162, 163, 164, 165, 166, 170 manufactured by Big Chemie Japan. 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2070, 2095, 2150, 2155, or Anti-Terra-U, 203, 204, or BYK. -P104, P104S, 220S, 6919, or Lactimon, Lactimon-WS or Bykumen et al., SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 160, manufactured by Japan Lubrizol Corporation. 0, 17000, 18000, 20000, 21000, 21000, 24000, 26000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500 etc., BASF Japan made EFKA-46, 47, 48, 452, 4008, 4010, 4015, 4020, 4047, 4050, 4050, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4010 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 554,1101,120,150,1501,1502,1503, etc., Ajinomoto Fine-Techno Co., Ltd. of AJISPER PA111, PB711, PB821, PB822, PB824, and the like.

  The resin type dispersant has a colorant affinity site having a property of adsorbing to the colorant, and a site compatible with the colorant carrier, and is adsorbed to the colorant to disperse the colorant in the colorant carrier Work to stabilize the Specific examples of the resin type dispersant include polyurethane, polycarboxylic acid ester such as polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid (partial) amine salt, polycarboxylic acid ammonium salt, polycarboxylic acid alkylamine salt , Polysiloxane, long chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, modified products thereof, amide formed by reaction of poly (lower alkyleneimine) with polyester having free carboxyl group, and salts thereof Etc., (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinyl pyrrolidone, etc. Resin, water soluble polymer, polyester, modified poly Acrylate-based, ethylene oxide / propylene oxide addition compound, phosphate ester-based and the like are used, they can be used alone or in admixture of two or more, not necessarily limited thereto.

  As the resin-type dispersant, an acidic resin-type dispersant having an aromatic carboxyl group is particularly preferable, and a polymer having a hydroxyl group at one end, an aromatic tricarboxylic acid anhydride and / or an aromatic tetracarboxylic acid dianhydride Most preferably, it is a dispersant obtained by reacting As such a resin type dispersant, for example, Japanese Patent No. 4020150, Japanese Patent Laid-Open No. 2007-140487, International Publication 2008/007776 Pamphlet, Japanese Patent Laid-Open No. 2010-163500, and Japanese Patent Laid-Open No. 2010-223988. Etc., and exerts excellent effects such as coexistence of fluidity and dispersibility.

  Among these, as a preferable resin type dispersant, an ethylenic unsaturated monomer is radically polymerized in the presence of a compound having two hydroxyl groups and one thiol group in the molecule described in WO 2008/007776 and the like. A polyester dispersant formed by reacting a hydroxyl group in a vinyl copolymer having two hydroxyl groups in one end region and an acid anhydride group in tetracarboxylic acid dianhydride is preferable. More preferably, it is a polyester dispersant characterized in that the tetracarboxylic acid dianhydride contains an aromatic tetracarboxylic acid dianhydride. The coloring composition for color filters using these polyester dispersants is preferable because it is excellent in dispersion stability of the pigment, and as a synthesis method, it is synthesized using the method described in WO 2008/007776 pamphlet etc. be able to.

Moreover, as a preferable resin type dispersing agent, the resin type dispersing agent shown by the following formula as described in Unexamined-Japanese-Patent No. 2007-140487 etc. is mentioned.
_{(HOOC-) m -R 27 - (} - COO - [- R 29 -COO-] q -R 28) t
[Wherein, R ₂₇ is a tetravalent tetracarboxylic acid compound residue, R ₂₈ is a monoalcohol residue, R ₂₉ is a lactone residue, m is 2 or 3, q is an integer of 1 to 50, t is 4 Represents -m). ]

  The coloring composition for color filters using the acidic resin type dispersing agent which has these aromatic carboxyl groups is very excellent in the dispersion stability of a pigment.

As a thermoplastic resin, for example, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, polyester resin Acrylic resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polybutadiene, polyethylene, polypropylene, polyimide resins and the like can be mentioned.
Moreover, as a thermosetting resin, an epoxy resin, benzoguanamine resin, rosin modified maleic resin, rosin modified fumaric resin, melamine resin, urea resin, a phenol resin etc. are mentioned, for example.

As the photosensitive resin, (meth) acrylic compounds having reactive substituents such as isocyanate group, aldehyde group and epoxy group on linear polymers having reactive substituents such as hydroxyl group, carboxyl group and amino group A resin is used in which a photocrosslinkable group such as a (meth) acryloyl group or a styryl group is introduced into the linear polymer by reacting an acid. In addition, a linear polymer containing an acid anhydride such as styrene-maleic anhydride copolymer or α-olefin-maleic anhydride copolymer is treated with a hydroxyl group-containing (meth) acrylic compound such as hydroxyalkyl (meth) acrylate. A half esterified one is also used.
It is preferable that it is 30-700 mass parts with respect to 100 mass parts of coloring agents, and, as for content of binder resin, it is more preferable that it is 60-450 mass parts. When the content of the binder resin is less than 30 parts by mass, the developing performance is lowered, and when it exceeds 700 parts by mass, it is not preferable from the viewpoint of curability of the coloring composition and poor hue.

As monomers and oligomers which are precursors of binder resins, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, polyethylene glycol di (meth) acrylate, pentaerythritol tri (meth ) Various acrylates such as acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tricyclodecanyl (meth) acrylate, melamine (meth) acrylate, epoxy (meth) acrylate and methacrylic acid Ester, (meth) acrylic acid, styrene, vinyl acetate, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, acrylonitrile and the like can be mentioned.
In addition, the content of the monomer and the oligomer is preferably 10 to 300 parts by mass with respect to 100 parts by mass of the colorant, and more preferably 10 to 200 parts by mass from the viewpoint of photocurability and developability. Particularly preferably, it is 15 to 150 parts by mass. When the content of the monomer and the oligomer is more than 300 parts by mass, it is not preferable because the shape defect of the filter segment occurs, and when the content is less than 10 parts by mass, the photocurability is insufficient.

