JP2012087287A - Compound for dye - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a compound having high molar absorptivity and useful as a dye.SOLUTION: The compound is expressed by formula (I) (wherein Ris a hydrogen atom or a 1C-20C monovalent aliphatic hydrocarbon group and -CH- contained in the aliphatic hydrocarbon group may be replaced with -O- or -CO-; Ris a hydrogen atom, a cyano group or a carbamoyl group; Ris a 1C-4C alkyl group and the hydrogen atom contained in the alkyl group may be replaced with a halogen atom; Rto Rare mutually independently a hydrogen atom, a 1C-8C alkyl group, a 1C-8C alkoxy group, a 2C-8C alkoxyalkyl group, a hydroxy group, a cyano group, a nitro group or -SOM, at least one of Rto Ris a nitro group and at least one thereof is -SOM, and M is a hydrogen atom or an alkali metal atom).

Description

  The present invention relates to compounds useful as dyes.

Dyes are used for color display using reflected light or transmitted light in the fields of fiber materials, liquid crystal display devices, ink jets, and the like.
As such a dye, for example, a compound represented by the following formula is known (Patent Document 1).

JP-A-2-153777

  The above compounds may not always be sufficient in terms of molar extinction coefficient.

［式（Ｉ）中、Ｒ^１は、水素原子又は炭素数１〜２０の１価の脂肪族炭化水素基を表し、該脂肪族炭化水素基に含まれる−ＣＨ_２−は、−Ｏ−又は−ＣＯ−で置き換わっていてもよい。
Ｒ^２は、水素原子、シアノ基又はカルバモイル基を表す。
Ｒ^３は、炭素数１〜４のアルキル基を表し、該アルキル基に含まれる水素原子は、ハロゲン原子で置換されていてもよい。
Ｒ^４〜Ｒ⁸は、互いに独立に、水素原子、炭素数１〜８のアルキル基、炭素数１〜８のアルコキシ基、炭素数２〜８のアルコキシアルキル基、ヒドロキシ基、シアノ基、ニトロ基又は−ＳＯ_３Ｍを表し、Ｒ^４〜Ｒ⁸のうち少なくとも１つはニトロ基を表し、少なくとも１つは−ＳＯ_３Ｍを表す。
Ｍは、水素原子又はアルカリ金属原子を表す。］ The present invention provides the following [1] to [6].
[1] A compound represented by the formula (I).

[In Formula (I), R ¹ represents a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, and —CH ₂ — contained in the aliphatic hydrocarbon group is —O— or It may be replaced by -CO-.
R ² represents a hydrogen atom, a cyano group or a carbamoyl group.
R ³ represents an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom contained in the alkyl group may be substituted with a halogen atom.
R ^{4 to} R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxyalkyl group having 2 to 8 carbon atoms, a hydroxy group, a cyano group, or a nitro group. or an -SO ₃ ^M, at least one of R 4 to R ⁸ is a nitro group, at least one represents -SO ₃ M.
M represents a hydrogen atom or an alkali metal atom. ]

［式（ＩＩ）中、Ｒ^１、Ｒ^２、Ｒ^３及びＭは、それぞれ上記と同じ意味を表す。］
［３］Ｒ^１が、−Ｌ^１−Ｘ^１−Ｒ^９である［１］又は［２］記載の化合物。
［Ｌ^１は、炭素数１〜８のアルカンジイル基を表す。Ｘ^１は、−ＣＯ−Ｏ−を表す。Ｒ^９は、水素原子又は炭素数１〜１７の１価の脂肪族炭化水素基を表し、該脂肪族炭化水素基に含まれる−ＣＨ_２−は、−Ｏ−又は−ＣＯ−で置き換わっていてもよい。］
［４］Ｘ^１が、＊−Ｏ−ＣＯ−である［３］記載の化合物。
［＊は、Ｌ^１との結合手を表す。］
［５］［１］〜［４］のいずれか記載の化合物を有効成分とする染料。
［６］［５］記載の染料、樹脂及び溶剤を含む着色感光性樹脂組成物。 [2] The compound according to [1] represented by formula (II).

[In formula (II), R ¹ , R ² , R ³ and M each have the same meaning as described above. ]
[3] The compound according to [1] or [2], wherein R ¹ is -L ¹ -X ¹ -R ⁹ .
[L ¹ represents an alkanediyl group having 1 to 8 carbon atoms. X ¹ represents —CO—O—. R ⁹ represents a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 17 carbon atoms, and —CH ₂ — contained in the aliphatic hydrocarbon group is replaced by —O— or —CO—. Also good. ]
[4] The compound according to [3], wherein X ¹ is * —O—CO—.
[* Represents a bond to ^{L 1.} ]
[5] A dye containing the compound according to any one of [1] to [4] as an active ingredient.
[6] A colored photosensitive resin composition comprising the dye, resin and solvent according to [5].

  The compound of the present invention has a large molar extinction coefficient.

