JP2015135396A - Color filter coloring composition and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a color filter coloring composition excellent in the heat resistance, the lightness and the contrast ratio; and a color filter without foreign matter generated in a coating.SOLUTION: A color filter coloring composition comprises at least a coloring agent, a binder resin and an organic solvent. The coloring agent contains a salt-forming compound of a cationic cyanine-based dye and a methidic acid anion, which is represented by the specified general formula (1-1). Also provided is a color filter.

Description

  The present invention relates to a colored composition for a color filter used for manufacturing a color filter used for a color liquid crystal display device, a color image pickup tube element, and the like, and a color filter including a filter segment formed using the same. is there.

  In recent years, liquid crystal display devices have been evaluated for space saving, light weight, power saving, and the like due to their thinness, and recently they have been rapidly spread to television applications. For television applications, it is required to further improve the performance such as brightness and contrast, and further improvement of the transmittance and enhancement of the contrast are desired for the color filter which is a member of the color liquid crystal display device. ing.

  As a method for producing the color filter, after forming a pattern with a photoresist, a dyeing method for dyeing the pattern, or by forming a transparent electrode of a predetermined pattern in advance, and using a pigment-containing resin dissolved and dispersed in a solvent by voltage application Electrodeposition method for ionization and pattern formation, printing method such as offset printing using ink containing thermosetting resin or ultraviolet curable resin, and coloring composition for color filter in which colorant such as pigment is dispersed in photoresist material The pigment dispersion method is known, and recently, the pigment dispersion method has become mainstream. However, a color filter using a pigment as a colorant disturbs the degree of polarization controlled by the liquid crystal due to light scattering by the pigment particles, resulting in a decrease in brightness and contrast of the color liquid crystal display device. There is a problem that it is easy.

  In order to solve the above problems, a technique has been proposed in which a dye, not a pigment, is dissolved as a colorant in a resin or the like (see, for example, Patent Document 1). Dyes generally have poor solubility in organic solvents, and because they are fragile pigment skeletons, they are remarkably insufficient in heat resistance and weather resistance, so that there are many problems as coloring compositions for color filters, making it difficult to put them into practical use. Among them, cyanine dyes are not sufficiently resistant because the azo bond, which is the chromophore, is weak against heat and light, and because they have low solubility in organic solvents, there are many problems as coloring compositions for color filters. . In order to solve such problems, it has been proposed to use a salt containing a cation derived from a cyanine dye and an anion derived from a phthalocyanine dye as a colorant for the blue filter segment. However, such a colorant cannot be used for the red filter segment from the viewpoint of hue and lightness even if the durability is improved.

As a method of improving the heat resistance, the cation derived from cyanine dyes, various anionic low molecular weight (Cl-, Br-, I-, ClO 4 -, OH-, carboxylate anion, sulfonate anion, borate anion, It has also been proposed to use a salt containing a monovalent organometallic complex anion) as a color filter colorant (see, for example, Patent Documents 3 and 4). However, even if a color filter is prepared using these dyes, the heat resistance is insufficient, and the organic solvent solubility is low, so that precipitation of foreign matters is observed on the color filter substrate, causing a decrease in brightness. However, it has not been put into practical use. Moreover, precipitation of foreign matters over time is recognized and storage stability is insufficient.

  On the other hand, as a means for improving the durability of cationic dyes such as triarylmethane and rhodamine, color filter colorants using a methide acid anion as a counter anion have also been proposed (see, for example, Patent Documents 5 and 6). However, triarylmethane dyes are extremely inferior in light resistance and heat resistance and are not at a practical level. In addition, since rhodamine dyes have high fluorescence of the dyes, a sufficient contrast ratio as a color filter cannot be secured at present. Accordingly, there is a need for a high-quality color filter that has excellent brightness, excellent durability, and a higher contrast ratio.

JP-A-6-75375 JP 2012-162706 A JP 2008-242324 A JP 2009-235392 A WO2010 / 123071 JP 2013-067776 A

  The objective of this invention is providing the coloring composition for color filters excellent in the brightness, heat resistance, and contrast ratio, and a color filter.

  As a result of intensive research to solve the above problems, the present inventors have obtained a salt-forming compound (general formula 1-1) obtained by reacting a methide acid anion with a cationic cyanine dye. It has been found that the color filter coloring composition contained has a high brightness, high heat resistance and a high contrast ratio, and that no foreign matter is generated on the coating film, and the present invention has been made based on this finding.

  That is, this invention is the coloring composition for color filters which consists of a coloring agent, binder resin, and an organic solvent at least, Comprising: A coloring agent is represented by the following general formula (1-1), a methide acid anion and a cation The present invention relates to a coloring composition for a color filter, comprising a salt-forming compound with a functional cyanine dye.

［［一般式（１−１）において、Ｄ + は下記一般式（１−２）で表されるカチオン性シアニン系染料を表し、
Ｒ¹〜Ｒ³はそれぞれ独立に、置換基を有してもよい脂肪族炭化水素基、または置換基を有してもよい芳香族炭化水素基を表す。］

[In the general formula (1-1), D + represents a cationic cyanine dye represented by the following general formula (1-2);
R ^{1 to} R ³ each independently represents an aliphatic hydrocarbon group that may have a substituent, or an aromatic hydrocarbon group that may have a substituent. ]

［一般式（１−２）において、Ａは置換基もしくは水素原子を有する炭素原子、または硫黄原子を表す。Ｒ⁴〜Ｒ¹¹はそれぞれ独立に、水素原子、ハロゲン原子、ニトロ基、置換もしくは無置換の炭素数１〜４のアルキル基、置換もしくは無置換の炭素数１〜４のアルコキシ基、置換もしくは無置換のアリール基、または置換もしくは無置換のアシル基を表す。Ｒ¹²は、水素原子、置換もしくは無置換の炭素数１〜４のアルキル基、またはハロゲン原子を表す。Ｒ¹³およびＲ¹⁴はそれぞれ独立に、水素原子、ハロゲン原子、重合性官能基を有する有機基、または置換もしくは無置換の炭素数１〜６のアルキル基を示す。］］

[In General Formula (1-2), A represents a carbon atom which has a substituent or a hydrogen atom, or a sulfur atom. R ^{4 to} R ¹¹ are each independently a hydrogen atom, a halogen atom, a nitro group, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms, substituted or unsubstituted It represents a substituted aryl group or a substituted or unsubstituted acyl group. R ¹² represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a halogen atom. R ¹³ and R ¹⁴ each independently represent a hydrogen atom, a halogen atom, an organic group having a polymerizable functional group, or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. ]]

In the formula (1-1), the present invention is characterized in that R ^{1 to} R ³ are each independently a halogenated alkyl group having 1 to 4 carbon atoms or a halogenated aromatic hydrocarbon group. The present invention relates to a coloring composition for a color filter.

  Further, the present invention relates to the color composition for color filters, further comprising a photopolymerizable monomer and / or a photopolymerization initiator.

  Furthermore, the present invention relates to a color filter comprising a filter segment formed from the colored composition for a color filter on a substrate.

  The present invention is a color filter coloring composition comprising at least a colorant, a binder resin, and an organic solvent, wherein a salt-forming compound of a specific methide acid anion of the present application and a specific cationic cyanine dye of the present application is used as the colorant. By using it, the coloring composition for color filters excellent in brightness, heat resistance, and contrast ratio can be obtained.

  Hereinafter, the present invention will be described in detail. Further, “CI” in this specification means a color index (CI).

<Colorant>
The coloring composition for a color filter of the present invention includes a salt-forming compound obtained by reacting a methide acid anion described later with a cationic cyanine dye, thereby providing an effect excellent in lightness, heat resistance, and contrast ratio. It will have. It is also preferable to use a pigment or dye in combination.

[Salt-Forming Compound Represented by General Formula (1-1)]
The salt-forming compound represented by the general formula (1-1) of the present invention includes a methide acid anion represented by the general formula (1-3) and a cationic cyanine type represented by the general formula (1-2). It can be obtained by salt formation with a dye.

［［一般式（１−１）において、Ｄ + は下記一般式（１−２）で表されるカチオン性シアニン系染料を表し、
Ｒ¹〜Ｒ³はそれぞれ独立に、置換基を有してもよい脂肪族炭化水素基、または置換基を有してもよい芳香族炭化水素基を表す。］

[In the general formula (1-1), D + represents a cationic cyanine dye represented by the following general formula (1-2);
R ^{1 to} R ³ each independently represents an aliphatic hydrocarbon group that may have a substituent, or an aromatic hydrocarbon group that may have a substituent. ]

［一般式（１−２）において、Ａは置換基もしくは水素原子を有する炭素原子、または硫黄原子を表す。Ｒ⁴〜Ｒ¹¹はそれぞれ独立に、水素原子、ハロゲン原子、ニトロ基、置換もしくは無置換の炭素数１〜４のアルキル基、置換もしくは無置換の炭素数１〜４のアルコキシ基、置換もしくは無置換のアリール基、または置換もしくは無置換のアシル基を表す。Ｒ¹²は、水素原子、置換もしくは無置換の炭素数１〜４のアルキル基、またはハロゲン原子を表す。Ｒ¹³およびＲ¹⁴はそれぞれ独立に、水素原子、ハロゲン原子、重合性官能基を有する有機基、または置換もしくは無置換の炭素数１〜６のアルキル基を示す。］］ (Cationic cyanine dye represented by formula (1-2))

[In General Formula (1-2), A represents a carbon atom which has a substituent or a hydrogen atom, or a sulfur atom. R ^{4 to} R ¹¹ are each independently a hydrogen atom, a halogen atom, a nitro group, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms, substituted or unsubstituted It represents a substituted aryl group or a substituted or unsubstituted acyl group. R ¹² represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a halogen atom. R ¹³ and R ¹⁴ each independently represent a hydrogen atom, a halogen atom, an organic group having a polymerizable functional group, or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. ]]

［一般式（１−３）におけるＲ¹〜Ｒ³は、一般式（１−１）におけるＲ¹〜Ｒ³と同義である。］ (Methido acid anion represented by general formula (1-3))

[R ¹ in the general formula (1-3) to R ³ have the same meanings as R ¹ to R ³ in the general formula (1-1). ]

In the general formula (1-1), examples of the “aliphatic hydrocarbon group” include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, Linear alkyl groups such as dodecyl, tridecyl, pentadecyl, hexadecyl, octadecyl, nonadecyl, pentadecyl; branched such as isopropyl, isobutyl, sec-butyl, tert-butyl, isooctyl Alkyl group; cycloalkyl groups such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, and cyclodecyl group, and the like.
In the general formula (1-1), examples of the “aromatic hydrocarbon group” include a phenyl group, a biphenylyl group, a naphthyl group, and the like.

  In the general formula (1-1), examples of the “substituent” include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, and isopentyl. Group, neopentyl group, aliphatic hydrocarbon group such as tert-pentyl group; polymerizable functional group such as (meth) acryloyl group, vinylaryl group, vinyloxy group, allyl group, epoxy group; phenyl group, o-tolyl group, aromatic hydrocarbon groups such as m-tolyl group, p-tolyl group, xylyl group, mesityl group, o-cumenyl group, m-cumenyl group, p-cumenyl group; methoxy group, ethoxy group, propoxy group, isopropoxy group , Butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, alkoxy group such as pentyloxy group; Aryloxy groups such as silyl groups; aralkyloxy groups such as benzyloxy groups; groups having an ester bond such as methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, acetoxy group, benzoyloxy group; methylsulfamoyl group, dimethyl group Sulfamoyl group, ethylsulfamoyl group, diethylsulfamoyl group, n-propylsulfamoyl group, di-n-propylsulfamoyl group, isopropylsulfamoyl group, diisopropylsulfamoyl group, n-butyl Alkylsulfamoyl groups such as sulfamoyl group and di-n-butylsulfamoyl group; methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, isopropylsulfonyl group, n-butylsulfonyl group, isobutylsulfonyl group, sec- Spotted A sulfonyl group, an alkylsulfonyl group such as tert- butylsulfonyl group; fluorine atom, a chlorine atom, a bromine atom, a halogen atom such as iodine atom; a nitro group, can be mentioned a cyano group.

As R < ¹ > -R < ³ > of General formula (1-1), it is preferable that they are a halogenated aliphatic hydrocarbon group and a halogenated aromatic hydrocarbon group especially. From the viewpoint of availability, R ^{1 to} R ³ are preferably the same.

In the general formula (1-1), examples of the “halogenated aliphatic hydrocarbon group” include trifluoromethyl group, difluoromethyl group, monofluoromethyl group, dichloromethyl group, monochloromethyl group, dibromomethyl group, difluoro Chloromethyl group, pentafluoroethyl group, tetrafluoroethyl group, trifluoroethyl group, trifluorochloroethyl group, difluoroethyl group, monofluoroethyl group, trifluoroiodoethyl group, heptafluoropropyl group, hexafluoropropyl group, Pentafluoropropyl group, tetrafluoropropyl group, trifluoropropyl group, difluoropropyl group, monofluoropropyl group, perfluorobutyl group, perfluorohexyl group, perfluorooctyl group, perfluorooctylethyl group, pen Group, heptafluoroisopropyl group, perfluoro-3-methylbutyl group, can be perfluoro-3-methylhexyl group and the like exemplified.
In the general formula (1-1), examples of the “halogenated aromatic hydrocarbon group” include a pentafluorophenyl group, a tetrafluorophenyl group, a trifluorophenyl group, a difluorophenyl group, a monofluorophenyl group, and a fluorochlorophenyl group. , Fluorochlorophenyl group, trichlorophenyl group, dichlorophenyl group, monochlorophenyl group, bromophenyl group, iodophenyl group, and difluorobromophenyl group.

As R < ¹ > -R < ³ > of general formula (1-1), a C1-C10 aliphatic hydrocarbon group or aromatic hydrocarbon group substituted by the fluorine atom among these is preferable, and it substitutes with a fluorine atom The aliphatic hydrocarbon group having 1 to 4 carbon atoms is more preferable, and a trifluoromethyl group is particularly preferable.

Specific examples of the methide acid anion include the following methide acid anions, but the present invention is not limited thereto. In addition, the counter of the methide acid anion (MC-1 to MC-26) shown below is Na ⁺ or K ⁺ or Cs ⁺ or tetrabutylammonium.

(Cationic cyanine dye represented by formula (1-2))
The cationic cyanine dye of the present application is a compound represented by the following general formula (1-2).

[In General Formula (1-2), A represents a carbon atom which has a substituent or a hydrogen atom, or a sulfur atom. R ^{4 to} R ¹¹ are each independently a hydrogen atom, a halogen atom, a nitro group, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms, substituted or unsubstituted It represents a substituted aryl group or a substituted or unsubstituted acyl group. R ¹² represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a halogen atom. R ¹³ and R ¹⁴ each independently represent a hydrogen atom, a halogen atom, an organic group having a polymerizable functional group, or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. ]]

In the general formula (1-2), examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. And
Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, an isopropoxy group, an isobutoxy group, a sec-butoxy group, and a tert-butoxy group.