  The coloring composition for color filters of the present invention may further contain a photopolymerizable monomer and / or a photopolymerization initiator. What contains these becomes a photosensitive coloring composition.

<Photopolymerizable monomer>
The photopolymerizable monomer which may be added to the coloring composition of the present invention includes a monomer or an oligomer which is cured by ultraviolet light, heat or the like to form a transparent resin.

Examples of monomers and oligomers that cure by ultraviolet light and heat to form a transparent resin include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate , Cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di ( Meta) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglyci Ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodeca Various acrylic and methacrylic esters such as (meth) acrylate, ester acrylate, methylolated melamine (meth) acrylate, epoxy (meth) acrylate, urethane acrylate, (meth) acrylic acid, styrene, vinyl acetate, Hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxy ester Examples include, but not limited to, chill (meth) acrylamide, N-vinylformamide, acrylonitrile and the like.
These photopolymerizable compounds can be used alone or in combination of two or more at an arbitrary ratio as needed.

  The content of the photopolymerizable monomer is preferably 5 to 400 parts by mass with respect to 100 parts by mass of the colorant, and more preferably 10 to 300 parts by mass from the viewpoint of photocurability and developability. .

<Photoinitiator>
A photopolymerization initiator is added to the coloring composition of the present invention to cure the composition by ultraviolet irradiation and to form a filter segment by photolithography, and a solvent development type or alkali development type photosensitive coloring composition It can be prepared in the form of

As the photopolymerization initiator, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1 Acetophenone compounds such as-[4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; benzoin, benzoin Methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or Benzoin compounds such as dil dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyl diphenyl sulfide, or 3,3 ', 4 Benzophenone compounds such as 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methyl thioxanthone, isopropyl thioxanthone, 2,4-diisopropyl thioxanthone, or 2,4-diethyl thioxanthone Thioxanthone compounds of the formula: 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphen) Nyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloro) Methyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2 -(4-Methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4-trichloromethyl- Triazine compounds such as (4'-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] Or oxime ester compounds such as O- (acetyl) -N- (1-phenyl-2-oxo-2- (4'-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6-trimethylbenzoyl) Phosphine compounds such as phenyl phosphine oxide or 2,4,6-trimethyl benzoyl diphenyl phosphine oxide; quinone compounds such as 9,10-phenanthrene quinone, camphor quinone, ethyl anthraquinone; borate compounds; carbazole compounds; An imidazole compound; or a titanocene compound etc. are used.
These photopolymerization initiators can be used alone or in combination of two or more at an arbitrary ratio as needed.

  The content of the photopolymerization initiator is preferably 2 to 200 parts by mass with respect to 100 parts by mass of the colorant, and more preferably 3 to 150 parts by mass from the viewpoint of photocurability and developability.

<Sensitizer>
Furthermore, the coloring composition of the present invention can contain a sensitizer.
As sensitizers, unsaturated ketones represented by chalcone derivatives, dibenzalacetone etc., 1,2-diketone derivatives represented by benzyl and camphorquinone etc., benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, polymethine dyes such as oxonol derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, Azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, Trapyrazino porphyrazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxalylo porphyrazine derivative, naphthalocyanine derivative, subphthalocyanine derivative, pyrylium derivative, thiopyrilium derivative, tetraphyrin derivative, anurene derivative, spiropyran derivative, spirooxazine Derivative, thiospiropyran derivative, metal arene complex, organic ruthenium complex, or Michler's ketone derivative, α-acyloxy ester, acyl phosphine oxide, methylphenyl glyoxylate, benzyl, 9, 10-phenanthrenequinone, camphorquinone, ethyl Anthraquinone, 4,4′-diethylisophthalophenone, 3,3 ′, or 4,4′-tetra (t-butylperoxycarbonyl) benzopheno And 4,4'-diethylaminobenzophenone and the like.
These sensitizers can be used alone or in combination of two or more at an arbitrary ratio as required.

  More specifically, edited by Ogawara Shin et al., "Dye Handbook" (1986, Kodansha), edited by Ogawara Shin et al., "Chemicals of functional dyes" (1981, CMC), edited by Ikemori Tadajiro et al. Specific examples thereof include, but are not limited to, the sensitizers described in “Specially functional materials” (1986, CMC). In addition, a sensitizer that absorbs light in the ultraviolet to near-infrared region can also be contained.

  The content of the sensitizer is preferably 3 to 60 parts by mass with respect to 100 parts by mass of the photopolymerization initiator contained in the coloring composition, and 5 to 50 parts by mass from the viewpoint of photocurability and developability. It is more preferable that

<Antioxidant>
The coloring composition for color filters of the present invention can contain an antioxidant. In order to prevent the photopolymerization initiator and the thermosetting compound contained in the coloring composition for color filter from being oxidized and yellowed due to a heat process at the time of heat curing or ITO annealing, the antioxidant is the transmittance of the coating film. Can be raised. Therefore, by including an antioxidant, it is possible to prevent yellowing due to oxidation in the heating step and to obtain a high transmittance of the coating film.

  The "antioxidant" in the present invention may be a compound having an ultraviolet light absorbing function, a radical trapping function, or a peroxide decomposing function, and specifically, a hindered phenol type or hindered amine type as an antioxidant. Examples thereof include phosphorus, sulfur, benzotriazole, benzophenone, hydroxylamine, salicylate and triazine compounds, and known ultraviolet light absorbers, antioxidants and the like can be used.