  The present invention is a compound represented by formula (I) (hereinafter sometimes referred to as compound (I)).

[In Formula (I), R ¹ represents a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, and —CH ₂ — contained in the aliphatic hydrocarbon group is —O— or It may be replaced by -CO-.
R ² represents a hydrogen atom, a cyano group or a carbamoyl group.
R ³ represents an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom contained in the alkyl group may be substituted with a halogen atom.
R ^{4 to} R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxyalkyl group having 2 to 8 carbon atoms, a hydroxy group, a cyano group, or a nitro group. or an -SO ₃ ^M, at least one of R 4 to R ⁸ is a nitro group, at least one represents -SO ₃ M.
M represents a hydrogen atom or an alkali metal atom. ]

Examples of the monovalent aliphatic hydrocarbon group represented by R ¹ include a methyl group, an ethyl group, a propyl group, an isobutyl group, a butyl group, a tert-butyl group, a hexyl group, a heptyl group, an octyl group, and a nonyl group. And alkyl groups such as a decyl group.
—CH ₂ — contained in the aliphatic hydrocarbon group may be replaced by —O— or —CO—. These groups, _{e.g., -C 2 H 4 -O-C} 6 H 12, -C 2 H 4 -O-C 2 H 4 -O-C 2 H 5, -C 2 H 4 -CO-C ₆ H ₁₂ , —C ₂ H ₄ —O—CO—O—C ₆ H ₁₂ , —C ₂ H ₄ —O—C ₂ H ₄ —CO—C ₆ H _{12 and the} like can be mentioned.

R ¹ is preferably -L ¹ -X ¹ -R ⁹ . It is preferable that R ¹ be -L ¹ -X ¹ -R ^{9 since} the solubility of the compound of the present invention in an organic solvent tends to be improved.
R ⁹ is a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 17 carbon atoms, and —CH ₂ — contained in the aliphatic hydrocarbon group is replaced by —O— or —CO—. Also good. Examples of the aliphatic hydrocarbon group representing R ⁹ include those having 1 to 17 carbon atoms among the groups listed as the monovalent aliphatic hydrocarbon group represented by R ¹ .
Examples of the monovalent aliphatic hydrocarbon group represented by R ⁹ in which —CH ₂ — is replaced by —O— or —CO— include —L ² —X ² —R ¹⁰ .
R ¹⁰ is a hydrogen atom, a methyl group or an ethyl group.

L ¹ and L ² are each independently an alkanediyl group having 1 to 8 carbon atoms, such as a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, butane. -1,4-diyl group, butane-1,3-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8- A diyl group etc. are mentioned.

X ¹ and X ² are —CO—O—. In particular, X ¹ is preferably * —O—CO— (* represents a bond to L ¹ ). When X ¹ is * —O—CO—, the compound of the present invention can be easily produced.

Examples of -L ¹ -X ¹ -R ⁹ include a group represented by any one of formulas (f-1) to (f-25). In each formula, ● represents a bond with a nitrogen atom. Of ^{these, -L 1 -X 1 -L 2 -X 2} -R 10, for example, groups represented by the formula (f-1) ~ formula (f-20). Among them, Formula (f-1), Formula (f-2), Formula (f-5), Formula (f-6), Formula (f-9), Formula (f-10), Formula (f-13) A group represented by any one of formula (f-14), formula (f-17), formula (f-18), formula (f-21) and formula (f-24), 2), the formula (f-6), the formula (f-10), the formula (f-14), the formula (f-18), the formula (f-21), and the formula (f-24). The group represented by any one of formula (f-2), formula (f-14), formula (f-21) and formula (f-24) is more preferred.

R ² is a hydrogen atom, a cyano group or a carbamoyl group. Of these, a cyano group is preferable.

Examples of the alkyl group having 1 to 4 carbon atoms represented by R ³ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group. A hydrogen atom contained in the alkyl group may be substituted with a halogen atom.
Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. As a C1-C4 alkyl group by which the hydrogen atom is substituted by the halogen atom, a trifluoromethyl group, a pentafluoroethyl group, etc. are mentioned, for example.
R ³ is preferably a methyl group or a trifluoromethyl group, and more preferably a methyl group.

R ^{4 to} R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxyalkyl group having 2 to 8 carbon atoms, a hydroxy group, a cyano group, or a nitro group. or an -SO ₃ ^M, at least one of R 4 to R ⁸ is a nitro group, at least one is a -SO ₃ M.

  M is a hydrogen atom or an alkali metal atom. Examples of the alkali metal include lithium, sodium, and potassium. As M, a hydrogen atom and a sodium atom are preferable, and a hydrogen atom is more preferable.

Examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, and n-octyl group. A linear alkyl group;
Isopropyl group, isobutyl group, sec-butyl group, isopentyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1- Methylhexyl group, 2-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group, 5-methylhexyl group, 1-ethylpentyl group, 2-ethylpentyl group, 3-ethylpentyl group, 1-propylbutyl Group, 1- (1-methylethyl) butyl group, 1- (1-methylethyl) -2-methylpropyl group, 1-methylheptyl group, 2-methylheptyl group, 3-methylheptyl group, 4-methylheptyl group Group, 5-methylheptyl group, 6-methylheptyl group, 1-ethylhexyl group, 2-ethylhexyl group, 3-ethylhexyl 4-ethylhexyl group, 1-n-propylpentyl group, 2-propylpentyl group, 1- (1-methylethyl) pentyl group, 1-butylbutyl group, 1-butyl-2-methylbutyl group, 1-butyl-3 -Methylbutyl group, 1- (1,1-dimethylethyl) butylbutyl group, tert-butyl group, 1,1-dimethylpropyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3- Dimethylbutyl group, 2,3-dimethylbutyl group, 1-ethyl-2-methylpropyl group, 1,1-dimethylpentyl group, 1,2-dimethylpentyl group, 1,3-dimethylpentyl group, 1,4- Dimethylpentyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3,3-dimethylpentyl group, 3,4-dimethyl Rupentyl group, 1-ethyl-1-methylbutyl group, 1-ethyl-2-methylbutyl group, 1-ethyl-3-methylbutyl group, 2-ethyl-1-methylbutyl group, 2-ethyl-3-methylbutyl group, 1, 1-dimethylhexyl group, 1,2-dimethylhexyl group, 1,3-dimethylhexyl group, 1,4-dimethylhexyl group, 1,5-dimethylhexyl group, 2,2-dimethylhexyl group, 2,3- Dimethylhexyl group, 2,4-dimethylhexyl group, 2,5-dimethylhexyl group, 3,3-dimethylhexyl group, 3,4-dimethylhexyl group, 3,5-dimethylhexyl group, 4,4-dimethylhexyl Group, 4,5-dimethylhexyl group, 1-ethyl-2-methylpentyl group, 1-ethyl-3-methylpentyl group, 1-ethyl-4-methylpentyl group 2-ethyl-1-methylpentyl group, 2-ethyl-2-methylpentyl group, 2-ethyl-3-methylpentyl group, 2-ethyl-4-methylpentyl group, 3-ethyl-1-methylpentyl group 3-ethyl-2-methylpentyl group, 3-ethyl-3-methylpentyl group, 3-ethyl-4-methylpentyl group, 1-propyl-1-methylbutyl group, 1-propyl-2-methylbutyl group, 1 -Propyl-3-methylbutyl group, 1- (1-methylethyl) -1-methylbutyl group, 1- (1-methylethyl) -2-methylbutyl group, 1- (1-methylethyl) -3-methylbutyl group, Examples thereof include branched alkyl groups such as 1,1-diethylbutyl group and 1,2-diethylbutyl group.

  Examples of the alkoxy group having 1 to 8 carbon atoms include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group and the like. .

  Examples of the alkoxyalkyl group having 2 to 8 carbon atoms include methoxymethyl group, methoxyethyl group, methoxypropyl group, methoxybutyl group, methoxypentyl group, 1-ethoxypropyl group, 2-ethoxypropyl group, 1-ethoxy- 1-methylethyl group, 1-methyl-2-ethoxyethyl group, 1- (1-methylethoxy) propyl group, 2- (1-methylethoxy) propyl group, 1- (1-methylethoxy) -1-methyl Examples include an ethyl group, 2- (1-methylethoxy) -1-methylethyl group, and 3-ethoxypropyl group.

The compound (I) is preferably a compound represented by the formula (II).

[In formula (II), R ¹ , R ² , R ³ and M each have the same meaning as described above. ]
When the compound (I) is a compound represented by the formula (II), the molar extinction coefficient tends to be further increased.

  In terms of ease of production, the compound (I) is more preferably a compound represented by the formula (III).

[In formula (III), R ¹ , R ² , R ³ and M each have the same meaning as described above. ]
In Formula (III), R ¹ is preferably a group represented by the above-L ¹ -X ¹ -R ⁹ , and among them, Formula (f-1), Formula (f-2), Formula (f-5) ), Formula (f-6), formula (f-9), formula (f-10), formula (f-13), formula (f-14), formula (f-17), formula (f-18) , A group represented by any one of formula (f-21) and formula (f-24) is preferable, and formula (f-2), formula (f-6), formula (f-10), formula (f- 14), a group represented by any one of the formula (f-18), the formula (f-21) and the formula (f-24) is more preferable, and the formula (f-2), the formula (f-14), the formula A group represented by any one of (f-21) and formula (f-24) is more preferable.
R ² is preferably a cyano group, and R ³ is preferably a methyl group or a trifluoromethyl group, more preferably a methyl group.

Examples of compound (I) include compound (I-1) to compound (I-102). R ^{1 to} R ⁸ described in Table 1 correspond to the formula (I-0). The column of R ¹ indicates the number of the group formula exemplified above. For example, compound (I-1) is a compound represented by the following formula (I-1).