  In the general formula (1-2), the aryl group includes a phenyl group, a biphenylyl group, a terphenylyl group, a quarterphenylyl group, a pentarenyl group, an indenyl group, a naphthyl group, a binaphthalenyl group, a tarnaphthalenyl group, a quarternaphthalenyl group, an azulenyl group. Group, heptalenyl group, biphenylenyl group, indacenyl group, fluoranthenyl group, acephenanthrenyl group, aceanthrilenyl group, phenalenyl group, fluorenyl group, anthryl group, bianthracenyl group, teranthracenyl group, quarteranthracenyl group Group, anthraquinolyl group, phenanthryl group, triphenylenyl group, pyrenyl group, chrycenyl group, naphthacenyl group, preadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group , Hexaphenyl group, hexacenyl group, rubicenyl group, coronenyl groups, trinaphthylenyl groups, heptacenyl groups, pyranthrenyl groups, there is ovalenyl group.

  In the general formula (1-2), examples of the acyl group include an acetyl group, an ethanoyl group, a propanoyl group, an isopropanoyl group, a butanoyl group, an isobutanoyl group, a sec-butanoyl group, and a tert-butanoyl group.

  As a substituent in General formula (1-2), a C1-C4 alkyl group, a C1-C4 alkoxy group, and an aryl group are mentioned.

  In the general formula (1-2), examples of the halogen atom include fluorine, chlorine, bromine, iodine and the like.

In the general formula (1-2), the organic group having a polymerizable functional group includes a polymerizable functional group, includes a carbon atom-hydrogen atom bond as a whole, and may include atoms other than carbon as necessary. Indicates a group composed of atomic groups. Specifically, there are a case where it consists of only a polymerizable functional group and a case where it contains a polymerizable functional group and a linking group. Here, examples of the polymerizable functional group include a (meth) acryloyl group, a vinyl group, an epoxy group, and an isocyanate group.
As the linking group (as viewed from the cyanine skeleton), an alkylene group (hereinafter referred to as -X-), -XO- group, -XNH- group, arylene group, aryleneoxy group, -XCONH- group,- XCOO- group, -XOCO- group, -XCOOX- group, -XOCOX- group, -XCOOXCOO- group, -XOCOXCOO- group, and the like.
Specific examples of the organic group having a polymerizable functional group are as shown in the following table (DC-5 to 8 etc.).

A carbon atom and R ⁴ , R ⁴ and R ⁵ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ⁷ and R ¹³ , A carbon atom and R ⁸ , R ⁸ and R ⁹ , R ⁹ and R ¹⁰ , R ¹⁰ and R ¹¹ , and R ¹¹ and R ¹⁴ may each independently / or simultaneously form an aliphatic saturated hydrocarbon or aromatic cyclic structure.

In general formula (1-2), R ^{4 to} R ⁷ and R ^{8 to} R ¹¹ preferably have at least one halogen atom from the viewpoint of brightness and contrast, and R ⁵ and R ⁹ are each a halogen atom. More preferably. Moreover, it is particularly preferable that the halogen atom is chlorine or bromine.

Specific examples of the cationic cyanine dye include the following cationic cyanine dyes, but the present invention is not limited thereto. Incidentally, the counter of the cationic cyanine dyes shown below (DC-1~DC-91) are, Cl ^- or Br ^- or I ^- is.

(Salt formation)
The salt-forming compound of the present invention stirs or vibrates an aqueous solution in which a methide acid anion and a cationic cyanine dye are dissolved, or stirs or vibrates an aqueous solution of a methide acid anion and an aqueous solution of a cationic cyanine dye. A salt-forming compound can be easily obtained by mixing under conditions. In the aqueous solution, the anionic group of the methide acid anion and the cationic group of the cationic cyanine dye are ionized, and these are ionically bonded, the ion-bonded portion becomes water-insoluble, and the salt-forming compound is precipitated. On the contrary, a salt composed of a counter cation of a methide acid anion and a counter anion of a cationic cyanine dye is water-soluble and can be removed by washing or the like. The methide acid anion and cationic cyanine dye used may be either a single type or a plurality of types having different structures.
When the cationic cyanine dye or the methide acid anion is insoluble in water, each is appropriately dissolved in a soluble solvent, heated and stirred, and then the solvent is distilled off under reduced pressure or normal pressure. A salt-forming compound may be obtained by obtaining a solid, adding water thereto and reslurry to remove the salt that is a by-product, and filtering off the solid by filtration. At this time, as a solvent to be used, a water-soluble organic solvent described later can be used.

  The salt-forming compound of the present invention is preferably a salt-forming compound obtained by removing a salt composed of a counter cation of a methide acid anion and a counter anion of a cationic cyanine dye. When a by-product (for example, NaCl) generated by salt formation exists in the salt-forming compound, the salt-forming compound may precipitate over time in the colored composition.

  As an aqueous solution used at the time of salt formation, a mixed solution of water and a water-soluble organic solvent may be used in order to dissolve the methide acid anion and the cationic cyanine dye. Examples of the water-soluble organic solvent include methanol, ethanol, n-propanol, isopropanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, n-butanol, isobutanol, 2- (methoxymethoxy) ethanol, 2- Butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, ethylene glycol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene Glycol, propylene glycolic monomethyl ether acetate, dipropylene glycol, dipropylene glycol Monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol, triethylene glycol monomethyl ether, polyethylene glycol, glycerin, tetraethylene glycol, dipropylene glycol, acetone, diacetone alcohol, aniline, pyridine, ethyl acetate, isopropyl acetate, methyl ethyl ketone , N, N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran (THF), dioxane, 2-pyrrolidone, 2-methylpyrrolidone, N-methyl-2-pyrrolidone, 1,2-hexanediol, 2,4,6-hexanetriol , Tetrafurfuryl alcohol, 4-methoxy-4-methylpentanone and the like. These water-soluble organic solvents are preferably used in an amount of 5 to 50% by weight, and most preferably 5 to 20% by weight, based on the total weight (100% by weight) of the aqueous solution.

  The ratio of the methide acid anion to the cationic cyanine dye is such that the molar ratio of the anion unit of the methide acid anion to the total cationic groups of the cationic cyanine dye is in the range of 10/1 to 1/4. It is more preferable if the salt-forming compound of the invention can be suitably adjusted and is in the range of 2/1 to 1/2.

<Other colorants that can be used in combination>
The colorant can be used in combination with a pigment or another dye. When used in combination with other colorants, it is preferable to use organic pigments in order to adjust the hue and improve resistance. When the salt-forming compound of the present invention and the organic pigment are used in combination, the use ratio of the salt-forming compound of the present invention and the organic pigment is 1 to 80 parts by weight of the salt-forming compound of the present invention with respect to 100 parts by weight of the organic pigment. Preferably there is. More preferably, it is 5 to 60 parts by weight. When the addition amount of the salt-forming compound of the present invention is within this range, a composition excellent in hue and reproducible chromaticity region can also be obtained.

  As the pigment used in combination, the following are used for each color filter segment. These pigments can be used alone or in admixture of two or more at any ratio as required.

[Pigment forming red filter segment]
As the red pigment forming the red filter segment, the red pigment or red dye described below can be used in combination.
Examples of red pigments include C.I. I. Pigment Red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 57: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 122, 146, 149, 166, 168, 169, 176, 177, 178, 179, 184, 185, 187, 200, 202, 208, 210, 221, 242, 246, 254, 255, 264, 268, 269, 270, 272, 273, 274, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, 287, the diketopyrrolopyrrole pigment described in JP-T-2011-523433, or JP2013-161025A Although the naphthol azo pigment etc. which are described in gazette are mentioned, It is not limited to these in particular. Among these, C.I. I. Pigment Red 177, 242, 254, and 269 are preferably used.
In order to form a red filter segment, a yellow or orange pigment may be used in combination. Examples of yellow or orange pigments include yellow pigments and orange pigments described below.

  Examples of yellow pigments include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 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, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 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, 82, 185, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, 220, 221 or the quinophthalone pigment described in Japanese Patent No. 4993026 is used, but is not particularly limited thereto. . Examples of the orange pigment include C.I. I. Pigment Orange 38, 43, 71, 73 or the like is used.

[Pigment forming blue filter segment]
Examples of the pigment forming the blue filter segment include blue pigments such as 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 2004-333817, Examples thereof include aluminum phthalocyanine pigments described in Japanese Patent No. 4893859 and the like. I. Purple violet pigments such as CI Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, and 50 can be used in combination, but are not particularly limited thereto.
Among these, from the viewpoint of brightness and contrast ratio, C.I. I. Pigment Blue 15: 1, 15: 6 is particularly desirable.

[Pigment forming green filter segment]
Examples of the pigment forming the green filter segment include C.I. I. Pigment Green 7, 10, 36, 37, 58, zinc phthalocyanine pigments described in JP 2008-19383 A, JP 2007-320986 A, JP 2004-70342 A, etc. Although the aluminum phthalocyanine pigment of description is mentioned, it is not specifically limited to these.
Among these, C.I. I. It is preferable to use pigment green 36 or 58.
In addition, a yellow pigment can be used in combination with the green coloring composition in order to adjust the hue. Among them, C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 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, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 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 and the quinophthalone pigment described in Japanese Patent No. 4993026 can be used in combination. In particular, it is not limited to these.
Among these, C.I. I. Pigment Yellow 138, 150 or the like is preferably used.

  In the coloring composition for a color filter of the present invention, the concentration of the coloring agent with respect to all the non-volatile components is preferably 10 to 90% by weight, more preferably 15 to 85% by weight from the viewpoint of obtaining sufficient color reproducibility. Most preferably, it is 20 to 80% by weight. When the concentration of the colorant component is less than 10% by weight, sufficient color reproducibility may not be obtained. When the concentration exceeds 90% by weight, the concentration of the colorant carrier such as a binder resin is lowered, and the color composition May become unstable.

(Miniaturization of pigment)
The pigment that can be used in the present invention is preferably used after being refined, but the refinement method is not particularly limited, and for example, any of wet grinding, dry grinding, and dissolution precipitation can be used. As illustrated, a salt milling process by a kneader method, which is a kind of wet grinding, can be performed.

  The primary particle size of the refined pigment is preferably 20 nm or more because of good dispersion in the colorant carrier. Moreover, since it can form a filter segment with high contrast ratio, it is preferable that it is 100 nm or less. A particularly preferable range is a range of 25 to 85 nm. The primary particle diameter of the pigment was measured by directly measuring the size of the primary particle from an electron micrograph of the pigment using a TEM (transmission electron microscope). Specifically, the minor axis diameter and major axis diameter of the primary particles of each pigment were measured, and the average was taken as the particle diameter of the pigment particles. Next, for 100 or more pigment particles, the volume of each particle is approximated to a cube having the obtained particle diameter to obtain an average volume, and the length of one side of the cube having this average volume is determined as the average primary The particle size.

  Salt milling is a process of heating a mixture of pigment, water-soluble inorganic salt, and water-soluble organic solvent using a kneader such as a kneader, trimix, two-roll mill, three-roll mill, ball mill, attritor, or sand mill. Then, after mechanically kneading, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt serves as a crushing aid, and the pigment is crushed using the high hardness of the inorganic salt during salt milling. By optimizing the conditions for salt milling the pigment, it is possible to obtain a pigment having a sharp particle size distribution with a very fine primary particle diameter and a wide distribution range.

  As the water-soluble inorganic salt, sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like can be used, but sodium chloride (salt) is preferably used from the viewpoint of cost. The water-soluble inorganic salt is preferably used in an amount of 50 to 2000 parts by weight, and most preferably 300 to 1000 parts by weight with respect to 100 parts by weight of the pigment, from the viewpoint of both processing efficiency and production efficiency.

  The water-soluble organic solvent functions to wet the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (mixes) in water and does not substantially dissolve the inorganic salt to be used. However, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety because the temperature rises during salt milling and the solvent is easily evaporated. For example, 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, Liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol and the like are used. The water-soluble organic solvent is preferably used in an amount of 5 to 1000 parts by weight, and most preferably 50 to 500 parts by weight, based on 100 parts by weight of the pigment.

  When the salt is milled, a resin may be added as necessary. The type of resin used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like can be used. The resin used is solid at room temperature, preferably insoluble in water, and more preferably partially soluble in the organic solvent. The amount of the resin used is preferably in the range of 5 to 200 parts by weight with respect to 100 parts by weight of the pigment.

[dye]
Next, dyes that can be used in combination with the salt-forming compound of the present invention will be described. Examples of the dyes that can be used in combination include compounds classified as dyes by the Color Index (published by The Society of Dyers and Colorists) and known dyes described in dyeing notes (Color Dyeing Co., Ltd.). Oil-soluble dyes, acid dyes, metal complex dyes, basic dyes, direct dyes, disperse dyes, mordant dyes, and the like. Of these, oil-soluble dyes, acid dyes, metal complex dyes, and basic dyes are preferred.
Also, according to chemical structure, azo dye, cyanine dye, triphenylmethane dye, phthalocyanine dye, anthraquinone dye, naphthoquinone dye, quinoneimine dye, methine dye, azomethine dye, squarylium dye, acridine dye, styryl dye, coumarin dye, quinoline And dyes and nitro dyes.

(Oil-soluble dye)
When an oil-soluble dye is used, a xanthene dye or an anthraquinone dye is preferable from the viewpoint of lightness.
Xanthene oil-soluble dyes include CI Solvent Red 35, CI Solvent Red 36, CI Solvent Red 42, CI Solvent Red 43, CI Solvent Red 44, and C.I. I. Solvent Red 45, C.I. Solvent Red 46, C.I. Solvent Red 47, C.I. Solvent Red 48, C.I. Solvent Red 49, C.I. Solvent Red 72, C.I. Solvent Red 73, CI Solvent Red 109, CI Solvent Red 140, CI Solvent Red 141, CI Solvent Red 237, CI Solvent Red 246, CI Solvent Violet 2, or CI Solvent Violet 10 or the like.

  Among them, CI solvent red 35, CI solvent red 36, CI solvent red 49, CI solvent red 109, CI solvent red, which are rhodamine-based oil-soluble dyes having high color development Red 237, CI Solvent Red 246, and CI Solvent Violet 2 are more preferable.

  Examples of anthraquinone oil-soluble dyes include CI Solvent Red 172, 222, CI Solvent Violet 60, and the like.

(Acid dyes)
Examples of triarylmethane acid dyes include CI Acid Blue 1, 3, 5, 7, 9, 11, 15, 17, 19, 22, 24, 38, 48, 75, 83, 90, 91, 93. 93: 1, 100, 103, 104, 109, 110, 119, 147, 269, 123, 213, CI Direct Blue 41, CI Acid Violet 17, 19, 21, 23, 25, 38 49, 72, direct blue 41, and the like.

Examples of xanthene acid dyes include C.I. I. Acid Red 51 (erythrosin (edible red No. 3)), C.I. I. Acid Red 52 (Acid Rhodamine), C.I. I. Acid Red 87 (Eosin G (edible red No. 103)), C.I. I. Acid Red 92 (Acid Phloxin PB (edible red No. 104)), C.I. I. Acid Red 289, C.I. I. Acid Red 388, Rose Bengal B (Edible Red No. 5), Acid Rhodamine G, C.I. I. It is preferable to use Acid Violet 9.
Among these, in terms of heat resistance and light resistance, C.I. I. Acid Red 87, C.I. I. Acid Red 92, C.I. I. Acid Red 388 or rhodamine acid dye C.I. I. Acid Red 52 (Acid Rhodamine), C.I. I. Acid Red 289, Acid Rhodamine G, C.I. I. It is more preferable to use Acid Violet 9.
Among these, in particular, C.I., which is a rhodamine acid dye, is excellent in color developability, heat resistance and light resistance. I. Acid Red 52, C.I. I. Most preferably, Acid Red 289 is used.