  Among these antioxidants, preferred are hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants or sulfur-based antioxidants from the viewpoint of achieving both the transmittance and sensitivity of the coating film. Agents. Also, more preferably, hindered phenol antioxidants, hindered amine antioxidants, or phosphorus antioxidants are used.

  Examples of hindered phenolic antioxidants include 2,4-bis [(laurylthio) methyl] -o-cresol, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl), 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di) -Tert-Butylanilino) -1,3,5-triazine, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,6-di-tert-butyl-4-4 Nonylphenol, 2,2'-Isobutylidene-bis- (4,6-dimethyl-phenol), 4,4'-Butylidene-bis- (2-t-butyl-5-methylphenol), 2,2'-thio- S- (6-t-Butyl-4-methylphenol), 2,5-di-t-amyl-hydroquinone, 2,2'-thiodiethyl bis- (3,5-di-t-butyl-4-hydroxyphenyl) ) -Propionate, 1,1,3-Tris- (2′-methyl-4′-hydroxy-5′-t-butylphenyl) -butane, 2,2′-methylene-bis- (6- (1-methyl) -Cyclohexyl) -p-cresol), 2,4-dimethyl-6- (1-methyl-cyclohexyl) -phenol, N, N-hexamethylene bis (3,5-di-tert-butyl-4-hydroxy-hydro) And the like. In addition, oligomer type and polymer type compounds having a hindered phenol structure can also be used.

  As the hindered amine antioxidant, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N-methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexamethylenediamine, 2-methyl-2- (2,2,6,6-tetramethyl-4) -Piperidyl) amino-N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) (1,2,3, 4-butane tetracarboxylate, poly [{6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl} {(2,2,6,6 -Tetramethyl-4-piperidi Imino} hexamethyl {(2,2,6,6-tetramethyl-4-piperidyl) imino}], poly [(6-morpholino-1,3,5-triazine-2,4-diyl) {(2, 2,6,6-Tetramethyl-4-piperidyl) imino} hexamethine {(2,2,6,6-tetramethyl-4-piperidyl) imino}], dimethyl succinate and 1- (2-hydroxyethyl)- Polycondensate with 4-hydroxy-2,2,6,6-tetramethylpiperidine, N, N'-4,7-tetrakis [4,6-bis {N-butyl-N- (1,2,2 , 6,6-Pentamethyl-4-piperidyl) amino} -1,3,5-triazin-2-yl] -4,7-diazadecane-1,10-diamine, etc. Other oligomeric types having a hindered amine structure as well as Rimmer type of compounds and the like can also be used.

  As a phosphorus antioxidant, tris (isodecyl) phosphite, tris (tridecyl) phosphite, phenyl isooctyl phosphite, phenyl isodecyl phosphite, phenyl di (tridecyl) phosphite, diphenyl isooctyl phosphite, diphenyl isodecyl Phosphite, diphenyl tridecyl phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, 4,4 'isopropylidene diphenol alkyl phosphite, tris nonyl phenyl phosphite, tris dinonyl phenyl phosphite, tris (2 , 4-di-t-butylphenyl) phosphite, tris (biphenyl) phosphite, distearyl pentaerythritol diphosphite, di (2 , 4-Di-t-butylphenyl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, phenyl bisphenol A pentaerythritol diphosphite, tetratridecyl 4,4'-butylidene bis (3-methyl-) 6-t-Butylphenol) diphosphite, hexatridecyl 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane triphosphite, 3,5-di-t-butyl -4-hydroxybenzyl phosphite diethyl ester, sodium bis (4-t-butylphenyl) phosphite, sodium-2,2-methylene-bis (4,6-di-t-butylphenyl) -phosphite, 1,3 -Bis (diphenoxy phosphonyloxy)-Ben Zen, ethyl phosphite bis (2,4-di-tert-butyl-6-methylphenyl) and the like. In addition, oligomer type and polymer type compounds having a phosphite structure can also be used.

  As a sulfur-based antioxidant, 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis [(octylthio) methyl]- o-cresol, 2,4-bis [(laurylthio) methyl] -o-cresol, etc. may be mentioned. In addition, oligomer type and polymer type compounds having a thioether structure can also be used.

  As the benzotriazole-based antioxidant, compounds of oligomer type and polymer type having a benzotriazole structure can be used.

  Specific examples of benzophenone-based antioxidants include 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2 -Hydroxy-4-octadecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2 And -hydroxy-4-methoxy-5sulfobenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2-hydroxy-4-chlorobenzophenone and the like. In addition, oligomer type and polymer type compounds having a benzophenone structure can also be used.

  As a triazine type antioxidant, a 2, 4- bis (allyl) 6- (2-hydroxyphenyl) 1, 3, 5- triazine etc. are mentioned. In addition, oligomer type and polymer type compounds having a triazine structure can also be used.

  Examples of the salicylate-based antioxidant include phenyl salicylate, p-octylphenyl salicylate, p-tertbutylphenyl salicylate and the like. In addition, oligomer type and polymer type compounds having a salicylate structure can also be used.

  These antioxidants can be used alone or in combination of two or more at an arbitrary ratio as required.

  The content of the antioxidant is more preferably 0.5 to 5.0% by mass based on the mass of the solid content of the photosensitive coloring composition for a color filter, because the lightness and sensitivity are good.

<Amine compounds>
In addition, the coloring composition of the present invention can contain an amine compound having a function of reducing dissolved oxygen.

  As such an amine compound, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoate Ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, and N, N-dimethyl paratoluidine etc. are mentioned.