Among them, compound (I-1) to compound (I-21), compound (I-43) to compound (I-45), compound (I-54) to compound (I-56), compound (I-65) -Compound (I-67), Compound (I-76)-Compound (I-78) and Compound (I-87)-Compound (I-102) are preferred, Compound (I-43)-Compound (I-44) ), Compound (I-54) to Compound (I-55), Compound (I-65) to Compound (I-66), Compound (I-76) to Compound (I-77), Compound (I-87) , Compound (I-91), Compound (I-95) and Compound (I-99) are more preferable, and Compound (I-43), Compound (I-65), Compound (I-87) and Compound (I- 95) is more preferable.
If compound (I) is any of these compounds, the molar extinction coefficient tends to be particularly high.

The compound of the present invention can be produced by diazo coupling a method described in JP-B-7-88633, a diazonium salt represented by the following formula (a2) and a pyridone compound represented by the formula (a3).
The diazonium salt represented by the formula (a2) can be obtained, for example, by diazotizing the amine represented by the formula (a1) with nitrous acid, nitrite or nitrite.

[In Formula (a1), Formula (a2), and Formula (a3), R ^{1 to} R ⁸ each have the same meaning as described above. A ¹ represents an inorganic anion or an organic anion. ]

Examples of the inorganic anion include fluoride ion, chloride ion, bromide ion, iodide ion, perchlorate ion, hypochlorite ion, and the like.
Examples of the organic anion, for _example, CH ³ COO ^_-, PhCOO -, and the like.
Preferably, chloride ion, bromide _ion, CH 3 COO ^-, and the like.

  The compound of the present invention can be produced by diazo coupling a diazonium salt represented by the formula (a2) and a pyridone compound represented by the formula (a3) in an aqueous solvent. The reaction temperature is preferably -5 ° C to 60 ° C, more preferably 0 ° C to 30 ° C. The reaction time is preferably 1 hour to 12 hours, more preferably 1 hour to 4 hours. Examples of the aqueous solvent include N-methylpyrrolidone and the like.

In the compound of the present invention, compound (Ib) wherein R ¹ is -L ¹ -X ¹ -R ⁹ and X ¹ is * -O-CO- (* represents the bonding position with L ^1. In the case of a compound represented by formula (Ib) (hereinafter sometimes referred to as “compound (Ib)”).

[式（Ｉｂ）中、Ｒ^２〜Ｒ^９及びＬ^１は、それぞれ上記と同じ意味を表す。]

[In Formula (Ib), R ^{2 to} R ⁹ and L ¹ each have the same meaning as described above. ]

  The azo compound represented by the formula (b4) is obtained by diazo coupling the diazonium salt represented by the formula (a2) and the pyridone compound represented by the following formula (b3) by the same method as described above. Can be manufactured.

［式（ｂ３）及び式（ｂ４）中、Ｒ^２〜Ｒ^９及びＬ^１は、それぞれ上記と同じ意味を表す。］

[In formula (b3) and formula (b4), R ^{2 to} R ⁹ and L ¹ each represent the same meaning as described above. ]

Next, an azo compound represented by the formula (b4) and R ⁹ —CO—Z ¹ (R ⁹ represents the same meaning as described above, and Z ¹ represents a chlorine atom or a bromine atom) are present in the presence of an organic solvent. Compound (Ib) can be obtained by performing the reaction under the following conditions. The reaction temperature is preferably 30 ° C to 180 ° C, more preferably 50 ° C to 120 ° C. The reaction time is preferably 1 hour to 12 hours, more preferably 1 hour to 4 hours.

  Examples of the organic solvent include hydrocarbon solvents such as toluene and xylene, halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, and chloroform, nitro hydrocarbon solvents such as nitrobenzene, ketone solvents such as methyl isobutyl ketone, and 1-methyl-2. -Amide solvents such as pyrrolidone.

The amount of R ⁹ —CO—Z ¹ used is 1 mol or more and 8 mol or less, preferably 1 mol or more and 4 mol or less, with respect to 1 mol of the azo compound represented by the formula (b4).

In the compound of the present invention, compound (I) wherein R ¹ is -L ¹ -X ¹ -R ⁹ and X ¹ is * -CO-O- (* represents the bonding position with L ^1. In other words, a method for producing a compound represented by formula (Ic) (hereinafter sometimes referred to as “compound (Ic)”) will be described.

[In formula (Ic), R ^{2 to} R ⁹ and L ¹ each have the same meaning as described above. ]

The azo compound represented by the formula (c4) is obtained by diazo coupling the diazonium salt represented by the formula (a2) and the pyridone compound represented by the following formula (c3) by the same method as described above. Can be manufactured.

[In formula (c3) and formula (c4), R ^{2 to} R ⁹ and L ¹ each represent the same meaning as described above. ]

Next, the azo compound represented by the formula (c4) and R ⁹ —OH (wherein R ⁹ represents the same meaning as described above) are reacted in the presence of an organic solvent, whereby the compound (Ic) is reacted. Obtainable. The reaction temperature is preferably 30 ° C to 180 ° C, more preferably 50 ° C to 120 ° C. The reaction time is preferably 1 hour to 12 hours, more preferably 1 hour to 4 hours.
Examples of the organic solvent used here include the same solvents as those used in the reaction of the azo compound represented by formula (b4) and R ⁹ —CO—Z ¹ .