  As an anthraquinone acid dye, CI Acid Blue 23, 25, 27, 35, 40, 41, 43, 45, 47, 49, 51, 53, 55, 56, 62, 68, 69, 78, 80 81: 1, 11, 124, 127, 127: 1, 140, 150, 175, 215, 230, 277, 344, CI Acid Violet 41, 42, 43, CI Acid Green 25, 27 Or direct violet 17 and the like.

Examples of azo acid dyes include CI Acid Red 1, 3, 4, 6, 8, 11, 12, 14, 18, 26, 27, 33, 37, 53, 57, 88, 106, 108. 111, 114, 131, 137, 138, 151, 154, 158, 159, 173, 184, 186, 215, 257, 266, 296, 337;
CI Acid Orange 7, 10, 12, 19, 20, 22, 28, 30, 52, 56, 74, 127;
CI Acid Violet 11, 56, 58;
CI Acid Yellow 1, 17, 18, 23, 25, 36, 38, 42, 44, 54, 59, 72, 78, 151;
CI Acid Brown 2, 4, 13, 248;
CI Acid Blue 92, 102, 113, 117 and the like.

(Basic dye)
When a basic dye is used, a triarylmethane dye or a xanthene dye is preferable from the viewpoint of lightness.
Examples of the triarylmethane basic dye include C.I. I. Basic Violet 1 (Methyl Violet), 3 (Crystal Violet), 14 (Magenta), C.I. I. Basic Blue 1 (Basic Cyanine 6G), 5 (Basic Cyanine EX), 7 (Victoria Pure Blue BO), 26 (Victoria Blue B conc.), C.I. I. Basic Green 1 (Brilliant Green GX), 4 (Malachite Green) and the like. Among them, C.I. I. It is preferable to use Basic Blue 7, Green 4, Green 1, and Violet 3.

  Examples of rhodamine-based basic dyes include C.I. I. Basic Red 1 (Rhodamine 6G, 6GCP), 3 and 8 (Rhodamine G), C.I. I. Basic violet 10 (Rhodamine B) and the like. Among them, C.I. I. Basic Red 1, Violet 10 and Violet 11 are preferably used.

Examples of flavin basic dyes include C.I. I. Basic Yellow 1,
Examples of auramine basic dyes include C.I. I. Basic Yellow 2, 3,
Examples of the safranine basic dye include C.I. I. Basic Red 2,
Phloxine basic dyes include C.I. I. Basic Red 12,
Examples of the acridine basic dye include C.I. I. Basic Yellow 5,
Examples of the oxazine-based basic dye include C.I. I. Basic Blue 3,
Examples of thiazine-based basic dyes include C.I. I. Basic Blue 24,
Examples of methylene blue basic dyes include C.I. I. Basic Blue 9 (Methylene Blue FZ, Methylene Blue B), 25 (Basic Blue GO), 24 (New Methylene Blue NX) and the like. Among them, C.I. I. Basic Yellow 1, Blue 9, Blue 24 and Blue 25 are preferably used.

  Examples of azo basic dyes include Basic Red 22, Basic Red 76, Basic Yellow 57, Basic Brown 16, Basic Brown 17, and the like.

(Metal complex dyes)
Since the metal complex dye exhibits a fluorescence quenching effect with respect to a dye having fluorescence, it can be suitably used in the present invention.
Examples of the metal complex dye include C.I. I. Solvent Yellow 13, 19, 21, 25, 25: 1, 62, 79, 81, 82, 83, 83: 1, 88, 89, 90, 151, 161, C.I. I. Solvent Orange 5, 11, 20, 40: 1, 41, 45, 54, 56, 58, 62, 70, 81, 99, C.I. I. Solvent Red 8, 35, 83: 1, 84: 1, 90, 90: 1, 91, 92, 118, 119, 122, 124, 125, 127, 130, 132, 160, 208, 212, 214, 225, 233, 234, 243; C.I. I. Solvent Violet 2, 21, 21: 1, 46, 49, 58, 61; I. Solvent Blue 137; C.I. I. Solvent Brown 28, 42, 43, 44, 53, 62, 63; C.I. I. Acid Yellow 59, 121; C.I. I. Acid Orange 74, 162; C.I. I. Acid Red 211 is exemplified. Among these, from the viewpoint of fluorescence quenching, C.I. I. Solvent Yellow 21, 79, 81, 82, C.I. I. Solvent Orange 41, 54, 56, 62, 99, C.I. I. Solvent red 8, 118, 122, 127 are preferred. These metal complex dyes may be used alone or in combination of two or more.

<Binder resin>
The binder resin is one that disperses a colorant, particularly a salt-forming compound and a pigment, or one that dyes and permeates the salt-forming compound, and examples thereof include a thermoplastic resin. In the present invention, the colorant is composed of the salt-forming compound or the salt-forming compound and a pigment.

  The binder resin is preferably a resin having a spectral transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. Moreover, when using with the form of an alkali image development type color resist material, it is preferable to use the alkali-soluble vinyl resin which copolymerized the acidic group containing monomer. In order to further improve the photosensitivity, an energy ray curable resin having an ethylenically unsaturated active double bond can also be used.

  Examples of the thermoplastic resin include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, and polyurethane resin. Polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, polyimide resins, and the like.

  Examples of the alkali-soluble resin obtained by copolymerizing an acidic group-containing ethylenically unsaturated monomer include resins having an acidic group such as a carboxyl group or a sulfone group. Specific examples of the alkali-soluble resin include an acrylic resin having an acidic group, an α-olefin / (anhydrous) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, or Examples include isobutylene / (anhydrous) maleic acid copolymer. Among these, at least one resin selected from an acrylic resin having an acidic group and a styrene / styrene sulfonic acid copolymer, particularly an acrylic resin having an acidic group, is preferably used because of its high heat resistance and transparency.

  Energy ray curable resins having ethylenically unsaturated active double bonds include reactive substitution of isocyanate groups, aldehyde groups, epoxy groups, etc. on polymers having reactive substituents such as hydroxyl groups, carboxyl groups, amino groups, etc. A resin in which a photo-crosslinkable group such as a (meth) acryloyl group or a styryl group is introduced into the polymer by reacting a (meth) acrylic compound having a group or cinnamic acid is used. Further, a polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is half-esterified with a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. A modified version is also used.

  A thermoplastic resin having both alkali-soluble performance and energy ray curing performance is also preferred as the color filter coloring composition.

  The molecular weight of the binder resin used in the present invention is not particularly limited, but the converted weight average molecular weight measured by gel permeation chromatography (GPC) is preferably 5,000 to 100,000. More preferably, it is 7,000-50,000. It is preferable that the converted weight average molecular weight of the binder resin is 5,000 to 100,000, because film loss is unlikely to occur during development, and the non-pixel portion is liable to be easily removed during development. The number average molecular weight (Mn) is preferably in the range of 2,500 to 40,000, and the value of Mw / Mn is preferably 10 or less.

  Here, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are HLC-8220GPC (manufactured by Tosoh Corporation) as a device, and TSK-GEL SUPER HZM-N is connected in series as a column. Is a molecular weight in terms of polystyrene measured using THF.

  When the binder resin is used as a coloring composition for a color filter, a colorant adsorbing group and a carboxyl group that acts as an alkali-soluble group during development, an aliphatic group that acts as an affinity group for the colorant carrier and solvent, and an aromatic group The balance of groups is important for the dispersibility, penetrability, developability, and durability of the colorant, and it is preferable to use a resin having an acid value of 20 to 300 mgKOH / g. When the acid value is less than 20 mgKOH / g, the solubility in the developing solution is poor and it is difficult to form a fine pattern. When it exceeds 300 mgKOH / g, a fine pattern does not remain by development.

  The binder resin is preferably used in an amount of 20 to 500 parts by weight with respect to 100 parts by weight of the colorant. If it is less than 20 parts by weight, the film formability and various resistances will be insufficient, and if it is more than 500 parts by weight, the concentration of the colorant will be low and color characteristics may not be exhibited.

<Thermosetting compound>
In the present invention, it is preferable to further include a thermosetting compound in combination with the thermoplastic resin which is a binder resin. When producing a color filter using the coloring composition for a color filter of the present invention, by including a thermosetting compound, it reacts at the time of firing the filter segment to increase the crosslinking density of the coating film, so that the heat resistance of the filter segment is increased. This improves the effect of suppressing pigment aggregation during firing of the filter segment and improving the contrast ratio.

  Examples of thermosetting compounds include epoxy compounds and / or resins, benzoguanamine compounds and / or resins, rosin-modified maleic acid compounds and / or resins, rosin-modified fumaric acid compounds and / or resins, melamine compounds and / or resins, Examples include urea compounds and / or resins, and phenol compounds and / or resins, but the present invention is not limited thereto. In the coloring composition for a color filter of the present invention, an epoxy compound and / or a resin are preferably used.

The epoxy compound may be a low molecular compound or a high molecular weight compound such as a resin.
Examples of such epoxy compounds include bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols (phenol, alkyl substituted phenol, aromatic substituted phenol, naphthol, alkyl substituted naphthol, dihydroxy Benzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.) Condensates, phenols and various diene compounds (dicyclopentadiene, terpenes, Polymers with nylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc., phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.) ), Polyphenols and aromatic dimethanols (benzenedimethanol, α, α, α ′, α′-benzenedimethanol, biphenyldimethanol, α, α, α ′, α′-biphenyldimene) Methanol, etc.), polycondensates of phenols and aromatic dichloromethyls (α, α'-dichloroxylene, bischloromethylbiphenyl, etc.), polycondensates of bisphenols and various aldehydes, alcohols Etc. glycidylated Glycidyl ether epoxy resins, alicyclic epoxy resins, glycidyl amine-based epoxy resin, glycidyl ester type epoxy resins, but are not limited to these would normally epoxy compound used. These may be used alone or in combination of two or more.

  As a commercial item, for example, Epicoat 807, Epicoat 815, Epicoat 825, Epicoat 827, Epicoat 828, Epicoat 190P, Epicoat 191P (above are trade names; manufactured by Yuka Shell Epoxy Co., Ltd.), Epicoat 1004, Epicoat 1256 (or more) Is a trade name; manufactured by Japan Epoxy Resin Co., Ltd., TECHMORE VG3101L (trade name; manufactured by Mitsui Chemicals, Inc.), EPPN-501H, 502H (trade name; manufactured by Nippon Kayaku Co., Ltd.), JER 1032H60 (trade name) ; Japan Epoxy Resin Co., Ltd.), JER 157S65, 157S70 (Product Name; Japan Epoxy Resin Co., Ltd.), EPPN-201 (Product Name; Nippon Kayaku Co., Ltd.), JER152, JER154 Name: Japan Epoxy Resin Co., Ltd. , EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020 (above are trade names; manufactured by Nippon Kayaku Co., Ltd.), Celoxide 2021, EHPE-3150 (above are trade names: manufactured by Daicel Chemical Industries, Ltd.) , Denacol EX-810, EX-830, EX-851, EX-512, EX-421, EX-313, EX-201, EX-111 (the above are trade names; manufactured by Nagase ChemteX Corporation) However, it is not limited to these.

  The compounding amount of the epoxy compound is preferably 0.5 to 300 parts by weight, and more preferably 1.0 to 50 parts by weight with respect to 100 parts by weight of the colorant. If the amount is less than 0.5 part by weight, the effect of improving heat resistance is small. If the amount is more than 300 parts by weight, a problem may occur when forming a filter segment by photolithography.

  Moreover, in order to assist hardening of a thermosetting compound, the coloring composition for color filters of this invention may contain the hardening | curing agent, the hardening accelerator, etc. as needed. As the curing agent, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like are effective, but are not particularly limited, and can react with thermosetting compounds. Any curing agent may be used as long as it is. 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- D Ru-4-methylimidazole, etc.), phosphorus compounds (eg, triphenylphosphine, 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 weight part is preferable with respect to 100 weight part of thermosetting compounds.

<Organic solvent>
In the coloring composition of the present invention, the colorant is sufficiently dispersed and permeated in the colorant carrier, and is applied on a substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm. An organic solvent can be included to facilitate the formation.

  Examples of the organic solvent include ethyl lactate, benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl -1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m -Diethylbenzene, m-dichlorobenzene, N, N-dimethylacetamide, N, N- Methylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, Ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol Monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate , Diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether Dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol mono Ethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, Louis Seo ketone, methyl cyclohexanol, acetic acid n- amyl acetate n- butyl, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters.

  Among them, since the salt-forming compound used in the present invention and the optional pigment are well dispersed and dissolved, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl It is preferable to use glycol acetates such as ether acetate, alcohols such as benzyl alcohol and 3-methoxybutanol, and ketones such as cyclohexanone. In particular, it is most preferable to use 3-methoxybutanol from the viewpoint of solubility in a salt-forming compound.

  These organic solvents can be used individually by 1 type or in mixture of 2 or more types. When two or more kinds of mixed solvents are used, it is preferable that 65 to 95% by weight of the above-mentioned preferable organic solvent is contained.

  In addition, the organic solvent can be used in an amount of 500 to 4000 parts by weight with respect to 100 parts by weight of the colorant because the colored composition can be adjusted to an appropriate viscosity to form a filter segment having a desired uniform film thickness. Is preferred.

<Dispersion>
When the coloring composition of the present invention further contains a pigment in a colorant carrier composed of a salt-forming compound, the binder resin and a solvent, it is preferably combined with a dispersing aid such as a dye derivative or a resin-type dispersant. It can be produced by finely dispersing using various dispersing means such as a present roll mill, a two-roll mill, a sand mill, a kneader, or an attritor. The colored composition of the present invention can also be produced by mixing pigments, salt-forming compounds, other colorants and the like separately dispersed in a colorant carrier.

[Dispersion aid]
When dispersing the colorant in the colorant carrier, a dispersion aid such as a pigment derivative, a resin-type dispersant, and a surfactant can be appropriately used. The dispersion aid is excellent in dispersion of the colorant and has a great effect of preventing reaggregation of the colorant after dispersion. When used, a color filter having a high spectral transmittance can be obtained.
In the present invention, the salt-forming compound is also expected to play a role as a pigment dispersion aid.

  Examples of the dye derivative include a compound obtained by introducing a basic substituent, an acidic substituent, or a phthalimidomethyl group which may have a substituent into an organic pigment, anthraquinone, acridone, or triazine. 63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, etc. can be used. These can be used alone or in combination of two or more.

  The blending amount of the dye derivative is preferably 0.5% by weight or more, more preferably 1% by weight or more, most preferably from the viewpoint of improving the dispersibility of the additive pigment, based on the total amount of the additive pigment (100% by weight). 3% by weight or more. Further, from the viewpoint of heat resistance and light resistance, the total amount of the additive pigment is preferably 40% by weight or less, more preferably 35% by weight or less, based on the total amount (100% by weight).

  The resin-type dispersant has a pigment-affinity part that has the property of adsorbing to the additive pigment and a part that is compatible with the colorant carrier, and adsorbs to the additive pigment to stabilize dispersion in the colorant carrier. It works. Specific examples of resin-type dispersants include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamine salts. , Polysiloxane, long-chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, modified products thereof, amides formed by reaction of poly (lower alkyleneimine) and polyester having a free carboxyl group, and salts thereof Oil-soluble dispersants such as, (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, etc. Resin, water-soluble polymer, polyester, modified poly Acrylate-based, ethylene oxide / propylene oxide adduct, phosphoric ester or the like is used, they may be used alone or in combination, it is not necessarily limited thereto.

   Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, and 170 manufactured by Big Chemie Japan. 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155 or Anti-Terra-U, 203, 204, or BYK- P104, P104S, 220S, 6919, 21116 or LACTIMON, LACTIMON-WS or BYKUMEN, etc., SOLPERSE-3000, 9000, 13000, 13240, 13650, 13940 manufactured by Nippon Lubrizol Co., Ltd. 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc., BASF EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 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.

  Surfactants include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate Anionic surfactants such as lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate; Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphates, polyoxyethylene sorbitan monostearate and polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyldimethylamino Examples include amphoteric surfactants such as alkylbetaines such as betaine acetate and alkylimidazolines, and these can be used alone or in admixture of two or more, but are not necessarily limited thereto.

  The amount of the resin-type dispersant and surfactant added is preferably 0.1 to 55% by weight, more preferably 0.1 to 45% by weight, based on the total amount of the added pigment (100% by weight). It is. When the blending amount of the resin-type dispersant and the surfactant is less than 0.1% by weight, it is difficult to obtain the added effect. When the blending amount is more than 55% by weight, the dispersion is adversely affected by the excessive dispersant. May affect.

<Photopolymerizable monomer>
The colored composition of the present invention can be used as a photosensitive colored composition for a color filter by further adding a photopolymerizable monomer and / or a photopolymerization initiator.

  The photopolymerizable monomer of the present invention includes monomers or oligomers that are cured by ultraviolet rays or heat to produce a transparent resin, and these can be used alone or in combination of two or more.

Examples of monomers and oligomers that are cured by ultraviolet rays or heat to produce a transparent resin include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 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 ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglycy 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 Nyl (meth) acrylate, ester acrylate, methylolated melamine (meth) acrylate ester, epoxy (meth) acrylate, urethane acrylate and other acrylic esters and methacrylate esters, (meth) acrylic acid, styrene, vinyl acetate, Hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl Examples include, but are not necessarily limited to, til (meth) acrylamide, N-vinylformamide, acrylonitrile and the like.
These photopolymerizable monomers can be used singly or in combination of two or more at any ratio as required.

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

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

Examples of the photopolymerization initiator include 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 benzyl dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, or 3,3 ′, Benzophenone compounds such as 4,4′-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethylthioxanthone Thioxanthone compounds such as 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxy) Enyl) -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 an oxime ester compound such as O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6-trimethylbenzoyl) ) Phosphine compounds such as phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone; borate compounds; carbazole compounds An imidazole compound; or a titanocene compound.
These photoinitiators can be used individually by 1 type or in mixture of 2 or more types by arbitrary ratios as needed.

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

<Sensitizer>
Furthermore, the coloring composition for a color filter of the present invention can contain a sensitizer.
Sensitizers include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives , Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, Azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, Trapirazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphyrin derivatives, annulene derivatives, spiropyran derivatives, spirooxazine Derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, or Michler's ketone derivatives, α-acyloxy esters, acylphosphine oxides, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl Anthraquinone, 4,4'-diethylisophthalophenone, 3,3 'or 4,4'-tetra (t-butylperoxycarbonyl) benzophen Non, 4,4′-diethylaminobenzophenone and the like.
These sensitizers can be used singly or in combination of two or more at any ratio as necessary.

 More specifically, edited by Shin Okawara et al., “Dye Handbook” (1986, Kodansha), edited by Shin Okawara et al., “Chemistry of Functional Dye” (1981, CMC), edited by Tadasaburo Ikemori et al. Examples include, but are not limited to, sensitizers described in "Special Functional Materials" (1986, CMC). In addition, a sensitizer that absorbs light from the ultraviolet region to the near infrared region can also be contained.

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

<Multifunctional thiol>
The coloring composition for a color filter of the present invention can contain a polyfunctional thiol that functions as a chain transfer agent.
The polyfunctional thiol may be a compound having two or more thiol groups. For example, hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene Glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, Pentaerythritol tetrakisthiopropionate, trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercap -s- triazine, 2- (N, N- dibutylamino) -4,6-dimercapto -s- triazine. These polyfunctional thiols can be used singly or in combination of two or more in any ratio as necessary.

  The content of the polyfunctional thiol is preferably 0.1 to 30% by weight, more preferably 1 to 20% by weight based on the weight (100% by weight) of the total solid content of the color filter coloring composition. . If the content of the polyfunctional thiol is less than 0.1% by weight, the effect of adding the polyfunctional thiol is insufficient, and if it exceeds 30% by weight, the sensitivity is too high and the resolution is lowered.

<Antioxidant>
The coloring composition for a color filter of the present invention can contain an antioxidant. Antioxidants are used to prevent the photopolymerization initiators and thermosetting compounds contained in the color filter coloring composition from oxidizing and yellowing due to thermal processes during thermal curing and ITO annealing. Can be high. Therefore, by including an antioxidant, yellowing due to oxidation during the heating step can be prevented, and a high coating film transmittance can be obtained.
The “antioxidant” in the present invention may be a compound having an ultraviolet absorbing function, a radical scavenging function, or a peroxide decomposing function. Specifically, as an antioxidant, a hindered phenol type, a hindered amine type are used. , Phosphorus-based, sulfur-based, benzotriazole-based, benzophenone-based, hydroxylamine-based, salicylate-based, and triazine-based compounds, and known ultraviolet absorbers, antioxidants, and the like can be used.

  Among these antioxidants, a hindered phenol antioxidant, a hindered amine antioxidant, a phosphorus antioxidant, or a sulfur antioxidant is preferable from the viewpoint of achieving both transmittance and sensitivity of the coating film. Agents. More preferably, they are hindered phenolic antioxidants, hindered amine antioxidants, or phosphorus antioxidants.

  These antioxidants can be used singly or in combination of two or more at any ratio as required. When the content of the antioxidant is 0.5 to 5.0% by weight based on the solid content weight of the color filter coloring composition (100% by weight), brightness and sensitivity are more preferable.

<Amine compound>
Moreover, the coloring composition of this invention can be made to contain the amine compound which has a function which reduces the dissolved oxygen. Such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoate. Examples include ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, and N, N-dimethylparatoluidine.

<Leveling agent>
In order to improve the leveling property of the composition on the transparent substrate, it is preferable to add a leveling agent to the colored composition of the present invention. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning, BYK-333 manufactured by Big Chemie. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK Chemie. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can be used in combination. In general, the leveling agent content is preferably 0.003 to 0.5% by weight based on the total weight of the coloring composition (100% by weight).

  Particularly preferred as a leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, having a hydrophilic group but low solubility in water, and when added to a coloring composition, It has the characteristics of low surface tension reduction ability, and it is useful to have good wettability to the glass plate despite its low surface tension reduction ability. Those that can sufficiently suppress the chargeability can be preferably used. As a leveling agent having such preferable characteristics, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. Examples of the polyalkylene oxide unit include a polyethylene oxide unit and a polypropylene oxide unit, and dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

  In addition, the bonding form of the polyalkylene oxide unit with dimethylpolysiloxane includes a pendant type in which the polyalkylene oxide unit is bonded in the repeating unit of dimethylpolysiloxane, a terminal-modified type in which the end of dimethylpolysiloxane is bonded, and dimethylpolysiloxane. Any of linear block copolymer types in which they are alternately and repeatedly bonded may be used. Dimethylpolysiloxane having a polyalkylene oxide unit is commercially available from Toray Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ. -2207, but is not limited thereto.

  An anionic, cationic, nonionic or amphoteric surfactant can be supplementarily added to the leveling agent. Two or more kinds of surfactants may be mixed and used.

  Anionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene 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 stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Examples include esters.

  Examples of the chaotic surfactant that is supplementarily added to the leveling agent include alkyl quaternary ammonium salts and their ethylene oxide adducts. Nonionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate And amphoteric surfactants such as alkyl dimethylamino acetic acid betaine and alkylimidazolines, and fluorine-based and silicone-based surfactants.

<Other additive components>
The colored composition of the present invention can contain a storage stabilizer in order to stabilize the viscosity of the composition over time. Moreover, in order to improve adhesiveness with a transparent substrate, adhesion improving agents, such as a silane coupling agent, can also be contained.

  Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and methyl ethers thereof, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Organic phosphines, phosphites and the like can be mentioned. The storage stabilizer can be used in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of the colorant.

  Examples of the adhesion improver include vinyl silanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane and vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β- (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-aminopropyltrie Xisilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl Examples include 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 weight, preferably 0.05 to 5 parts by weight, with respect to 100 parts by weight of the colorant in the coloring composition.

<Removal of coarse particles>
The coloring composition of the present invention is mixed with coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably 0.5 μm or more and coarse particles by means of centrifugation, sintered filter, membrane filter or the like. It is preferable to remove dust. Thus, it is preferable that a coloring composition does not contain a particle | grain of 0.5 micrometer or more substantially. More preferably, it is 0.3 μm or less.

<Color filter>
Next, the color filter of the present invention will be described. The color filter of this invention comprises the filter segment formed using the coloring composition for color filters of this invention. Examples of the color filter include those having a red filter segment, a green filter segment, and a blue filter segment, or those having a magenta filter segment, a cyan filter segment, and a yellow filter segment.

  As the transparent substrate, glass plates such as soda lime glass, low alkali borosilicate glass and non-alkali alumino borosilicate glass, and resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate are used. In addition, a transparent electrode made of indium oxide, tin oxide, or the like may be formed on the surface of the glass plate or the resin plate in order to drive the liquid crystal after forming the panel.

<Color filter manufacturing method>
The color filter of the present invention can be produced by a printing method or a photolithography method.

  The formation of filter segments by printing methods allows patterning by simply printing and drying the colored composition prepared as a printing ink, making it a low cost and excellent mass productivity as a color filter manufacturing method. Yes. Furthermore, it is possible to print a fine pattern having high dimensional accuracy and smoothness by the development of printing technology. In order to perform printing, it is preferable that the ink does not dry and solidify on the printing plate or on the blanket. Further, it is important to control the fluidity of the ink on the printing press, and the viscosity of the ink can be adjusted with a dispersant or extender pigment.

  When the filter segment is formed by photolithography, the colored composition prepared as a solvent developing type or alkali developing type colored resist material is applied on a transparent substrate by spray coating, spin coating, slit coating, roll coating or the like. By a method, it applies so that a dry film thickness may be set to 0.2-5 micrometers. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film. Then, after immersing in a solvent or alkali developer or spraying the developer by spraying or the like to remove the uncured portion to form a desired pattern, the same operation is repeated for other colors to produce a color filter. be able to. Furthermore, in order to accelerate the polymerization of the colored resist material, heating can be performed as necessary. According to the photolithography method, a color filter with higher accuracy than the above printing method can be manufactured.

  In development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, 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 UV exposure sensitivity, after coating and drying the colored resist material, a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. Then, ultraviolet exposure can be performed.

  The color filter of the present invention can be produced by an electrodeposition method, a transfer method, etc. in addition to the above method, but the colored composition of the present invention can be used in any method. The electrodeposition method is a method for producing a color filter by using a transparent conductive film formed on a substrate and forming each color filter segment on the transparent conductive film by electrophoresis of colloidal particles. . The transfer method is a method in which a filter segment is formed in advance on the surface of a peelable transfer base sheet, and this filter segment is transferred to a desired substrate.

  A black matrix can be formed in advance before forming each color filter segment on a transparent substrate or a reflective substrate. As the black matrix, a chromium, chromium / chromium oxide multilayer film, an inorganic film such as titanium nitride, or a resin film in which a light-shielding agent is dispersed is used, but is not limited thereto. In addition, a thin film transistor (TFT) may be formed in advance on the transparent substrate or the reflective substrate, and then each color filter segment may be formed. In addition, an overcoat film, a transparent conductive film, or the like is formed on the color filter of the present invention as necessary.

  The color filter is bonded to the counter substrate using a sealant, and after injecting liquid crystal from the injection port provided in the seal part, the injection port is sealed, and if necessary, a polarizing film or a retardation film is placed outside the substrate. A liquid crystal display panel is manufactured by bonding.

  Such liquid crystal display panels include twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), and optically convented bend (OCB). It can be used in a liquid crystal display mode in which colorization is performed using a color filter such as the above.

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. Unless otherwise specified, “parts” and “%” mean “parts by weight” and “% by weight”.

  Moreover, the measuring method of the average primary particle diameter of a pigment and the weight average molecular weight (Mw) of resin is as follows.

(Average primary particle diameter of pigment)
The average primary particle diameter of the pigment was measured by a method of directly measuring the size of primary particles from an electron micrograph using a transmission (TEM) electron microscope. Specifically, the minor axis diameter and major axis diameter of the primary particles of each pigment were measured, and the average was taken as the particle diameter of the primary pigment particles. Next, for 100 or more pigment particles, the volume (weight) of each particle was obtained by approximating the obtained particle size cube, and the volume average particle size was defined as the average primary particle size.

(Resin weight average molecular weight (Mw), number average molecular weight (Mn))
Here, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are HLC-8220GPC (manufactured by Tosoh Corporation) as a device, and TSK-GEL SUPER HZM-N is connected in series as a column. Is a molecular weight in terms of polystyrene measured using THF.

<Binder resin production method>
(Preparation of binder resin solution 1)
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer was charged with 70.0 parts of cyclohexanone, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, 7.4 parts of paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.), A mixture of 0.4 part of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for another 3 hours to obtain an acrylic resin solution. After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. The methoxypropyl acetate was added to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. The binder resin solution 1 was prepared by adding. The weight average molecular weight (Mw) was 26000.

(Preparation of binder resin solution 2)
207 parts of cyclohexanone was charged into a separable four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe, and a stirring device, heated to 80 ° C., and the flask was purged with nitrogen. 20 parts of acid, 20 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toa Gosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 2,2′-azobisisobutyronitrile 1.33 parts of the mixture was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a copolymer solution.
Next, after the nitrogen gas was stopped and stirred while injecting dry air for 1 hour with respect to the total amount of the copolymer solution obtained, the mixture was cooled to room temperature, and then 2-methacryloyloxyethyl isocyanate (Karenz manufactured by Showa Denko KK). MOI) A mixture of 6.5 parts, 0.08 part dibutyltin laurate and 26 parts cyclohexanone was added dropwise at 70 ° C. over 3 hours.
About 2 g of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. Then, cyclohexanone was added to the previously synthesized resin solution so that the non-volatile content was 20% by weight. Prepared. The weight average molecular weight (Mw) was 18000.

(Preparation of binder resin solution 3)
207 parts of cyclohexanone was charged into a separable four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe, and a stirring device, heated to 80 ° C., and the flask was purged with nitrogen. 20 parts of acid, 20 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of glycerol monomethacrylate, and 1.33 of 2,2′-azobisisobutyronitrile Part of the mixture was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a copolymer solution.
Next, after the nitrogen gas was stopped and stirred while injecting dry air for 1 hour with respect to the total amount of the copolymer solution obtained, after cooling to room temperature, 6.5 parts of 2-methacryloyloxyl ethyl isocyanate, A mixture of 0.08 part dibutyltin laurate and 26 parts cyclohexanone was added dropwise at 70 ° C. over 3 hours.
About 2 g of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. Then, cyclohexanone was added to the previously synthesized resin solution so that the non-volatile content was 20% by weight. Prepared. The weight average molecular weight (Mw) was 19000.