<Leveling agent>
It is preferable to add a leveling agent to the colored composition of the present invention in order to improve the leveling properties of the composition on a transparent substrate. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in its main chain is preferred. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning, BYK-333 manufactured by BYK Chemie, and the like. As a specific example of dimethylsiloxane which has a polyester structure in a principal chain, BYK-310 by BYK-Chemie company, BYK-370, etc. are mentioned. The dimethylsiloxane having a polyether structure in the main chain and the dimethylsiloxane having a polyester structure in the main chain can also be used in combination. In general, the content of the leveling agent is preferably 0.003 to 0.5% by mass based on the total mass of the coloring composition (100% by mass).

  Particularly preferred as a leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, which has a low solubility in water while having a hydrophilic group, and when it is added to a coloring composition, It is characterized by low surface tension reduction ability, and in addition to low surface tension reduction ability, it is useful that the wettability to the glass plate is good, and the addition amount at which defects of the coating film due to foaming do not appear. Those which can sufficiently suppress the chargeability can be preferably used. As a leveling agent which has such a preferable characteristic, dimethylpolysiloxane which has a polyalkylene oxide unit can use it preferably. The polyalkylene oxide unit may be a polyethylene oxide unit or a polypropylene oxide unit, and the dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

  In addition, the bonding form of the polyalkylene oxide unit to dimethylpolysiloxane is a pendent type in which the polyalkylene oxide unit is bonded to a repeating unit of dimethylpolysiloxane, a terminal-modified type bonded to the terminal of dimethylpolysiloxane, and dimethylpolysiloxane It may be any of linear block copolymer types alternately and repeatedly bonded. Dimethylpolysiloxanes having polyalkylene oxide units are commercially available from Toray Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ-2203. -2-207, but not limited thereto.

The leveling agent may be supplemented with an anionic, cationic, nonionic or amphoteric surfactant. The surfactant may be used as a mixture of two or more.
Examples of anionic surfactants to be added to leveling agents include polyoxyethylene alkyl ether sulfate, sodium dodecyl benzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, alkyl diphenyl ether disulfonic acid Sodium lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearic acid, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphoric acid Ester etc. are mentioned.

  Examples of the cationic surfactant added to the leveling agent include alkyl quaternary ammonium salts and ethylene oxide adducts thereof. As a nonionic surfactant which is added to the leveling agent as auxiliaries, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate And alkylbetaines such as alkyldimethylaminoacetic acid betaines; amphoteric surfactants such as alkylimidazolines; and fluorine-based and silicone-based surfactants.

<Hardening agent, hardening accelerator>
Moreover, in order to assist hardening of a thermosetting resin, the coloring composition of this invention may contain the hardening agent, the hardening accelerator, etc. as needed. As a curing agent, a phenolic resin, an amine compound, an acid anhydride, an active ester, a carboxylic acid compound, a sulfonic acid compound and the like are effective, but not particularly limited thereto, a thermosetting resin Any curing agent may be used as long as it can react with it. Among these, a compound having two or more phenolic hydroxyl groups in one molecule, and an amine curing agent are preferably mentioned. Examples of the curing accelerator include amine compounds (for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl -N, N-dimethylbenzylamine etc.), quaternary ammonium salt compounds (eg, triethylbenzylammonium chloride etc.), blocked isocyanate compounds (eg, dimethylamine etc.), imidazole derivative bicyclic amidine compounds and salts thereof (eg, Imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2- Tyl-4-methylimidazole etc.), phosphorus compounds (eg triphenylphosphine etc.), guanamine compounds (eg melamine, guanamine, acetoguanamine, benzoguanamine etc.), S-triazine derivatives (eg 2,4-diamino-6) -Methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6- Methacryloyloxyethyl-S-triazine / isocyanuric acid adduct etc. can be used. These may be used alone or in combination of two or more. As content of the said hardening accelerator, 0.01-15 mass parts is preferable with respect to 100 mass parts of thermosetting resins.

<Other additive components>
The coloring composition of the present invention can contain a storage stabilizer in order to stabilize the viscosity over time. Further, in order to enhance the adhesion to the transparent substrate, an adhesion improver such as a silane coupling agent may be contained.

  Examples of storage stabilizers include quaternary ammonium chlorides such as benzyl trimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and methyl ethers thereof, t-butyl pyrocatechol, tetraethyl phosphine, tetraphenyl phosphine, etc. Organic phosphine, phosphite and the like can be mentioned. The storage stabilizer can be used in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of the colorant.

  Adhesion improvers include vinyltris (β-methoxyethoxy) silane, vinylethoxysilane, vinylsilanes such as vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β- (3,3, 4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (amino Ethyl) γ-aminopropyl trie Xysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl Silane coupling agents such as aminosilanes such as -γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, with respect to 100 parts by mass of the colorant in the coloring composition.

  The coloring composition for color filters of the present invention is a method of dispersing a coloring agent in a coloring agent carrier solution, or dispersing a coloring agent in water or an organic solvent to prepare a pigment dispersion and then mixing it with the coloring agent carrier solution Manufactured by the method of Although there is no restriction | limiting in particular in the dispersion method of a pigment, The method of using a bead mill, a sand mill, a ball mill, 3-roll mill, 2-roll mill etc. is preferable. The colorant and the compound represented by the general formula (1) can be separately dispersed in the colorant carrier solution and then mixed, but in order to improve the dispersibility of the colorant, the colorant is dispersed. At that time, it is preferable to add the compound represented by the general formula (1).