The amount of R 9 ^-OH are the azo compound to 1 mole of the formula (c4), is usually 1 mole or more 8 mole or less, preferably 4 mol or less 1 mole or more.

In the reaction, it is more preferable to add an acidic catalyst so that the reaction proceeds smoothly. Examples of the acidic catalyst include mineral acids such as sulfuric acid and hydrochloric acid.
Although the usage-amount of these catalysts is arbitrary, Preferably it is 0.01-4 mol with respect to 1 mol of R < ⁹ > -OH, More preferably, it is 0.8-2 mol.

  The method for obtaining the target compound of the present invention from the reaction mixture is not particularly limited, and various known techniques can be employed. For example, the reaction mixture can be mixed with an acid (such as acetic acid) and water, and the precipitated crystals can be collected by filtration. The acid is preferably prepared by preparing an aqueous solution of the acid in advance, and then adding the reaction mixture to the aqueous solution. The temperature when adding the reaction mixture is usually 10 ° C. or higher and 50 ° C. or lower, preferably 20 ° C. or higher and 50 ° C. or lower, more preferably 20 ° C. or higher and 30 ° C. or lower. Moreover, after adding a reaction mixture to the aqueous solution of an acid, it is preferable to stir at the same temperature for about 0.5 to 2 hours. The crystal collected by filtration is preferably washed with water or the like and then dried. Moreover, you may refine | purify further by well-known methods, such as recrystallization, as needed.

The compounds of the present invention are useful as dyes.
The dye of the present invention is a dye containing the compound of the present invention as an active ingredient. The dye of the present invention is particularly useful as a dye used for a color filter of a display device such as a liquid crystal display device because of its high solubility in an organic solvent.

  The colored photosensitive resin composition of the present invention contains the dye of the present invention as a colorant (hereinafter sometimes referred to as “colorant (A)”), and further contains a resin (B) and a solvent (E). The colored photosensitive resin composition of the present invention preferably further contains a polymerizable compound (C) and a polymerization initiator (D).

In addition to the dye of the present invention, the colorant (A) may further contain a pigment and / or a dye different from the dye of the present invention.
As dyes different from the dyes of the present invention, the Color Index (published by The Society of Dyers and Colorists), Solvent, Acid, Basic, reactive, direct And dyes classified as (Direct), Disperse, or Vat. More specifically, dyes having the following color index (CI) numbers can be mentioned, but the dye is not limited thereto.
C. I. Solvent Yellow 25, 79, 81, 82, 83, 89;
C. I. Acid Yellow 7, 23, 25, 42, 65, 76;
C. I. Reactive Yellow 2, 76, 116;
C. I. Direct yellow 4, 28, 44, 86, 132;
C. I. Disperse Yellow 54,76;
C. I. Solvent orange 41, 54, 56, 99;
C. I. Acid Orange 56, 74, 95, 108, 149, 162;
C. I. Reactive Orange 16;
C. I. Direct orange 26;
C. I. Solvent Red 24, 49, 90, 91, 118, 119, 122, 124, 125, 127, 130, 132, 160, 218;
C. I. Acid Red 73, 91, 92, 97, 138, 151, 211, 274, 289;
C. I. Acid Violet 102;
C. I. Solvent Green 1,5;
C. I. Acid Green 3, 5, 9, 25, 28;
C. I. Basic Green 1;
C. I. Bat Green 1 etc.

Examples of the pigment include organic pigments and inorganic pigments usually used for pigment dispersion resists. Examples of inorganic pigments include metal compounds such as metal oxides and metal complex salts. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony and other metal compounds. Oxides or mixed metal oxides may be mentioned.
Specific examples of organic pigments and inorganic pigments include compounds classified as Pigment under the Color Index (published by The Society of Dyers and Colorists). More specifically, pigments having the following color index (CI) numbers can be mentioned, but the invention is not limited to these.

C. I. Pigment yellow 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173 and 180;
C. I. Pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65 and 71;
C. I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 215, 216, 224, 242, 254, 255 and 264;
C. I. Pigment violet 14, 19, 23, 29, 32, 33, 36, 37 and 38;
C. I. Pigment Green 7, 10, 15, 25, 36, 47 and 58 etc.

The content of the colorant (A) is preferably 5 to 60% by mass with respect to the solid content in the colored photosensitive resin composition. Here, solid content means the sum total of the component except a solvent in a coloring photosensitive resin composition.
The content of the dye of the present invention contained in the colorant (A) is preferably 3 to 100% by mass.
The dye of the present invention, the dye different from the dye of the present invention, and the pigment may be used alone or in combination of two or more.