(Preparation of binder resin solution 4)
A separable four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe and a stirring device was charged with 370 parts of cyclohexanone, heated to 80 ° C., and the atmosphere in the flask was replaced with nitrogen. 18 parts of milphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 10 parts of benzyl methacrylate, 18.2 parts of glycidyl methacrylate, 25 parts of methyl methacrylate, and 2,2′-azobisisobutyronitrile 2.0 Part of the mixture was added dropwise over 2 hours. After dropping, the reaction was further carried out at 100 ° C. for 3 hours, and then 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 100 ° C. for 1 hour. Next, the inside of the container was replaced with air, 0.5 parts of trisdimethylaminophenol and 0.1 part of hydroquinone were added to 9.3 parts of acrylic acid (100 mol% of glycidyl group), and 120 ° C. Then, the reaction was continued for 6 hours, and when the acid value of the solid content reached 0.5, the reaction was terminated to obtain a copolymer solution.
Further, 19.5 parts of tetrahydrophthalic anhydride (100 mol% of the generated hydroxyl group) and 0.5 parts of triethylamine were added and reacted at 120 ° C. for 3.5 hours to obtain a carboxyl group and a copolymer solution.
After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. Thus, a binder resin solution 4 was prepared. The weight average molecular weight (Mw) was 19000.

<Production method of fine pigment>
(Blue refined pigment (P-1): PB15: 6)
Phthalocyanine blue pigment C.I. I. Pigment Blue 15: 6 (Toyocolor Co., Ltd. “Lionol Blue ES”) 100 parts, 800 parts of crushed salt and 100 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (Inoue Seisakusho) and kneaded at 70 ° C. for 12 hours. did. The mixture was added to 3000 parts of warm water, stirred at a high speed mixer for about 1 hour while being heated to about 70 ° C. to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It dried and obtained 98 parts of blue refinement | purification pigments (P-1). The average primary particle diameter of the obtained pigment was 28.3 nm.

(Purple refined pigment (P-2): PV23)
Dioxazine-based purple pigment C.I. I. 120 parts of Pigment Violet 23 (“Fast Violet RL” manufactured by Clariant), 1600 parts of ground sodium chloride, and 100 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 90 ° C. for 18 hours. The mixture was poured into 5000 parts of warm water, stirred at a high speed mixer for about 1 hour while being heated to about 70 ° C. to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It dried and obtained 118 parts purple refinement | purification pigment (P-2). The average primary particle diameter of the obtained pigment was 26.4 nm.

(Red fine pigment (P-3): PR254)
Diketopyrrolopyrrole red pigment C.I. I. 120 parts of Pigment Red 254 ("IRGAZIN RED 2030" manufactured by BASF), 1000 parts of ground sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (Inoue Seisakusho) and kneaded at 60 ° C for 10 hours. The mixture was added to 2000 parts of warm water, heated to about 80 ° C. and stirred with a high speed mixer for about 1 hour to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It dried and obtained 115 parts of red refined pigment (P-3). The average primary particle diameter of the obtained pigment was 24.8 nm.

(Yellow fine pigment (P-4): PY150)
Nickel complex yellow pigment C.I. I. 100 parts of Pigment Yellow 150 (“E-4GN” manufactured by LANXESS), 700 parts of sodium chloride, and 180 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. The mixture was poured into 2000 parts of warm water, stirred at a high speed mixer for about 1 hour while being heated to about 80 ° C. to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It dried and obtained 95 parts of yellow refined pigments (P-4). The average primary particle diameter of the obtained pigment was 39.2 nm.

(Green refined pigment (P-5): PG36)
Phthalocyanine green pigment C.I. I. 120 parts of Pigment Green 36 (“Lionol Green 6YK” manufactured by Toyocolor Co., Ltd.), 1600 parts of sodium chloride, and 270 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 12 hours. The mixture was poured into 5000 parts of warm water, stirred at a high speed mixer for about 1 hour while being heated to about 70 ° C. to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It dried and obtained 117 parts of green refined pigment (P-5). The average primary particle diameter of the obtained pigment was 32.6 nm.

(Red fine pigment (P-6): PR177)
Anthraquinone red pigment C.I. I. 120 parts of Pigment Red 177 (“chromophthaled red A2B” manufactured by BASF), 1000 parts of ground sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 10 hours. The mixture was poured into 2000 parts of warm water, stirred at a high speed mixer for about 1 hour while being heated to about 80 ° C. to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It dried and obtained 115 parts of red refined pigment (P-6). The average primary particle diameter of the obtained pigment was 38.9 nm.

<Method for producing pigment paste>
(Preparation of pigment paste PP-1)
The following mixture was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. A colored composition (PP-1) was produced by filtration using a filter.
Finer pigment (P-1): 10.0 parts Binder resin solution 1: 35.0 parts Cyclohexanone: 20.0 parts Propylene glycol monomethyl ether acetate: 20.0 parts Resin-type dispersant: 15.0 parts (Ajinomoto Fine (20% PGMAc solution of “Ajisper PB821” manufactured by Techno)

(Preparation of pigment paste PP-2 to 6)
Pigment pastes (PP-2 to 6) were obtained in the same manner as the pigment paste (PP-1), except that the type of fine pigment described in Table 1 was changed.

<Synthesis Method of Cationic Cyanine Dye>
The following cationic cyanine dyes were referred to J. Org. Chem., 1995, 60 (8), pp 2411–2422, J. Am. Chem. Soc., 2011, 133 (40), pp 15870–15873. .
According to the following reaction schemes 1 to 3, the cationic cyanine dyes A-1 to 7, B-1 to 4, C-1 to 5, D-1 to 5, E-1 to 5 and F-1 to the present invention. 5 were synthesized respectively.

(Synthesis of Cationic Cyanine Dye A-1)
Cationic cyanine dye A-1 first synthesized intermediate A-1, and then synthesized cationic cyanine dye A-1 as the target product in the next step. (Reaction Scheme 1)

Reaction scheme 1

(Synthesis of Intermediate A-1)
To a 100 mL four-necked flask equipped with a thermometer, a dropping funnel and a condenser, 2,3,3-trimethylindolenine 5 g, iodoethane 7.35 g, and acetonitrile 10 mL were added and heated to reflux for 24 hours. After cooling to room temperature, the solvent was distilled off with an evaporator to precipitate a solid. Thereto, 40 mL of diethyl ether was added, washed and filtered with suction. 8.61 g of product was obtained. The yield was 87%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 188.25 (molecular weight 188.14).

(Synthesis of A-1)
Intermediate A-1 (8.61 g) and acetic anhydride (15 mL) were added to a 100 mL four-necked flask equipped with a thermometer, a dropping funnel, a condenser, and a nitrogen flow tube, and triethyl orthoformate was added thereto using a dropping funnel. The solution was added dropwise and heated to reflux. After 1 hour, the mixture was cooled to room temperature to precipitate a solid. The precipitated solid was filtered off with suction and washed with 30 mL of ethyl acetate and 30 mL of ion-exchanged water. The mixture was heat-dried overnight at 40 ° C. with a hot air dryer to obtain 6.16 g of the product. The yield was 88%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 385.33 (molecular weight 385.26).

中間体A−１のヨードエタンをヨードブタンに変更した以外は、中間体A−１と同様に合成し、９．４９ gの生成物（中間体A−２）を得た。収率は８８％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝２１６．２９（分子量２１６．１７）で目的物であることを確認した。中間体A−２を用いた以外は、A−１と同様に合成し、６．６８ gの生成物（A−２）を得た。収率は８５％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝４４１．４５（分子量４４１．３３）で目的物であることを確認した。 (Synthesis of cationic cyanine dye A-2)

The synthesis was performed in the same manner as Intermediate A-1 except that iodoethane in Intermediate A-1 was changed to iodobutane, to obtain 9.49 g of the product (Intermediate A-2). The yield was 88%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 216.29 (molecular weight 216.17). The synthesis was performed in the same manner as in A-1 except that Intermediate A-2 was used, and 6.68 g of product (A-2) was obtained. The yield was 85%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 441.45 (molecular weight: 441.33).

中間体A−１のヨードエタンをヨードヘキサンに変更した以外は、中間体A−１と同様に合成し、９．７９ gの生成物（中間体A−３）を得た。収率は８４％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝２４４．３５（分子量２４４．２１）で目的物であることを確認した。中間体A−３を用いた以外は、A−１と同様に合成し、６．９２ gの生成物（A−３）を得た。収率は８４％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝４９７．５１（分子量４９７．３９）で目的物であることを確認した。 (Synthesis of Cationic Cyanine Dye A-3)

Synthesis was carried out in the same manner as in Intermediate A-1, except that iodoethane in Intermediate A-1 was changed to iodohexane to obtain 9.79 g of product (Intermediate A-3). The yield was 84%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 244.35 (molecular weight 244.21). The synthesis was performed in the same manner as in A-1, except that Intermediate A-3 was used, to obtain 6.92 g of the product (A-3). The yield was 84%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 497.51 (molecular weight 497.39).

中間体A−１のヨードエタンを３−ヨードプロピレンに変更した以外は、中間体A−１と同様に合成し、９．０４ gの生成物（中間体A−４）を得た。収率は８８％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝２００．２８（分子量２００．１４）で目的物であることを確認した。中間体A−４ を用い、反応温度を８０ ℃に変更した以外は、A−１と同様に合成した。４．６０ gの生成物（A−４）を得た。収率は６２％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝４０９．３６（分子量４０９．２６）で目的物であることを確認した。 (Synthesis of Cationic Cyanine Dye A-4)

Synthesis was performed in the same manner as Intermediate A-1, except that iodoethane in Intermediate A-1 was changed to 3-iodopropylene, and 9.04 g of product (Intermediate A-4) was obtained. The yield was 88%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 200.28 (molecular weight 200.14). This was synthesized in the same manner as A-1 except that the intermediate A-4 was used and the reaction temperature was changed to 80 ° C. 4.60 g of product (A-4) was obtained. The yield was 62%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 409.36 (molecular weight 409.26).

(Synthesis of Cationic Cyanine Dye A-5)
As for the cationic cyanine dye A-5, first, the intermediate A-5 was synthesized, and then the objective product, the cationic cyanine dye A-5, was synthesized in the next step. (Reaction Scheme 2)

Reaction scheme 2

(Synthesis of Intermediate A-5)
In a 100 mL four-necked flask equipped with a thermometer, a dropping funnel and a condenser, 2,3,3-trimethylindolenine 5 g, 2- (4-bromo-butoxymethyl) -oxirane 9.85 g, potassium iodide 5. 21 g and 10 mL of acetonitrile were added, and the mixture was heated to reflux for 24 hours. After cooling to room temperature, the solvent was distilled off with an evaporator to precipitate a solid. Thereto, 40 mL of diethyl ether was added, washed and filtered with suction. 5.87 g of product (intermediate A-5) was obtained. The yield was 52%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). m / z = 288.31 (molecular weight 288.20).

(Synthesis of A-5)
The compound was synthesized in the same manner as A-4, except that Intermediate A-5 was used. 5.54 g of product (A-5) was obtained. The yield was 58%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 585.49 (molecular weight 585.37).

中間体A−５の２−（４−ブロモ−ブトキシメチル）−オキシランを（４−ブロモ−ブチル）−カルバミック酸ビニルエステルに変更した以外は、中間体A−５と同様に合成し、７．９３ gの生成物（中間体A−６）を得た。収率は５９％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝３０１．３１（分子量３０１．１９）で目的物であることを確認した。中間体A−６を用いた以外はA−４と同様に合成し、３．７６ gの生成物（A−６）を得た。収率は５５％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝６１１．４８（分子量６１１．３６）で目的物であることを確認した。 (Synthesis of Cationic Cyanine Dye A-6)

6. Synthesis was performed in the same manner as Intermediate A-5, except that 2- (4-bromo-butoxymethyl) -oxirane of Intermediate A-5 was changed to (4-bromo-butyl) -carbamic acid vinyl ester. 93 g of product (intermediate A-6) was obtained. The yield was 59%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 301.31 (molecular weight 301.19). Synthesis was carried out in the same manner as A-4 except that Intermediate A-6 was used, and 3.76 g of product (A-6) was obtained. The yield was 55%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 611.48 (molecular weight 611.36).

(Synthesis of Cationic Cyanine Dye A-7)
The cationic cyanine dye A-7 is prepared by first synthesizing the intermediate A-7a, then synthesizing the intermediate A-7b in the next step, and then the objective product, the cationic cyanine dye A- 7 was synthesized. (Reaction Scheme 3)

Reaction scheme 3

(Synthesis of Intermediate A-7a)
Synthesis was performed in the same manner as Intermediate A-5 except that 2- (4-bromo-butoxymethyl) -oxirane of Intermediate A-5 was changed to 3-bromopropionic acid, and 5.87 g of product (intermediate) Body A-7a) was obtained. The yield was 52%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). m / z = 232.25 (molecular weight 232.13), which confirmed the intended product.

(Synthesis of Intermediate A-7b)
In a 100 mL three-necked flask equipped with a thermometer, a dropping funnel and a condenser tube, 9.81 g of intermediate A-7a, 15 mL of dichloromethane, 0.40 g of 4- (N, N dimethyl) aminopyridine, 2-hydroxyethyl methacrylate 2 .55 g, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride 3.44 g was added, and the mixture was stirred at room temperature for 24 hours. Liquid separation operation was performed twice with 30 mL of ion-exchanged water, and then the organic layer was washed twice with 50 mL of saturated saline. After adding 5 g of magnesium sulfate and stirring for 30 minutes, the magnesium sulfate was filtered and the solvent was distilled off. The mixture was heated and dried overnight at 40 ° C. in a vacuum drier to obtain 5.46 g of the product (intermediate A-7b). The yield was 71%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 344.31 (molecular weight 344.19).

(Synthesis of A-7)
The compound was synthesized in the same manner as A-4 except that Intermediate A-7b was used. 5.54 g of product (A-7) was obtained. The yield was 58%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 824.38 (molecular weight 824.25).

中間体A−１の２,３,３−トリメチルインドレニンを２,３,３−トリメチル−４,５−ベンゾ−３H−インドールに変更した以外は、中間体A−１と同様に合成し、７．５９ gの生成物（中間体Ｂ−１）を得た。収率は８７％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝２３８．２８（分子量２３８．１６）で目的物であることを確認した。中間体B−１を用いた以外は、A−１と同様に合成し、５．７９ gの生成物（Ｂ−１）を得た。収率は９１％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝４８５．４２（分子量４８５．３０）で目的物であることを確認した。 (Synthesis of Cationic Cyanine Dye B-1)

Synthesized in the same manner as Intermediate A-1, except that 2,3,3-trimethylindolenine in Intermediate A-1 was changed to 2,3,3-trimethyl-4,5-benzo-3H-indole, 7.59 g of product (Intermediate B-1) was obtained. The yield was 87%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 238.28 (molecular weight 238.16). The synthesis was performed in the same manner as A-1 except that Intermediate B-1 was used, and 5.79 g of product (B-1) was obtained. The yield was 91%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 485.42 (molecular weight 485.30).