When the coloring composition for color filter contains two or more kinds of pigments etc., after mixing two or more kinds of pigments etc., the obtained pigment mixture is mixed in the colorant carrier by a known method. It can be finely dispersed and manufactured. In addition, the coloring composition for color filter can also be produced by mixing each pigment and the like finely dispersed in the colorant carrier.
When the colorant is dispersed in the colorant carrier, dispersion aids such as surfactants and dye derivatives can be used as appropriate. The dispersion aid can be used in an amount of 0.1 to 40 parts by mass with respect to 100 parts by mass of the colorant.

  As surfactant, polyoxyethylene alkyl ether sulfate, sodium dodecyl benzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate, lauryl sulfate monoethanolamine, lauryl Anionic surfactants such as triethanolamine sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate ester; Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene ethylene glycol Nonyl surfactants such as alkyl ether phosphate, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate; cationic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyl dimethylamino Alkyl betaines such as betaine acetate, and amphoteric surfactants such as alkyl imidazolines. These can be used alone or in combination of two or more.

  Furthermore, in the coloring composition for color filters of the present invention, the colorant is sufficiently dispersed in the colorant carrier so that the dry film thickness is 0.5 to 3.0 μm on a transparent substrate such as a glass substrate. A solvent can be included to facilitate application to form the filter segment. As the solvent, for example, cyclohexanone, ethyl cellosolve acetate, butyl cellosolve acetate, 1-methoxy-2-propyl acetate, diethylene glycol dimethyl ether, ethyl benzene, ethylene glycol diethyl ether, xylene, ethyl cellosolve, methyl-n-amyl ketone, propylene glycol monomethyl ether toluene Examples thereof include methyl ethyl ketone, ethyl acetate, methanol, ethanol, isopropyl alcohol, butanol, isobutyl ketone, petroleum solvents and the like, and these are used alone or in combination. The solvent can be used in an amount of 800 to 4000 parts by mass with respect to 100 parts by mass of the colorant.

  The coloring composition for color filters of the present invention can be prepared in the form of a printing ink for gravure offset, a printing ink for waterless offset, an ink for silk screen printing, a solvent development type or an alkali development type coloring resist material. The colored resist material may be a colorant carrier, a thermosetting resin, a thermoplastic resin or a photosensitive resin and a monomer, and, if necessary, a composition containing a photopolymerization initiator, a colorant, and a compound represented by the general formula (1) And a pigment derivative and a metal complex compound dispersed therein.

The colorant is preferably contained in a proportion of 1 to 7% by mass in the coloring composition containing a solvent when the filter segment is formed by photolithography, and when the filter segment is formed by the printing method And 1 to 50% by mass in a coloring composition containing a solvent. In any case, the colorant is contained in the final filter segment (solid content of the coloring composition) in a proportion of preferably 10 to 55% by mass, more preferably 20 to 50% by mass, with the remainder being the colorant carrier And the resinous binder provided by
The coloring composition for a color filter of the present invention may be coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more, by means of centrifugation, sintered filter, membrane filter, etc. It is preferable to carry out the removal of the mixed dust.

Next, the color filter of the present invention will be described.
The color filter of the present invention comprises one or more color filter segments formed using the coloring composition for color filters of the present invention on a transparent or reflective substrate. There are those having filter segments of three colors G) (green) and B (blue), and those having filter segments of three colors Y (yellow), M (magenta) and C (cyan). . The filter segments of each color can be formed by printing or photolithography.

As the transparent substrate, a glass plate such as quartz glass, borosilicate glass, alumina silicate glass, soda lime glass coated with silica on the surface, or a resin plate such as polycarbonate, polymethyl methacrylate or polyethylene terephthalate is used.
As the reflective substrate, silicon, or one obtained by forming aluminum, silver, silver / copper / palladium alloy thin film or the like on the above-mentioned transparent substrate is used.

  The formation of each color filter segment by the printing method can be patterned simply by repeating printing and drying of the coloring composition prepared as the various printing inks described above. Therefore, as a method for producing a color filter, it is excellent in mass productivity at low cost. ing. Furthermore, with the development of printing technology, printing of fine patterns with high dimensional accuracy and smoothness can be performed. In order to print, it is preferable to set it as a composition which an ink does not dry and solidify on the printing plate or on a blanket. In addition, it is important to control the flowability of the ink on the printing press, and the viscosity of the ink can be adjusted by a dispersant or an extender pigment.

  When forming each color filter segment by photolithography, spray coating, spin coating, slit coating, roll coating, on a transparent or reflective substrate, of the coloring composition prepared as the above-mentioned solvent development type or alkali development type coloring resist material The coating is applied to a dry film thickness of 0.2 to 5 μm by a coating method such as, and optionally dried to form a pigment-dispersed coating film. Then, ultraviolet exposure is performed through a mask having a predetermined pattern in contact with or non-contact with the film. Thereafter, the developer is immersed in a solvent or an alkaline developer, or the developer is sprayed to remove an uncured portion to form a desired pattern, and then the same operation is repeated for other colors to produce a color filter. be able to. Furthermore, in order to accelerate | stimulate superposition | polymerization of a coloring resist material, heating can also be given as needed. According to the photolithography method, it is possible to manufacture a color filter with higher accuracy than the printing method.

In the development, an aqueous solution of sodium carbonate, sodium hydroxide or the like is used as an alkali developing solution, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution.
In order to increase the ultraviolet exposure sensitivity, after applying and drying the colored resist material, a water-soluble or alkali-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to form a film for preventing polymerization inhibition by oxygen. After that, ultraviolet exposure can also be performed.