  The resin (B) is not particularly limited, and any resin may be used. The resin (B) is preferably an alkali-soluble resin, and more preferably a resin containing a structural unit derived from (meth) acrylic acid. Here, (meth) acrylic acid represents acrylic acid and / or methacrylic acid.

  Specific examples of the resin (B) include methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene copolymer, methacrylic acid / benzyl methacrylate / isobornyl methacrylate copolymer, methacrylic acid / styrene. / Benzyl methacrylate / N-phenylmaleimide copolymer, methacrylic acid / styrene / glycidyl methacrylate copolymer, and the like.

The weight average molecular weight in terms of polystyrene of the resin (B) is preferably 5,000 to 35,000, and more preferably 6,000 to 30,000.
The acid value of the resin (B) is preferably 50 to 150, and more preferably 60 to 135.
Content of resin (B) is 7-65 mass% normally with respect to solid content of a coloring photosensitive resin composition, Preferably it is 13-60 mass%.

  The polymerizable compound (C) is not particularly limited as long as it is a compound that can be polymerized by an active radical, an acid, or the like generated from the polymerization initiator (D). For example, the compound etc. which have a polymerizable carbon-carbon unsaturated bond are mentioned.

The polymerizable compound (C) is preferably a photopolymerizable compound having 3 or more polymerizable groups. Examples of the photopolymerizable compound having 3 or more polymerizable groups include pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate and the like. Is mentioned. The photopolymerizable compounds (C) may be used alone or in combination of two or more.
The content of the polymerizable compound (C) is preferably 5 to 65% by mass, more preferably 10 to 60% by mass, based on the solid content of the colored photosensitive resin composition.

As said polymerization initiator (D), an active radical generator, an acid generator, etc. are mentioned. Active radical generators generate active radicals by the action of heat or light. Examples of the active radical generator include alkylphenone compounds, thioxanthone compounds, triazine compounds, and oxime compounds.
Examples of the alkylphenone compound include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, Examples include benzyldimethyl ketal, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, and the like.

  Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like.

  Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4 -Methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl)- 6- [2- (5-Methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (Trichloromethyl 6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

  Examples of the oxime compound include O-acyloxime compounds, and specific examples thereof include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N -Benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine, N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] Ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy) benzoyl} -9H -Carbazol-3-yl] ethane-1-imine and the like.

  Examples of the active radical generator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1, 2'-biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compound and the like may be used.

Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenyl, Onium salts such as methyl benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, and nitrobenzyl tosylate And benzoin tosylate.
The polymerization initiators (D) may be used alone or in combination of two or more.

  The content of the polymerization initiator (D) is preferably 0.1 to 30% by mass, more preferably 1 to 20% by mass, based on the total amount of the resin (B) and the polymerizable compound (C). is there. When the content of the polymerization initiator is within the above range, it is preferable because the sensitivity is increased, the exposure time is shortened, and the productivity is improved.

  Examples of the solvent (E) include ethers, aromatic hydrocarbons, ketones other than those described above, alcohols, esters, amides, and the like.

  Examples of the ether include tetrahydrofuran, tetrahydropyran, 1,4-dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, pro Glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate and the like.

Examples of the aromatic hydrocarbon include benzene, toluene, xylene, mesitylene and the like.
Examples of the ketone include acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, 4-hydroxy-4-methyl-2-pentanone, cyclopentanone, And cyclohexanone.
Examples of the alcohol include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin.

  Examples of the ester include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, and lactic acid. Ethyl, butyl lactate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropion Ethyl acetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-methoxy-2-methylpropionic acid Chill, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, γ -Butyrolactone etc. are mentioned.

Examples of the amide include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like.
These solvents may be used alone or in combination of two or more.

  Content of the solvent (E) in a colored photosensitive resin composition becomes like this. Preferably it is 70-95 mass% with respect to a colored photosensitive resin composition, More preferably, it is 75-90 mass%.

  The colored photosensitive resin composition of the present invention includes, as necessary, surfactants, fillers, other polymer compounds, adhesion promoters, antioxidants, ultraviolet absorbers, light stabilizers, chain transfer agents, and the like. Various additives may be included.

The compounds of the present invention are useful as dyes. Since it has a high molar extinction coefficient and shows solubility in organic solvents, it is particularly useful as a dye for use in color filters of display devices such as liquid crystal display devices.
In addition, the colored photosensitive resin composition of the present invention has various colored images such as a display device (for example, a known liquid crystal display device or an organic EL device) having a color filter as a part of its constituent parts, a solid-state imaging device, or the like. It can be used in a known manner for equipment related to the above.

  Next, the present invention will be described more specifically with reference to examples. In Examples and Comparative Examples, “%” and “part” representing content or use amount are based on mass unless otherwise specified.

  In the following examples, the structure of the compound was confirmed by NMR (JMM-ECA-500; manufactured by JEOL Ltd.).