中間体B−１のヨードエタンをヨードブタンに変更した以外は、中間体B−１と同様に合成し、８．２７ gの生成物（中間体Ｂ−２）を得た。収率は８８％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝２６６．３０（分子量２６６．１９）で目的物であることを確認した。中間体B−２を用いた以外は、A−１と同様に合成し、６．３３ gの生成物（Ｂ−２）を得た。収率は９０％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝５４１．４８（分子量５４１．３６）で目的物であることを確認した。 (Synthesis of cationic cyanine dye B-2)

The intermediate B-1 was synthesized in the same manner as the intermediate B-1, except that the iodoethane was changed to iodobutane to obtain 8.27 g of the product (intermediate B-2). The yield was 88%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 266.30 (molecular weight 266.19). The synthesis was performed in the same manner as A-1 except that Intermediate B-2 was used, to obtain 6.33 g of the product (B-2). The yield was 90%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 541.48 (molecular weight 541.36).

中間体B−１のヨードエタンをヨードヘキサンに変更した以外は、中間体B−１と同様に合成し、８．５６ gの生成物（中間体Ｂ−３）を得た。収率は８５％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝２９４．３２（分子量２９４．２２）で目的物であることを確認した。中間体B−３を用いた以外は、A−１と同様に合成し、６．４８ gの生成物（Ｂ−３）を得た。収率は８８％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝５９７．５５（分子量５９７．４２）で目的物であることを確認した。 (Synthesis of cationic cyanine dye B-3)

The intermediate B-1 was synthesized in the same manner as the intermediate B-1 except that iodoethane was changed to iodohexane to obtain 8.56 g of the product (intermediate B-3). The yield was 85%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 294.32 (molecular weight 294.22). The synthesis was performed in the same manner as in A-1 except that Intermediate B-3 was used, and 6.48 g of the product (B-3) was obtained. The yield was 88%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 597.55 (molecular weight 597.42).

中間体B−１のヨードエタンを３−ヨードプロピレンに変更した以外は、中間体B−１と同様に合成し、４．９６ gの生成物（中間体Ｂ−４）を得た。収率は５５％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝２５０．３５（分子量２５０．１６）で目的物であることを確認した。中間体B−４を用いた以外は、A−４と同様に合成し、２．６８ gの生成物（Ｂ−４）を得た。収率は６４％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝５６９．４１（分子量５６９．３０）で目的物であることを確認した。 (Synthesis of cationic cyanine dye B-4)

Synthesis was carried out in the same manner as in Intermediate B-1, except that iodoethane in Intermediate B-1 was changed to 3-iodopropylene, and 4.96 g of product (Intermediate B-4) was obtained. The yield was 55%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 250.35 (molecular weight 250.16). The synthesis was performed in the same manner as A-4 except that Intermediate B-4 was used to obtain 2.68 g of the product (B-4). The yield was 64%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 569.41 (molecular weight: 569.30).

中間体A−１の２,３,３−トリメチルインドレニンを５−ブロモ−２,３,３−トリメチルインドレニンに変更した以外は、中間体A−１と同様に合成し、７．５３ gの生成物（中間体Ｃ−１）を得た。収率は９１％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝２６６．１８（分子量２６６．０５）で目的物であることを確認した。中間体C−１を用いた以外は、A−１と同様に合成し、５．８９ gの生成物（Ｃ−１）を得た。収率は９２％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝５４１．２０（分子量５４１．０８）で目的物であることを確認した。 (Synthesis of cationic cyanine dye C-1)

This was synthesized in the same manner as Intermediate A-1, except that 2,3,3-trimethylindolenine in Intermediate A-1 was changed to 5-bromo-2,3,3-trimethylindolenine, and 7.53 g Product (intermediate C-1) was obtained. The yield was 91%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). The product was confirmed to be the target product with a cationic component m / z = 266.18 (molecular weight 266.05). The synthesis was carried out in the same manner as A-1 except that Intermediate C-1 was used, and 5.89 g of product (C-1) was obtained. The yield was 92%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed to be the target product by a cationic component m / z = 541.20 (molecular weight: 541.08).

中間体C−１のヨードエタンをヨードブタンに変更した以外は、中間体C−１と同様に合成し、７．８０ gの生成物（中間体Ｃ−２）を得た。収率は８８％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝２９４．２０（分子量２９４．０９）で目的物であることを確認した。中間体C−２を用いた以外は、A−１と同様に合成し、６．０４ gの生成物（Ｃ−２）を得た。収率は９０％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝５９９．５９（分子量５９９．４６）で目的物であることを確認した。 (Synthesis of cationic cyanine dye C-2)

Synthesis was carried out in the same manner as in Intermediate C-1, except that iodoethane in Intermediate C-1 was changed to iodobutane, and 7.80 g of product (Intermediate C-2) was obtained. The yield was 88%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). The product was confirmed to be the target product with a cationic component m / z = 294.20 (molecular weight 294.09). The synthesis was performed in the same manner as in A-1 except that Intermediate C-2 was used to obtain 6.04 g of the product (C-2). The yield was 90%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 599.59 (molecular weight 599.46).

中間体C−１のヨードエタンをヨードヘキサンに変更した以外は、中間体C−１と同様に合成し、８．０４ gの生成物（中間体Ｃ−３）を得た。収率は８５％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝３２２．２４（分子量３２２．１２）で目的物であることを確認した。中間体C−３を用いた以外は、A−１と同様に合成し、６．１４ gの生成物（Ｃ−３）を得た。収率は８８％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝６５３．３３（分子量６５３．２１）で目的物であることを確認した。 (Synthesis of cationic cyanine dye C-3)

Synthesis was carried out in the same manner as in Intermediate C-1, except that iodoethane in Intermediate C-1 was changed to iodohexane to obtain 8.04 g of product (Intermediate C-3). The yield was 85%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 322.24 (molecular weight 322.12). The synthesis was performed in the same manner as in A-1 except that Intermediate C-3 was used, and 6.14 g of the product (C-3) was obtained. The yield was 88%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 653.33 (molecular weight 653.21).

中間体C−１のヨードエタンを３−ヨードプロピレンに変更した以外は、中間体C−１と同様に合成し、４．４３ gの生成物（中間体Ｃ−４）を得た。収率は５２％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝２７８．１６（分子量２７８．０５）で目的物であることを確認した。中間体C−４ を用いた以外は、A−４と同様に合成し、２．５０ gの生成物（Ｃ−４）を得た。収率は６６％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝５６５．２１（分子量５６５．０８）で目的物であることを確認した。 (Synthesis of cationic cyanine dye C-4)

Synthesis was carried out in the same manner as in Intermediate C-1, except that the iodoethane in Intermediate C-1 was changed to 3-iodopropylene, and 4.43 g of product (Intermediate C-4) was obtained. The yield was 52%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 278.16 (molecular weight 278.05). The synthesis was performed in the same manner as in A-4 except that Intermediate C-4 was used to obtain 2.50 g of the product (C-4). The yield was 66%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 565.21 (molecular weight 565.08).

中間体Ａ−７ａの２,３,３-トリメチルインドレニンを５−ブロモ−２,３,３−トリメチルインドレニンに変更した以外は、中間体Ａ−７ａと同様に合成し５．０６ gの生成物（中間体Ｃ−５ａ）を得た。収率は５５％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝３１０．１６（分子量３１０．０４）で目的物であることを確認した。
中間体Ｃ−５ａ を用いた以外は中間体Ａ−７ｂと同様に合成し、４．５７ gの生成物（中間体Ｃ−５ｂ）を得た。収率は７２％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝４２２．２２（分子量４２２．１０）で目的物であることを確認した。中間体C−５bを用いた以外は、A−７と同様に合成し４．７４ gの生成物（Ｃ−５）を得た。収率は５８％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝８５３．２８（分子量８５３．１７）で目的物であることを確認した。 (Synthesis of Cationic Cyanine Dye C-5)

Synthesis was performed in the same manner as Intermediate A-7a, except that 2,3,3-trimethylindolenine in Intermediate A-7a was changed to 5-bromo-2,3,3-trimethylindolenine. The product (intermediate C-5a) was obtained. The yield was 55%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 310.16 (molecular weight 310.04).
The synthesis was performed in the same manner as in Intermediate A-7b except that Intermediate C-5a was used to obtain 4.57 g of the product (Intermediate C-5b). The yield was 72%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 422.22 (molecular weight 422.10). The synthesis was performed in the same manner as in A-7 except that Intermediate C-5b was used to obtain 4.74 g of the product (C-5). The yield was 58%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 853.28 (molecular weight 853.17).

中間体Ａ−１の２,３,３−トリメチルインドレニンを５−クロロ−２,３,３−トリメチルインドレニンに変更した以外は、中間体A−１と同様に合成し、８．１２ gの生成物（中間体Ｄ−１）を得た。収率は９０％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝２２２．２３（分子量２２２．１０）で目的物であることを確認した。
中間体D−１を用いた以外は、A−１と同様に合成し、６．１５ gの生成物（Ｄ−１）を得た。収率は９１％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝４５３．３０（分子量４５３．１９）で目的物であることを確認した。 (Synthesis of cationic cyanine dye D-1)

Synthesis was performed in the same manner as Intermediate A-1, except that 2,3,3-trimethylindolenine in Intermediate A-1 was changed to 5-chloro-2,3,3-trimethylindolenine, and 8.12 g Product (intermediate D-1) was obtained. The yield was 90%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 222.23 (molecular weight 222.10).
The synthesis was performed in the same manner as in A-1 except that Intermediate D-1 was used, and 6.15 g of product (D-1) was obtained. The yield was 91%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 453.30 (molecular weight 453.19).

中間体Ｄ−１のヨードエタンをヨードブタンに変更した以外は、中間体Ｄ−１と同様に合成し、８．５８ gの生成物（中間体Ｄ−２）を得た。収率は８８％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝２５０．２８（分子量２５０．１４）で目的物であることを確認した。中間体D−２を用いた以外は、A−１と同様に合成し、６．４４ gの生成物（Ｄ−２）を得た。収率は８９％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝５０９．３８（分子量５０９．２５）で目的物であることを確認した。 (Synthesis of cationic cyanine dye D-2)

The synthesis was performed in the same manner as in the intermediate D-1, except that the iodoethane of the intermediate D-1 was changed to iodobutane to obtain 8.58 g of the product (intermediate D-2). The yield was 88%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 250.28 (molecular weight 250.14). The synthesis was performed in the same manner as in A-1, except that Intermediate D-2 was used, and 6.44 g of product (D-2) was obtained. The yield was 89%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 509.38 (molecular weight 509.25).

中間体Ｄ−１のヨードエタンをヨードヘキサンに変更した以外は、中間体D−１と同様に合成し、９．１１ gの生成物（中間体Ｄ−３）を得た。収率は８７％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝２７８.２７（分子量２７８．１７）で目的物であることを確認した。中間体D−３を用いた以外は、A−１と同様に合成し、６．８５ gの生成物（Ｄ−３）を得た。収率は８８％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝５６５．４４（分子量５６５．３１）で目的物であることを確認した。 (Method for synthesizing cationic cyanine dye D-3)

Synthesize | combined similarly to the intermediate D-1 except having changed the iodoethane of the intermediate D-1 into the iodohexane, and obtained the product (intermediate D-3) of 9.11 g. The yield was 87%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a desired product with a cationic component m / z = 278.27 (molecular weight 278.17). The synthesis was performed in the same manner as in A-1 except that Intermediate D-3 was used, and 6.85 g of product (D-3) was obtained. The yield was 88%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 565.44 (molecular weight 565.31).

中間体Ｄ−１のヨードエタンを３−ヨードプロピレンに変更した以外は、中間体D−１と同様に合成し、５．６０ gの生成物（中間体Ｄ−４）を得た。収率は６０％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝２３４．２１（分子量２３４．１０）で目的物であることを確認した。中間体D−４ を用いた以外は、A−４と同様に合成し、２．９１ gの生成物（Ｄ−４）を得た。収率は６２％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝４７７．３０（分子量４７７．１９）で目的物であることを確認した。 (Method for synthesizing cationic cyanine dye D-4)

The synthesis was carried out in the same manner as in Intermediate D-1, except that iodoethane in Intermediate D-1 was changed to 3-iodopropylene, and 5.60 g of product (Intermediate D-4) was obtained. The yield was 60%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 234.21 (molecular weight 234.10). The synthesis was carried out in the same manner as A-4 except that Intermediate D-4 was used to obtain 2.91 g of the product (D-4). The yield was 62%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 477.30 (molecular weight 477.19).

中間体Ａ−５の２,３,３−トリメチルインドレニンを５−クロロ−２,３,３−トリメチルインドレニンに変更した以外は、中間体A−５と同様に合成し、４．５７ gの生成物（中間体Ｄ−５）を得た。収率は５７％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝３２２．２８（分子量３２２．１６）で目的物であることを確認した。中間体D−５ を用いた以外は、A−５と同様に合成し、３．７４ gの生成物（Ｄ−５）を得た。収率は６５％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝６５３．４１（分子量６５３．２９）で目的物であることを確認した。 (Method for synthesizing cationic cyanine dye D-5)

This was synthesized in the same manner as Intermediate A-5 except that 2,3,3-trimethylindolenine in Intermediate A-5 was changed to 5-chloro-2,3,3-trimethylindolenine, and 4.57 g Product (intermediate D-5) was obtained. The yield was 57%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 322.28 (molecular weight 322.16). The synthesis was performed in the same manner as in A-5 except that Intermediate D-5 was used to obtain 3.74 g of the product (D-5). The yield was 65%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 6533.41 (molecular weight 653.29).

中間体A−１の２,３,３−トリメチルインドレニンを２,３,３,５−テトラメチルインドレニンに変更した以外は、中間体A−１と同様に合成し、８．４６ gの生成物（中間体Ｅ−１）を得た。収率は８９％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝２０２．３５（分子量２０２．１６）で目的物であることを確認した。中間体E−１を用いた以外は、A−１と同様に合成し、６．３２ gの生成物（Ｅ−１）を得た。収率は９１％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝４１３．４８（分子量４１３．３６）で目的物であることを確認した。 (Method for synthesizing cationic cyanine dye E-1)

Synthesis was similar to Intermediate A-1, except that 2,3,3-trimethylindolenine of Intermediate A-1 was changed to 2,3,3,5-tetramethylindolenine, and 8.46 g The product (intermediate E-1) was obtained. The yield was 89%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 202.35 (molecular weight 202.16). The synthesis was performed in the same manner as in A-1 except that Intermediate E-1 was used, and 6.32 g of product (E-1) was obtained. The yield was 91%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 413.48 (molecular weight 413.36).

中間体Ｅ−１のヨードエタンをヨードブタンに変更した以外は、中間体E−１と同様に合成し、９．０７ gの生成物（中間体Ｅ−２）を得た。収率は８８％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝２３０．３１（分子量２３０．１９）で目的物であることを確認した。中間体E−２を用いた以外は、A−１と同様に合成し、６．４４ gの生成物（Ｅ−２）を得た。収率は８５％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝４６９．４６（分子量４６９．３６）で目的物であることを確認した。 (Method for synthesizing cationic cyanine dye E-2)

Synthesis was carried out in the same manner as in Intermediate E-1, except that iodoethane in Intermediate E-1 was changed to iodobutane, and 9.07 g of product (Intermediate E-2) was obtained. The yield was 88%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 230.31 (molecular weight 230.19). The synthesis was performed in the same manner as in A-1 except that Intermediate E-2 was used to obtain 6.44 g of the product (E-2). The yield was 85%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 469.46 (molecular weight 469.36).