The color filter of the present invention can be produced by the electrodeposition method, transfer method, etc. in addition to the above method, but the coloring composition for color filter of the present invention can be used in any method. In the electrodeposition method, a color filter is manufactured by electrodepositing each color filter segment on the transparent conductive film by electrophoresis of colloidal particles using a transparent conductive film formed on a transparent or reflective substrate. It is a method.
The transfer method is a method in which a layer of a coloring composition is formed in advance on the surface of a transferable transfer base sheet, and the layer of the coloring composition is transferred to a desired transparent or reflective substrate.

  If the black matrix is formed in advance before forming the filter segments on the transparent substrate or the reflective substrate, the contrast ratio of the liquid crystal display panel can be further enhanced. As the black matrix, although a multilayer film of chromium or chromium / chromium oxide, an inorganic film such as titanium nitride, or a resin film in which a light shielding agent is dispersed is used, it is not limited thereto. Alternatively, thin film transistors (TFTs) may be formed in advance on the transparent substrate or the reflective substrate, and then filter segments may be formed. By forming the filter segments on the TFT substrate, the aperture ratio of the liquid crystal display panel can be increased and the luminance can be improved.

An overcoat film, a columnar spacer, a transparent conductive film, a liquid crystal alignment film, etc. are formed on the color filter of the present invention as needed.
The color filter and the opposite substrate are pasted together using a sealing agent, the liquid crystal is injected from the injection port provided in the seal portion and then the injection port is sealed, and the polarizing film and the retardation film are sealed outside the substrate if necessary. The liquid crystal display panel is manufactured by bonding them together.
Such liquid crystal display panels include twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA) and optically compensated bend (OCB). Etc. can be used for liquid crystal display mode which performs coloring using a color filter.

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereby. In the examples, “parts” and “%” represent “parts by mass” and “mass%”, respectively. Also, "PGMAC" means propylene glycol monomethyl ether acetate.

<Method of producing pigment>
(Production of isoindoline pigment intermediate)
10 parts of 40% methylamine methanol solution was added to 14.7 parts of ethyl cyanoacetate, and heating stirring was performed for 2 hours at the boiling point. After cooling to 50 ° C., 300 parts of methanol and 19 parts of 1,3-diiminoisoindoline were added, and the mixture was further stirred at 50 ° C. for 2 hours, and then cooled to room temperature. Washing was carried out three times with 100 parts of methanol to obtain a compound (A) which is an isoindoline pigment intermediate.

(Production of isoindoline-based pigment compositions A and B)
To 30 parts of the compound (A) obtained by Preparation Example 1, 19 parts of barbituric acid dissolved in 1000 parts of 60% aqueous acetic acid was added, reacted at 70 to 90 ° C., and cooled to room temperature. Washing with water was carried out to obtain an isoindoline based pigment composition A containing a compound (B) and a compound (A) of the following structure. Next, the isoindoline pigment composition A was further washed with water once more to obtain an isoindoline pigment composition B. The isoindoline-based pigment composition B has a by-product content equivalent to that of the prior art.

The compound obtained by the above preparation is subjected to identification of the compound by ¹ H-NMR and LC / MS, and a compound (A) as a by-product and an isoindoline-based pigment composition A and B containing the compound (B) It was confirmed that was obtained.
In addition, 25 mL of DMF was added to 100 mg of each of the obtained isoindoline-based pigment compositions A and B, applied to an ultrasonic bath, and passed through a filter with a pore diameter of 0.2 μm. Thereafter, the pigment and by-products were quantified by LC / MS measurement, and the by-product concentration was measured.

(Production of isoindoline-based pigment compositions C to F)
After adding 2000 ml of methyl ethyl ketone to 100 g of the above-mentioned isoindoline pigment composition A, the mixture was stirred at 60 ° C. for 12 hours. After filtering out the pigment, the press cake is dried at 70 ° C. in an air forced circulation drying cabinet, crushed with an atomizer (mesh size 0.8 mm) to prevent aggregation, and isoindoline based pigment composition C described in Table 1 Obtained.
Furthermore, another washing with methyl ethyl ketone was performed to obtain an isoindoline-based pigment composition D described in Table 1.
Similarly, the isoindoline pigment composition A is washed twice with methanol instead of methyl ethyl ketone, and the isoindoline pigment composition E described in Table 1 is washed with methanol once to obtain the isoindoline pigment composition F. I got
The by-product concentrations of the isoindoline based pigment compositions C to F were measured in the same manner as the isoindoline based pigment compositions A and B.
The content of by-products in the isoindoline based pigment composition is: isoindoline based pigment composition A> isoindoline based pigment composition B> isoindoline based pigment composition F> isoindoline based pigment composition E> isoindoline based The order of the pigment composition C> isoindoline-based pigment composition D is as follows.
The isoindoline-based pigment compositions A to F are all CI Pigment Yellow 185 pigments.

(Adjustment of organic color materials)
The organic coloring material described in Table 1 was prepared by mixing a dye derivative with the produced isoindoline pigment composition. Also, the amount of by-products in the pigment composition was specified as% in the pigment. The major products in Table 1 are isoindoline pigments.

(Production of micronized green pigment (PG 58-1))
Phthalocyanine-based green pigment C.I. I. Pigment Green 58 ("FASTOGEN GREEN A110" manufactured by DIC Corporation), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged in a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 80 ° C for 6 hours. Next, this kneaded material is added to 8000 parts of hot water, stirred for 2 hours while heating to 80 ° C. to form a slurry, repeated filtration, washing with water to remove sodium chloride and diethylene glycol, and then dried overnight at 85 ° C. , To obtain a finely divided green pigment (PG 58-1).