Example 1
After adding 246 parts of water to 24.6 parts of sodium 4-nitroaniline-2-sulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.), 4.51 parts of sodium hydroxide was added and dissolved. Under ice cooling, 21.2 parts of sodium nitrite was added, and then 64.1 parts of 35% hydrochloric acid was added little by little to dissolve and stirred for 2 hours to obtain a suspension containing a diazonium salt.

  Meanwhile, acetoacetic acid ethyl ester (Tokyo Chemical Industry Co., Ltd.) 26.0 parts, methyl cyanoacetate (Tokyo Chemical Industry Co., Ltd.) 20.8 parts, and 2-aminoethanol (Wako Pure Chemical Industries, Ltd.) 24.4 parts were mixed and stirred at 95 ° C. for 24 hours. The reaction solution was cooled to room temperature, added to a mixed solution of 304 parts of water and 35 parts of 35% hydrochloric acid, and stirred at room temperature for 1 hour. The precipitated crystals were obtained as a suction filtration residue and dried to obtain 20.4 parts of a compound represented by the formula (d1).

  Next, 18.9 parts of the compound represented by the formula (d1) was suspended in 378 parts of water, and the pH was adjusted to 9.0 using sodium hydroxide. The suspension containing the diazonium salt was added dropwise thereto using a pump over 15 minutes. After completion of dropping, the mixture was further stirred for 30 minutes to obtain a yellow suspension. Stir for 1 hour. The yellow solid obtained by filtration was dried at 60 ° C. under reduced pressure to obtain 43.4 parts of a compound represented by the formula (d2).

<Identification of compound represented by formula (d2)>
¹ H-NMR (DMSO-d6): 2.54 (3H), 4.14 (2H), 4.26 (2H), 5.23 (1H), 8.00 (1H), 8.21 (1H ), 8.44 (1H), 15.08 (1H)

To 10.0 parts of the compound represented by the formula (d2), 7.39 parts of the compound represented by the formula (d3) was added, followed by stirring at 70 ° C. for 3 hours in a solvent of N-methylpyrrolidone. After completion of the reaction, the obtained mixture was charged in water, and the precipitated crystals were obtained as a residue of suction filtration and dried to obtain 12.0 parts of a compound represented by the formula (I-43). ^The structure was confirmed by ¹ H-NMR.

<Identification of compound represented by formula (I-43)>
¹ H-NMR (DMSO-d6): 1.10 (3H), 2.49 (2H), 2.49 (2H), 2.56 (3H), 3.96 (2H), 4.10 (2H) ), 4.23 (2H), 8.04 (1H), 8.26 (1H), 8.45 (1H), 11.77 (1H), 15.52 (1H)

Example 2
To 20.0 parts of the compound represented by the above formula (d2), 2.31 parts of the compound represented by the following formula (d4) was added, followed by stirring at 70 ° C. for 3 hours in a solvent of N-methylpyrrolidone. After completion of the reaction, the obtained mixture was charged into water, and the precipitated crystals were obtained as a residue of suction filtration and dried to obtain 11.3 parts of a compound part represented by the formula (I-65). ^The structure was confirmed by ¹ H-NMR.

<Identification of Compound Represented by Formula (I-65)>
¹ H-NMR (DMSO-d6): 0.75 (3H), 0.77 (3H), 1.08 (2H), 1.18 (2H), 1.37 (2H), 1.42 (2H) ), 2.16 (1H), 2.55 (3H), 4.11 (2H), 4.23 (2H), 8.03 (1H), 8.27 (1H), 8.47 (1H) , 11.61 (1H), 15.03 (1H)

Example 3
After adding 250 parts of water to 24.8 parts of sodium 5-nitroaniline-2-sulfonate, 4.55 parts of sodium hydroxide was added and dissolved. Under ice cooling, 21.2 parts of sodium nitrite was added, and then 64.6 parts of 35% hydrochloric acid was added little by little to dissolve and stirred for 2 hours to obtain a suspension containing a diazonium salt.

  Meanwhile, acetoacetic acid ethyl ester (Tokyo Chemical Industry Co., Ltd.) 26.0 parts, methyl cyanoacetate (Tokyo Chemical Industry Co., Ltd.) 20.8 parts, and 2-aminoethanol (Wako Pure Chemical Industries, Ltd.) 24.4 parts were mixed and stirred at 95 ° C. for 24 hours. The reaction solution was cooled to room temperature, added to a mixed solution of 304 parts of water and 35 parts of 35% hydrochloric acid, and stirred at room temperature for 1 hour. The precipitated crystals were obtained as a suction filtration residue and dried to obtain 20.4 parts of a compound represented by the formula (d1).

  Next, 18.9 parts of the compound represented by the formula (d1) was suspended in 380 parts of water, and the pH was adjusted to 9.0 using sodium hydroxide. The suspension containing the diazonium salt was added dropwise thereto using a pump over 15 minutes. After completion of dropping, the mixture was further stirred for 30 minutes to obtain a yellow suspension. Stir for 1 hour. The yellow solid obtained by filtration was dried at 60 ° C. under reduced pressure to obtain 43.0 parts of a compound represented by the formula (d5).