中間体Ｅ−１のヨードエタンをヨードヘキサンに変更した以外は、中間体E−１と同様に合成し、９．３４ gの生成物（中間体Ｅ−３）を得た。収率は８４％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝２５８．３５（分子量２５８．２２）で目的物であることを確認した。中間体E−３を用いた以外は、A−１と同様に合成した。６．２５ gの生成物（Ｅ−３）を得た。収率は７９％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝５２５．５３（分子量５２５．４２）で目的物であることを確認した。 (Method for synthesizing cationic cyanine dye E-3)

The intermediate E-1 was synthesized in the same manner as the intermediate E-1, except that the iodoethane was changed to iodohexane to obtain 9.34 g of the product (intermediate E-3). The yield was 84%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 258.35 (molecular weight: 258.22). The compound was synthesized in the same manner as A-1 except that Intermediate E-3 was used. 6.25 g of product (E-3) was obtained. The yield was 79%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 525.53 (molecular weight 525.42).

中間体E−１のヨードエタンを３−ヨードプロピレンに変更した以外は、中間体E−１と同様に合成し、６．１１ gの生成物（中間体Ｅ−４）を得た。収率は６２％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝２１４．２８（分子量２１４．１６）で目的物であることを確認した。中間体E−４ を用いた以外は、A−４と同様に合成し、２．９３ gの生成物（Ｅ−４）を得た。収率は５８％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝４３７．４１（分子量４３７．３０）で目的物であることを確認した。 (Method for synthesizing cationic cyanine dye E-4)

Synthesize | combined like the intermediate body E-1 except having changed the iodoethane of the intermediate body E-1 into 3-iodopropylene, and obtained the product (intermediate E-4) of 6.11 g. The yield was 62%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 214.28 (molecular weight 214.16). The synthesis was performed in the same manner as A-4 except that Intermediate E-4 was used to obtain 2.93 g of the product (E-4). The yield was 58%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 437.41 (molecular weight 437.30).

中間体A−６の２,３,３−トリメチルインドレニンを２,３,３,５−テトラメチルインドレニンにに変更した以外は、中間体A−６と同様に合成し、７．４０ gの生成物（中間体Ｅ−５）を得た。収率は５８％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝３１５．３３（分子量３１５．２１）で目的物であることを確認した。中間体E−５ を用いた以外は、A−６と同様に合成し、３．９８ gの生成物（Ｅ−５）を得た。収率は６２％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝６３９．５１（分子量６３９．３９）で目的物であることを確認した。 (Synthesis Method of Cationic Cyanine Dye E-5)

This was synthesized in the same manner as Intermediate A-6 except that 2,3,3-trimethylindolenine in Intermediate A-6 was changed to 2,3,3,5-tetramethylindolenine, and 7.40 g Product (intermediate E-5) was obtained. The yield was 58%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 315.33 (molecular weight 315.21). The synthesis was carried out in the same manner as A-6 except that Intermediate E-5 was used to obtain 3.98 g of the product (E-5). The yield was 62%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 639.51 (molecular weight 639.39).

中間体A−１の２,３,３−トリメチルインドレニンを５−メトキシ−２,３,３−トリメチルインドレニンに変更した以外は、中間体A−１と同様に合成し、８．０３ gの生成物（中間体Ｆ−１）を得た。収率は８８％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝２１８．２６（分子量２１８．１５）で目的物であることを確認した。中間体F−１を用いた以外は、A−１と同様に合成し、６．０６ gの生成物（Ｆ−１）を得た。収率は９１％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝４４５．４１（分子量４４５．２９）で目的物であることを確認した。 (Synthesis Method of Cationic Cyanine Dye F-1)

Synthesis was performed in the same manner as Intermediate A-1, except that 2,3,3-trimethylindolenine in Intermediate A-1 was changed to 5-methoxy-2,3,3-trimethylindolenine, and 8.03 g Product (intermediate F-1) was obtained. The yield was 88%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 218.26 (molecular weight 218.15). The synthesis was carried out in the same manner as A-1 except that Intermediate F-1 was used to obtain 6.06 g of the product (F-1). The yield was 91%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 445.41 (molecular weight: 445.29).

中間体F−１のヨードエタンをヨードブタンに変更した以外は、中間体F−１と同様に合成し、８．５８ gの生成物（中間体Ｆ−２）を得た。収率は８７％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝２４６．３２（分子量２４６．１９）で目的物であることを確認した。中間体F−２を用いた以外は、A−１と同様に合成し、６．３６ gの生成物（Ｆ−２）を得た。収率は８８％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝５０１．４６（分子量５０１．３５）で目的物であることを確認した。 (Method for synthesizing cationic cyanine dye F-2)

Synthesis was carried out in the same manner as Intermediate F-1 except that iodoethane in Intermediate F-1 was changed to iodobutane to obtain 8.58 g of the product (Intermediate F-2). The yield was 87%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 246.32 (molecular weight 246.19). The synthesis was performed in the same manner as in A-1 except that Intermediate F-2 was used to obtain 6.36 g of the product (F-2). The yield was 88%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 501.46 (molecular weight 501.35).

中間体F−１のヨードエタンをヨードヘキサンに変更した以外は、中間体F−１と同様に合成し、９．０１ gの生成物（中間体Ｆ−３）を得た。収率は８５％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝２７４．３３（分子量２７４．２２）で目的物であることを確認した。中間体F−３を用いた以外は、A−１と同様に合成し、６．６１ gの生成物（Ｆ−３）を得た。収率は８６％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝５５７．５１（分子量５５７．４１）で目的物であることを確認した。 (Method for synthesizing cationic cyanine dye F-3)

The intermediate F-1 was synthesized in the same manner as the intermediate F-1, except that the iodoethane was changed to iodohexane to obtain 9.01 g of the product (intermediate F-3). The yield was 85%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 274.33 (molecular weight 274.22). The synthesis was performed in the same manner as in A-1 except that Intermediate F-3 was used to obtain 6.61 g of the product (F-3). The yield was 86%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 555.51 (molecular weight 557.41).

中間体F−１のヨードエタンを３−ヨードプロピレンに変更した以外は、中間体F−１と同様に合成し、６．２３ gの生成物（中間体Ｆ−４）を得た。収率は６６％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝２３０．２６（分子量２３０．１５）で目的物であることを確認した。中間体F−４ を用いた以外は、A−４と同様に合成し、３．１７ gの生成物（Ｆ−４）を得た。収率は６１％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝４６９．４０（分子量４６９．２８）で目的物であることを確認した。 (Method for synthesizing cationic cyanine dye F-4)

Synthesize | combined like the intermediate F-1 except having changed the iodoethane of the intermediate F-1 into 3-iodopropylene, and obtained the product (intermediate F-4) of 6.23 g. The yield was 66%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 230.26 (molecular weight 230.15). The synthesis was performed in the same manner as in A-4 except that Intermediate F-4 was used to obtain 3.17 g of the product (F-4). The yield was 61%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 469.40 (molecular weight 469.28).

中間体A−７aの２,３,３-トリメチルインドレニンを５−メトキシ−２,３,３−トリメチルインドレニンに変更した以外は、中間体A−７bと同様に合成し、５．５５ gの生成物（中間体Ｆ−５ａ）を得た。収率は５４％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝２６２．２８（分子量２６２．１４）で目的物であることを確認した。中間体F−５a を用いた以外は、A−７bと同様に合成し、５．２９ gの生成物（中間体Ｆ−５ｂ）を得た。収率は７４％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝３７４．３９（分子量３７４．２６）で目的物であることを確認した。中間体F−５bを用いた以外は、A−７と同様に合成し、５．４２ gの生成物（Ｆ−５）を得た。収率は５８％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝ ７５７．４９（分子量７５７．３７）で目的物であることを確認した。 (Method for synthesizing cationic cyanine dye F-5)

This was synthesized in the same manner as Intermediate A-7b, except that 2,3,3-trimethylindolenine in Intermediate A-7a was changed to 5-methoxy-2,3,3-trimethylindolenine, and 5.55 g Product (intermediate F-5a) was obtained. The yield was 54%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 262.28 (molecular weight 262.14). The synthesis was performed in the same manner as A-7b except that Intermediate F-5a was used to obtain 5.29 g of the product (Intermediate F-5b). The yield was 74%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 374.39 (molecular weight 374.26). The synthesis was performed in the same manner as A-7 except that the intermediate F-5b was used to obtain 5.42 g of the product (F-5). The yield was 58%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a desired product with a cationic component m / z = 757.49 (molecular weight 757.37).

ＰＴＦＥ撹拌子（１５ｍｍ、φ＝６ｍｍ）を入れた３つ口フラスコに、温度計を取り付け、塩化カルシウムを通した窒素気流下で１．０Ｍメチルマグネシウムブロミド−テトラヒドロフラン溶液（東京化成工業製）２１５．７ｇを加えて氷冷後、内温１５℃以下でトリフルオロメタンスルホニルフルオリド１１ｇを添加した。一旦内温４０℃まで加熱撹拌し、再びトリフルオロメタンスルホニルフルオリド５ｇ加え、室温にて２４時間撹拌した。０．３Ｍ塩化カリウム水溶液を２００加えてよく撹拌した後、エバポレーターにてテトラヒドロフランを留去した。析出物を吸引ろ過にてろ別し、得られたろ物を水による再結晶にて精製し、カリウムトリス（トリフルオロメタンスルホニル）メチドとして収量８．２ｇで得た（メチド酸アニオン（Ｇ−１））。¹⁹Ｆ-ＮＭＲにて目的物であることを確認した。 <Synthesis Method of Cationic Cyanine Dye>
Hereinafter, the methide acid anion was referred to Japanese Patent Application Laid-Open No. 2009-155206.
(Synthesis of methide acid anion G-1)

A thermometer was attached to a three-necked flask containing a PTFE stirrer (15 mm, φ = 6 mm), and a 1.0 M methylmagnesium bromide-tetrahydrofuran solution (manufactured by Tokyo Chemical Industry Co., Ltd.) under a nitrogen stream through calcium chloride 215. After adding 7 g and cooling with ice, 11 g of trifluoromethanesulfonyl fluoride was added at an internal temperature of 15 ° C. or lower. The mixture was once heated and stirred to an internal temperature of 40 ° C., 5 g of trifluoromethanesulfonyl fluoride was added again, and the mixture was stirred at room temperature for 24 hours. After adding 200M 0.3M potassium chloride aqueous solution and stirring well, tetrahydrofuran was distilled off by the evaporator. The precipitate was filtered off with suction filtration, and the obtained residue was purified by recrystallization with water to obtain 8.2 g of potassium tris (trifluoromethanesulfonyl) methide (methideate anion (G-1)). . It was confirmed to be the target product by ¹⁹ F-NMR.

Ｇ−１の合成において、トリフルオロメタンスルホニルフルオリドに代えてパーフルオロ-1-ブタンスルホニルフルオリドを使用した以外は同様にして、（メチド酸アニオン（Ｇ−２））を得た。 (Synthesis of methide acid anion G-2)

In the synthesis of G-1, (methide acid anion (G-2)) was obtained in the same manner except that perfluoro-1-butanesulfonyl fluoride was used instead of trifluoromethanesulfonyl fluoride.

Ｇ−１の合成において、トリフルオロメタンスルホニルフルオリドに代えて4-ニトロベンゼンスルホニルフルオリドを使用した以外は同様にして、（メチド酸アニオン（Ｇ−３））を得た。 (Synthesis of methide acid anion G-3)

In the synthesis of G-1, (methide acid anion (G-3)) was obtained in the same manner except that 4-nitrobenzenesulfonyl fluoride was used instead of trifluoromethanesulfonyl fluoride.

<Method for producing salt-forming compound>
(Salt-forming compound (ZC-1))
A salt-forming compound (ZC-1) comprising a cationic cyanine dye and a methide acid anion (G-1) was produced by the following procedure.
Dissolve 11.69 parts of methide acid anion (G-1) and 10 parts of cationic cyanine dye (A-1) in a mixed solvent of 100 parts of water, 300 parts of methanol, 100 parts of methyl ethyl ketone, and 100 parts of acetone. The mixture was stirred at 60 ° C. for 240 minutes and sufficiently reacted. Then, the solid which is a salt-forming compound was taken out by removing the solvent under reduced pressure using an evaporator and concentrating. To this solid, 1000 parts of water was added and stirred at 25 ° C. for 180 minutes, followed by suction filtration to remove by-product salts. The salt-forming compound remaining on the filter paper was further washed by sprinkling 400 parts of water to completely remove the by-product salt, and then the salt-forming compound was taken out. The taken out salt forming compound was dried with a dryer to obtain 12.1 parts of a salt forming compound (ZC-1) of a cationic cyanine dye (A-1) and a methide acid anion (G-1). It was.

(Salt-forming compound (ZC-2 to ZC-38))
Various cationic cyanine dyes and various methidic acids, in the same manner as the salt-forming compound (ZC-1), except that the types and parts by weight of the cationic cyanine dye and the methide acid anion were changed to the contents shown in Table 2. A salt-forming compound (ZC-2 to ZC-38) comprising an anion was produced.

(Salt-forming compound (ZC-39 to ZC-42))
Various types of cationic cyanine dyes and methide acid anions were used in the same manner as the salt-forming compound (ZC-1) except that the types and parts by weight of the cationic dyes and anions shown in Table 3 were changed. Salt-forming compounds (ZC-39 to ZC-42) composed of a cationic dye and various anions were produced.

<Method for producing dye paste and coloring composition>
[Example 1]
(Preparation of dye paste DP-1)
The following mixture was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. A colored composition (DP-1) was produced by filtration using a filter.
Salt-forming compound (ZC-1): 10.0 parts Binder resin solution 1: 50.0 parts Cyclohexanone: 20.0 parts Propylene glycol monomethyl ether acetate: 20.0 parts

(Preparation of colored composition (DB-1))
Next, when the pigment paste (PP-3) and the dye paste (DP-1) are dried, the chromaticity of the coating film is x = 0 in the microspectrophotometer ("OSP-SP100" C light source manufactured by Olympus Optical Co., Ltd.). The color composition (DB-1) was obtained by adjusting the compounding ratio such that .661, y = 0.323 and stirring and mixing with a disper for 1 hour.

[Examples 2-38, Comparative Examples 1-4]
(Preparation of dye paste (DP-2 to DP-42) and coloring composition (DB-2 to 42))
Dye pastes DP-2 to DP-42 were prepared in the same manner as the dye paste DP-1, except that the types of salt-forming compounds shown in Table 4 were changed.
Next, colored compositions (DB-2 to 42) were produced in the same manner as the colored composition DB-1, except that the types of pigment paste and dye paste shown in Tables 5 and 6 were changed.

<Evaluation of coloring composition>
About the obtained coloring composition (DB-1-42), the test regarding heat resistance, the brightness, contrast ratio, and foreign material evaluation was done by the following method. The result of a test is shown to Tables 5-6.