(Method of producing resin type dispersant X1-1)
(Resin type dispersant X1-1 solution)
100 parts of methyl methacrylate, 100 parts of n-butyl acrylate, and 40 parts of propylene glycol monomethyl ether acetate were charged into a reaction vessel equipped with a gas introduction pipe, a condenser, a stirring blade, and a thermometer, and purged with nitrogen gas. The reaction vessel is heated to 80 ° C., 12 parts of 3-mercapto-1,2-propanediol are added, and 0.2 parts of 2,2′-azobisisobutyro nitrile is divided into 20 portions to 30 It was added every minute and reacted at 80 ° C. for 12 hours, and solid content measurement confirmed that 95% was reacted. Next, 30 parts of pyromellitic anhydride, 190 parts of propylene glycol monomethyl ether acetate, 0.40 parts of 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst are added, and 7 at 120 ° C. It was made to react for time. It was confirmed by titration that 98% or more of the acid anhydride was half-esterified, and the reaction was terminated. Thus, a resin-type dispersant X1-1 solution having an aromatic carboxyl group and a poly (meth) acrylate skeleton having an acid value of 63 mg KOH / g per solid content and a non-volatile content of 40% by mass was obtained.

(Preparation of acrylic resin solution)
800 parts of cyclohexanone is put in a reaction vessel, and heated to 100 ° C. while injecting nitrogen gas into the vessel, and 60.0 parts of methacrylic acid, 65.0 parts of methyl methacrylate, 65.0 parts of butyl methacrylate from the dropping tube at the same temperature. A mixture of 60.0 parts of 2-hydroxyethyl methacrylate and 10.0 parts of azobisisobutyronitrile was added dropwise over 1 hour to carry out a polymerization reaction. After dropping, the mixture is further reacted at 80 ° C. for 3 hours, then, a solution of 2.0 parts of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone is added, and the reaction is further continued at 80 ° C. for 1 hour to obtain weight average molecular weight A solution of about 40,000 acrylic resins was obtained.
After cooling to room temperature, approximately 2 g of the resin solution is sampled, dried by heating at 180 ° C. for 20 minutes, non-volatile content is measured, and cyclohexanone is added to the previously synthesized resin solution so that the non-volatile content is 20%. An acrylic resin solution was prepared.

Example 1
(Preparation of Colored Composition (MY-1))
After stirring and mixing the isoindoline pigment composition C and the dye derivative (the compound represented by the formula (13)) with various materials so as to be uniform, Eiger mill (Eiger Japan Co., Ltd.) using zirconia beads having a diameter of 0.5 mm. After dispersing for 5 hours with “Mini model M-250 MKII” manufactured by the manufacturer, the solution is filtered with a 5.0 μm filter, and after adding the metal complex compound, ultrasonication is performed for 1 hour to obtain a colored composition (MY-1). ) Was produced.
Hereinafter, solid content mass is shown.
Isoindoline based pigment composition C 9.60 parts Dye derivative (compound represented by formula (13)) 2.4 parts Metal complex compound-bis (hexafluoroacetylacetonato) Co (II) hydrate (Tokyo Chemical Industry Co., Ltd.) Made in Japan 0.6 parts Resin type dispersant (X1-1) 8.5 parts Acrylic resin solution 11.5 parts Propylene glycol monomethyl ether acetate 67.4 parts

Ｅｔはエチル基を示す。
Formula (13)

Et represents an ethyl group.

[Examples 2 to 34, Comparative Examples 1 to 7]
(Production of Colored Composition MY-2 to 41)
The same method as in the case of the colored composition (MY-1) except that the isoindoline-based pigment composition and the metal complex compound are changed to the materials described in Table 2 in the production of the colored composition (MY-1) , Colored composition MY-2 to 41 was obtained.
<Evaluation of coloring composition>
Evaluation of the contrast ratio (CR) of a coating film and coloring power was performed by the following method using the obtained coloring composition (MY-1-41). Table 2 shows the evaluation results.

(Evaluation of coloring ability)
Using a spin coater, the obtained colored composition (MY-1 to 41) was placed on a glass substrate of 100 mm × 100 mm and 1.1 mm thickness, and the chromaticity value of x (C) = 0.455 was around the center value. As a result, three levels of coated substrates were manufactured by changing the number of rotations. Drying conditions were 20 minutes at 70 ° C. and 30 minutes at 230 ° C. after application. Furthermore, the contrast ratio of the substrate and the chromaticity at the C light source were measured, and the film thickness at the chromaticity x (C) = 0.455 was determined from the data of three points by the first-order correlation method. The film thickness was evaluated in the following four stages.
◎: less than 0.75 μ (very good)
○: 0.75 μ or more, less than 1 μ (good)
Δ: 1 μ or more, less than 1.25 μ (slightly good)
X: 1.25 μ or more (defect)

(Evaluation of contrast ratio)
Contrast ratio measurements were performed using the substrate used for tinting measurements.
The evaluation of the contrast ratio was evaluated in the following four stages.
◎: 1500 or more (very good)
○: 1000 or more and less than 1500 (good)
:: 500 or more, less than 1000 (somewhat good)
X: less than 500 (defective)

S. O. 41: C.I. I. Solvent orange 41
S. O. 54: C.I. I. Solvent orange 54
S. O. 56: C.I. I. Solvent orange 56
S. O. 62: C.I. I. Solvent orange 62
S. O. 99: C.I. I. Solvent orange 99
S. R. 8: C.I. I. Solvent red 8
S. R. 91: C.I. I. Solvent red 91
S. R. 118: C.I. I. Solvent red 118
S. R. 122: C.I. I. Solvent red 122
S. R. 127: C.I. I. Solvent red 127
S. Y. 21: C.I. I. Solvent yellow 21
S. Y. 62: C.I. I. Solvent yellow 62
S. Y. 79: C.I. I. Solvent Yellow 79
S. Y. 81: C.I. I. Solvent yellow 81
S. Y. 82: C.I. I. Solvent yellow 82
S. Y. 83: C.I. I. Solvent yellow 83
S. Y. 83: 1: C.I. I. Solvent Yellow 83: 1

  As shown in Table 2, the colored compositions having a content of by-products of 5% by mass or less all did not have an X in the item of coloring power. Furthermore, by combining an isoindoline-based pigment composition (A) having a content of by-products of 5% by mass or less with a metal complex compound (B), it is possible to realize a high contrast ratio and high coloring power. There is.

[Examples 35 to 68, Comparative Examples 8 to 14]
(Green photosensitive coloring composition (YR-1 to 41))
The mixture of the composition and the amount (parts by mass) shown in Table 3 is stirred and mixed so as to be uniform, and then filtered with a filter with a pore diameter of 1.0 μm to obtain photosensitive coloring compositions (YR-1 to 41). The
In addition, corresponding to the yellow coloring compositions (MY-1 to 41), green photosensitive coloring compositions (YR-1 to 41) were formed.

表中の数値の単位は、質量部である。

The units of numerical values in the table are parts by mass.

・ Green colored composition (GP-1)
The following mixture is stirred and mixed so as to be uniform, and then dispersed for 3 hours with an Eiger mill ("Mini model M-250 MKII" manufactured by Eiger Japan) using zirconia beads of 0.5 mm in diameter, and then the pore diameter is 5. It filtered with a 0 micrometer filter, and the non-volatile component produced the 20 mass% green coloring composition (GP-1).
Refined green pigment (PG 58-1): 11.0 parts Acrylic resin solution: 22.5 parts Propylene glycol monomethyl ether acetate (PGMAC): 66.5 parts

<Evaluation of photosensitive coloring composition>
The coloring power of the obtained photosensitive coloring composition (YR-1-41) and evaluation of contrast ratio were performed with the following method. Table 4 shows the evaluation results.

(Evaluation of coloring ability)
Using photosensitive resin composition (YR-1 to 41) on a glass substrate of 100 mm x 100 mm and 1.1 mm thickness, using a spin coater, the center value will be around chromaticity x (C) = 0.455 As a result, three levels of coated substrates were manufactured by changing the number of rotations. Drying conditions were 20 minutes at 70 ° C. and 30 minutes at 230 ° C. after application. Furthermore, the contrast ratio of the substrate and the chromaticity at the C light source were measured, and the film thickness at the chromaticity x (C) = 0.455 was determined from the data of three points by the first-order correlation method. The film thickness was evaluated in the following four stages.
◎: less than 2.2 μm (very good)
○: Film thickness 2.2 μm or more, less than 2.5 μm (good)
Δ: Film thickness of 2.5 μm or more and less than 2.8 μm (slightly good)
X: film thickness of 2.8 μm or more (defect)

(Evaluation of contrast ratio)
Contrast ratio measurements were performed using the substrate used for tinting measurements. The evaluation of the contrast ratio was evaluated in the following four stages.
◎: 1500 or more (very good)
○: 1000 or more and less than 1500 (good)
:: 500 or more, less than 1000 (somewhat good)
X: less than 500 (defective)

  As shown in Table 4, in the systems using organic coloring materials (YP-1 to 5) having a content of by-products of 5% by mass or less, in any of the items of coloring strength, x is not given, Furthermore, the combination of the metal complex compound (B) achieves high contrast ratio and high coloring power.

Claims (7)

An isoindoline-based pigment composition (A) containing an isoindoline pigment and a by-product, a metal complex compound (B), a dye derivative, and a coloring composition for a color filter containing a binder resin, wherein the by-product is It is a compound shown by following General formula (1), and 5 mass% or less is contained with respect to the sum total of an iso indoline pigment and the compound shown by General formula (1), The coloring composition for color filters characterized by the above-mentioned.
General formula (1)

(Wherein, X represents O or NH. R _{1 to} R ₄ each independently represent a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent) An alicyclic group which may have a group, an aralkyl group which may have a substituent, a heterocyclic group which may have a substituent, an alkoxy group which may have a substituent, and a substituent Aryloxy group, alkylthio group which may have a substituent, arylthio group which may have a substituent, alkylamino group which may have a substituent, dialkyl which may have a substituent Amino group, arylamino group which may have a substituent, diarylamino group which may have a substituent, halogen atom, nitro group, sulfo group, carboxyl group, formyl group, which may have a substituent A phthalimidomethyl group or sulfo optionally having a substituent An amide group.)
The coloring composition for a color filter according to claim 1, wherein a mass ratio of the compound represented by the general formula (1) to the dye derivative is in the range of 0.05 to 0.6.
From the group consisting of vanadium (V), chromium (Cr), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), and molybdenum (Mo) as the central metal of the metal complex compound (B) The coloring composition for color filters according to claim 1 or 2, which is at least one selected.
The mass ratio (organic color material / metal complex compound (B)) of the organic color material comprising the isoindoline based pigment composition (A) and the dye derivative to the metal complex compound (B) is 0.005 to 1.0 The coloring composition for color filters according to any one of claims 1 to 3, characterized in that
The coloring composition for color filters according to any one of claims 1 to 4, wherein the isoindoline-based pigment composition is a CI Pigment Yellow 185 pigment.
Furthermore, the photopolymerizable monomer and / or the photoinitiator is contained, The coloring composition for color filters in any one of the Claims 1-5 characterized by the above-mentioned.
  A color filter comprising a filter segment formed of the coloring composition for color filter according to any one of claims 1 to 6 on a substrate.