(Method for evaluating heat resistance of coating film)
The coloring composition (DB-1 to 42) is applied on a glass substrate of 100 mm × 100 mm and 1.1 mm thickness using a spin coater, then dried at 70 ° C. for 20 minutes, and then at 220 ° C. for 30 minutes. The coated substrate was prepared by heating and allowing to cool. The prepared coated substrate was heat-treated at 220 ° C., and the film thickness measured using a surface shape measuring device “Dektak 8 (manufactured by Veeco)” was about 2.0 μm. The chromaticity ([L * (1), a * (1), b * (1)]) of the obtained coating film with a C light source was measured with a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.). And measured. Further, as a heat resistance test, the sample was heated at 230 ° C. for 1 hour, and the chromaticity ([L * (2), a * (2), b * (2)]) with a C light source was measured. The color difference ΔEab * was determined and evaluated in the following three stages.
ΔEab * = √ ((L * (2)-L * (1)) ² + (a * (2)-a * (1)) ² + (b * (2)-b * (1)) ² )
A: ΔEab * is less than 1.5 ○: ΔEab * is 1.5 or more and less than 3.0 ×: ΔEab * is 3.0 or more, 5.0 or more

(Lightness evaluation method of coating film)
The coloring composition (DB-1 to 42) was applied on a 100 mm × 100 mm, 1.1 mm thick glass substrate with a spin coater so that x = 0.661, and baked in an oven at 230 ° C. for 30 minutes. Then, a coated substrate of the obtained colored composition was obtained. The brightness (spectral transmittance) was measured using the obtained coated substrate. The lightness (spectral transmittance) in the XYZ color system chromaticity diagram was measured using a spectrophotometer (OTSUKA LCF-1100M). Judgment criteria are as follows. X is a difficult level to use.
◎: 18.0 or more ○: 17.6 or more and less than 18.0 ×: less than 17.6

(Method for evaluating contrast ratio of coating film)
The coloring composition (DB-1 to 42) is formed on a glass substrate having a size of 100 mm × 100 mm and a thickness of 1.1 mm, using a spin coater, and the rotational speed is changed, and the film thickness after heat treatment at 230 ° C. is about 1 Three coated substrates were prepared so as to have a thickness of about 5 μm. Drying conditions were 20 minutes at 70 ° C. and 30 minutes at 230 ° C. after coating, respectively, and the film thickness and contrast ratio were measured, and the contrast at a film thickness of 1.5 μm was determined from the three-point data by the primary correlation method. It was. X is a difficult level to use.
◎: CR ≧ 10000 or more ○: CR = 5000 or more, less than 10000 Δ: CR = 3000 or more, less than 5000 ×: CR = less than 3000

(Coating foreign material test method)
A test substrate was prepared with the colored composition (DB-1 to 42) immediately after preparation, and the number of coating film deposits was counted for evaluation. First, a colored composition is applied on a 100 mm × 100 mm, 1.1 mm thick transparent glass substrate with a spin coater so that the film thickness after drying is about 2.0 μm, and heated in an oven at 230 ° C. for 20 minutes. A test substrate was obtained. Thereafter, surface observation was performed using a metal microscope “BX60” manufactured by Olympus System (magnification is 500 times), and the number of coating film deposits that could be observed in any five visual fields by transmission was counted.
◎: Less than 5 ○: 5 or more and less than 20 △: 20 or more and less than 100 ×: 100 or more

  A coloring composition (DB-1 to 38) containing a cationic cyanine dye specific to the present application and a salt forming compound of the specific methide acid anion as a coloring agent is very good in terms of heat resistance, contrast ratio, and brightness. It became a result. Further, among them, a colored composition having a halogen atom in a cationic cyanine dye and an aliphatic hydrocarbon group having 1 to 4 carbon atoms substituted on the methide acid anion with a fluorine atom (DB-12 to 21, 33, 34) gave particularly good results in lightness and contrast ratio as compared with other cationic cyanine dyes. However, a coloring composition (DB-39 to 40) containing a cationic dye that is not a cationic cyanine dye specific to the present application and a salt-forming compound of a methide acid anion as a coloring agent has a very large fluorescence derived from a xanthene dye. As a result, the contrast ratio was greatly inferior to that of the example. Further, the coloring composition (DB-41 to 42) containing a salt-forming compound of a cationic cyanine dye specific to the present application and an anion that is not a specific methide acid anion as a coloring agent has higher heat resistance than the Examples. The coating film was rough because it was greatly inferior, and as a result, the contrast ratio and brightness were greatly inferior.

<Production of photosensitive coloring composition (resist material)>
[Example 39]
(Resist material (R-1))
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 1.0 μm filter to prepare an alkali developing resist material (R-1).
Coloring composition (DB-1): 60.0 parts Binder resin solution 1: 11.0 parts Trimethylolpropane triacrylate: 4.2 parts (“NK Ester ATMPT” manufactured by Shin-Nakamura Chemical Co., Ltd.)
Photopolymerization initiator ("Irgacure 907" manufactured by BASF): 1.2 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.): 0.4 parts Cyclohexanone: 5.2 parts Propylene glycol monomethyl ether acetate: 18.0 parts

[Examples 40 to 79, Comparative Examples 5 to 8]
(Resist material (R-2 to 38, 42 to 45))
Hereafter, except having changed the coloring composition (DB-1) into the coloring composition shown in Tables 7-8, it carried out similarly to Example 39, and carried out alkali developing type resist material (R-2 to 38, 42 to 45). Produced.

[Example 77]
(Resist material (R-39))
The following mixture was stirred and mixed to be uniform, and then filtered through a 1.0 μm filter to prepare an alkali developing resist material (R-39).
Coloring composition (DB-18): 60.0 parts Binder resin solution 2: 11.0 parts Trimethylolpropane triacrylate: 4.0 parts ("NK ester ATMPT" manufactured by Shin-Nakamura Chemical Co., Ltd.)
Photopolymerization initiator ("Irgacure 907" manufactured by BASF): 1.2 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.): 0.4 parts Cyclohexanone: 5.2 parts Propylene glycol monomethyl ether acetate: 18.0 parts

[Example 78]
(Resist material (R-40))
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 1.0 μm filter to prepare an alkali developing resist material (R-40).
Coloring composition (DB-18): 60.0 parts Binder resin solution 3: 11.0 parts Trimethylolpropane triacrylate: 4.0 parts ("NK ester ATMPT" manufactured by Shin-Nakamura Chemical Co., Ltd.)
Photopolymerization initiator ("Irgacure 907" manufactured by BASF): 1.2 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.): 0.4 parts Cyclohexanone: 5.2 parts Propylene glycol monomethyl ether acetate: 18.0 parts

[Example 79]
(Resist material (R-41))
The following mixture was stirred and mixed to be uniform, and then filtered through a 1.0 μm filter to prepare an alkali developing resist material (R-41).
Coloring composition (DB-18): 60.0 parts Binder resin solution 4: 11.0 parts Trimethylolpropane triacrylate: 4.0 parts (“NK ester ATMPT” manufactured by Shin-Nakamura Chemical Co., Ltd.)
Photopolymerization initiator ("Irgacure 907" manufactured by BASF): 1.2 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.): 0.4 parts Cyclohexanone: 5.2 parts Propylene glycol monomethyl ether acetate: 18.0 parts

<Evaluation of photosensitive coloring composition (resist material)>
The obtained resist materials (R-1 to 45) were subjected to tests concerning heat resistance, lightness, contrast ratio, and foreign matter evaluation by the following methods. The test results are shown in Tables 7 and 8.

(Evaluation of heat resistance of coating film)
The obtained resist material (R-1 to 45) was applied onto a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater, and then dried at 70 ° C. for 20 minutes to obtain an ultrahigh pressure mercury lamp. Was exposed to ultraviolet light at an integrated light quantity of 150 mJ / cm ² and developed with an alkaline developer at 23 ° C. Subsequently, the coating-film board | substrate was produced by heating and standing to cool at 220 degreeC for 30 minutes. The prepared coated substrate was heat-treated at 220 ° C., and the film thickness measured using a surface shape measuring device “Dektak 8 (manufactured by Veeco)” was about 2.0 μm. The chromaticity ([L * (1), a * (1), b * (1)]) of the obtained coating film with a C light source was measured with a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.). And measured. Further, as a heat resistance test, the sample was heated at 230 ° C. for 1 hour, and the chromaticity ([L * (2), a * (2), b * (2)]) with a C light source was measured. The color difference ΔEab * was determined and evaluated in the following three stages.
ΔEab * = √ ((L * (2)-L * (1)) 2+ (a * (2)-a * (1)) 2+ (b * (2)-b * (1)) 2)
A: ΔEab * is less than 1.5 ○: ΔEab * is 1.5 or more and less than 3.0 ×: ΔEab * is 3.0 or more, 5.0 or more

(Brightness evaluation of coating film)
The obtained resist material (R-1 to 45) was applied onto a 100 mm × 100 mm, 1.1 mm thick glass substrate with a spin coater so that x = 0.661, and an exposure amount of 50 mJ / cm ² . After being exposed to ultraviolet light at 25 ° C., it was spray-developed with a 0.2 wt% sodium carbonate aqueous solution at 23 ° C. for 30 seconds and baked at 230 ° C. for 30 minutes in an oven. Obtained. The brightness (spectral transmittance) was measured using the obtained coated substrate. The lightness (spectral transmittance) in the XYZ color system chromaticity diagram was measured using a spectrophotometer (OTSUKA LCF-1100M). Judgment criteria are as follows. X is a difficult level to use.
◎: 18.0 or more ○: 17.6 or more and less than 18.0 ×: less than 17.6

(Evaluation of contrast ratio)
The obtained resist material (R-1 to 45) is formed on a glass substrate having a thickness of 100 mm × 100 mm and a thickness of 1.1 mm by using a spin coater and changing the number of rotations, so that the film thickness after heat treatment at 230 ° C. It is applied to three substrates so as to be about 1.5 μm, then dried at 70 ° C. for 20 minutes, and is exposed to ultraviolet light with an integrated light quantity of 150 mJ / cm ² using an ultrahigh pressure mercury lamp, Development was performed with an alkaline developer to obtain a coated substrate. Subsequently, after heating at 220 ° C. for 30 minutes and allowing to cool, the film thickness and contrast ratio of each of the obtained coating film substrates were measured, and the contrast at a film thickness of 1.5 μm was determined from the three points of data by the primary correlation method. X is a difficult level to use.
◎: CR ≧ 10000 or more ○: CR = 5000 or more, less than 10000 Δ: CR = 3000 or more, less than 5000 ×: CR = less than 3000

(Coating foreign material test method)
A test substrate was prepared using the obtained resist materials (R-1 to 45), and evaluation was performed by counting the number of coating film deposits. First, a colored composition is applied on a 100 mm × 100 mm, 1.1 mm thick transparent glass substrate with a spin coater so that the film thickness after drying is about 2.0 μm, and heated in an oven at 230 ° C. for 20 minutes. A test substrate was obtained. Thereafter, surface observation was performed using a metal microscope “BX60” manufactured by Olympus System (magnification is 500 times), and the number of coating film deposits that could be observed in any five visual fields by transmission was counted.
◎: Less than 5 ○: 5 or more and less than 20 △: 20 or more and less than 100 ×: 100 or more

  The coloring composition (R-1 to 41) containing a cationic cyanine dye specific to the present application and a salt forming compound of the specific methide acid anion as the coloring agent is very good in terms of heat resistance, contrast ratio, and brightness. It became a result. Among them, a colored composition (R-12 to 21, 33) having a halogen atom in a cationic cyanine dye and an aliphatic hydrocarbon group having 1 to 4 carbon atoms substituted on the methide acid anion with a fluorine atom. , 34, 39 to 41) were particularly good in lightness and contrast ratio as compared with other cationic cyanine dyes. However, a coloring composition (R-42 to 43) containing a cationic dye that is not a cationic cyanine dye specific to the present application as a coloring agent and a salt-forming compound of a methide acid anion has a very large fluorescence derived from a xanthene dye. As a result, the contrast ratio was greatly inferior to that of the example. In addition, the coloring composition (R-44 to 45) containing a salt-forming compound of a cationic cyanine dye specific to the present application and an anion that is not a specific methide acid anion as a colorant has higher heat resistance than the examples. The coating film was rough because it was greatly inferior, and as a result, the contrast ratio and brightness were greatly inferior.

<Manufacture of color filters>
First, the blue photosensitive coloring composition and the green photosensitive coloring composition used for preparation of a color filter were produced. In addition, the photosensitive coloring composition (R-18) was used about red.

(Preparation of blue photosensitive coloring composition (RB-1))
A mixture having the following composition was stirred and mixed to be uniform, and then filtered through a 1.0 μm filter to prepare a blue photosensitive coloring composition (RB-1).
Pigment paste (PP-1) 24.0 parts Pigment paste (PP-2) 10.0 parts Binder resin solution 1 15.2 parts Photopolymerizable monomer ("Aronix M400" manufactured by Toagosei Co., Ltd.) 3.3 parts Photopolymerization initiator ("Irgacure 907" manufactured by BASF) 2.0 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.4 parts 45.1 parts ethylene glycol monomethyl ether acetate

(Preparation of green photosensitive coloring composition (RG-1))
A mixture having the following composition was stirred and mixed to be uniform, and then filtered through a 1.0 μm filter to prepare a green photosensitive coloring composition (RG-1).
Pigment paste (PP-4) 17.0 parts Pigment paste (PP-5) 17.0 parts Binder resin solution 1 15.2 parts Photopolymerizable monomer ("Aronix M400" manufactured by Toagosei Co., Ltd.) 3.3 parts Photopolymerization initiator ("Irgacure 907" manufactured by BASF) 2.0 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.4 parts 45.1 parts ethylene glycol monomethyl ether acetate

(Production of color filter)
A black matrix was patterned on a glass substrate, and a red photosensitive coloring composition (R-18) was applied on the substrate with a spin coater so as to have a thickness of 2.0 μm to form a colored film. The film was irradiated with ultraviolet rays of 300 mJ / cm ² through a photomask using an ultrahigh pressure mercury lamp. Next, spray development was performed with an alkaline developer composed of a 0.2% by weight aqueous sodium carbonate solution to remove unexposed portions, followed by washing with ion-exchanged water. The substrate was heated at 230 ° C. for 20 minutes to obtain a red filter segment. Formed. By the same method, the green photosensitive coloring composition (RG-1) of the present invention has a thickness of 2 μm, and the blue photosensitive coloring composition (RB-1) has a thickness of 2 μm. Each was coated to form a green filter segment and a blue filter segment to obtain a color filter.

  By using the red photosensitive coloring composition (R-18) of the present invention, it was possible to produce a color filter having a high contrast ratio and high brightness.

Claims (4)

A color filter coloring composition comprising at least a colorant, a binder resin, and an organic solvent, wherein the colorant is represented by the following general formula (1-1): a methide acid anion and a cationic cyanine dye. A coloring composition for a color filter comprising a salt-forming compound.

[In the general formula (1-1), D + represents a cationic cyanine dye represented by the following general formula (1-2), and R ^{1 to} R ³ each independently have a substituent. Represents an aliphatic hydrocarbon group that may be substituted, or an aromatic hydrocarbon group that may have a substituent. ]

[In General Formula (1-2), A represents a carbon atom which has a substituent or a hydrogen atom, or a sulfur atom. R ^{4 to} R ¹¹ are each independently a hydrogen atom, a halogen atom, a nitro group, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms, substituted or unsubstituted It represents a substituted aryl group or a substituted or unsubstituted acyl group. R ¹² represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a halogen atom. R ¹³ and R ¹⁴ each independently represent a hydrogen atom, a halogen atom, an organic group having a polymerizable functional group, or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. ]] 2. The color filter according to claim 1, wherein in Formula (1-1), R ^{1 to} R ³ are each independently a halogenated alkyl group having 1 to 4 carbon atoms or a halogenated aromatic hydrocarbon group. Coloring composition.   Furthermore, the coloring composition for color filters of Claim 1 or 2 containing a photopolymerizable monomer and / or a photoinitiator.   A color filter comprising a filter segment formed from the colored composition for color filter according to claim 1 on a substrate.