<Identification of compound represented by formula (d5)>
¹ H-NMR (DMSO-d6): 2.53 (3H), 4.15 (2H), 4.24 (2H), 5.23 (1H), 7.82 (1H), 8.01 (1H ), 8.40 (1H), 15.07 (1H)

To 10.0 parts of the compound represented by the formula (d5), 7.39 parts of the compound represented by the formula (d3) was added, followed by stirring at 70 ° C. for 3 hours in a solvent of N-methylpyrrolidone. After completion of the reaction, the obtained mixture was charged in water, and the precipitated crystals were obtained as a suction filtration residue and dried to obtain 11.9 parts of a compound represented by the formula (I-87). ^The structure was confirmed by ¹ H-NMR.

<Identification of Compound Represented by Formula (I-87)>
¹ H-NMR (DMSO-d6): 1.10 (3H), 2.49 (2H), 2.49 (2H), 2.56 (3H), 3.96 (2H), 4.10 (2H ), 4.23 (2H), 7.82 (1H), 8.01 (1H), 8.40 (1H), 11.70 (1H), 15.52 (1H)

Example 4
2.34 parts of the compound represented by the above formula (d4) was added to 20.0 parts of the compound represented by the above formula (d5), and the mixture was stirred at 70 ° C. for 3 hours in a solvent of N-methylpyrrolidone. After completion of the reaction, the obtained mixture was charged in water, and the precipitated crystals were obtained as a suction filtration residue and dried to obtain 11.2 parts of a compound part represented by the formula (I-95). ^The structure was confirmed by ¹ H-NMR.

<Identification of Compound Represented by Formula (I-95)>
¹ H-NMR (DMSO-d6): 0.75 (3H), 0.77 (3H), 1.08 (2H), 1.18 (2H), 1.37 (2H), 1.42 (2H) ), 2.16 (1H), 2.55 (3H), 4.11 (2H), 4.23 (2H), 7.85 (1H), 8.10 (1H), 8.35 (1H) 11.80 (1H), 15.03 (1H)

Comparative Example 1
A compound represented by the formula (i) was obtained by the method described in JP-A-2-153777.

[Measurement of absorption spectrum]
The absorption spectra of the compounds obtained in Examples 1 to 4 and Comparative Example 1 were measured as follows.
Compound 0.10 g was dissolved in dimethylformamide to a volume of 250 cm ³ , 2 cm ^{3 of} which was diluted with ethyl lactate to a volume of 100 cm ³ (concentration: 0.0080 g / L), and an ultraviolet-visible spectrophotometer (V -650DS; manufactured by JASCO Corporation (quartz cell, optical path length: 1 cm), the absorption spectrum was measured. The results are shown in Table 2.

[Evaluation of solubility]
The solubility of the compounds obtained in Examples 1 to 4 and Comparative Example 1 in N-methylpyrrolidone (hereinafter abbreviated as NMP) and N, N′-dimethylformamide (hereinafter abbreviated as DMF) was as follows. Asked.
In a 50 mL sample tube, 0.03 g of the compound and 1 g of the above solvent were mixed, and then the sample tube was sealed and shaken with an ultrasonic shaker at 30 ° C. for 3 minutes. Then, after standing at room temperature for 30 minutes, the mixture was filtered, and the residue was visually observed. If insoluble matter could not be confirmed as a residue, the solubility was judged to be good and marked in Table 3, and if insoluble matter could be confirmed, the solubility was judged to be poor and listed in Table 3. X was marked. The results are shown in Table 3.

Example 5
[Preparation of colored photosensitive resin composition]
(A) Colorant: Compound (I-43): Compound synthesized in Example 1 20 parts (B-1) Resin: Methacrylic acid / benzyl methacrylate copolymer (molar ratio; 30/70; weight average molecular weight 10700, Acid value 70 mg KOH / g) 50 parts (C-1) polymerizable compound: dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) 50 parts (D-1) polymerization initiator: Irgacure OXE01 (oxime compound; manufactured by BASF Japan) ) 15 parts (E-1) Solvent: 680 parts of N, N′-dimethylformamide are mixed to obtain a colored photosensitive resin composition.

Example 6
[Preparation of colored photosensitive resin composition]
(A) Colorant: Compound (I-65): Compound synthesized in Example 2 20 parts (B-1) Resin: Methacrylic acid / benzyl methacrylate copolymer (molar ratio; 30/70; weight average molecular weight 10700, Acid value 70 mg KOH / g) 50 parts (C-1) polymerizable compound: dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) 50 parts (D-1) polymerization initiator: Irgacure OXE01 (oxime compound; manufactured by BASF Japan) ) 15 parts (E-1) Solvent: 680 parts of N, N′-dimethylformamide are mixed to obtain a colored photosensitive resin composition.

Example 7
[Preparation of colored photosensitive resin composition]
(A) Colorant: Compound (I-87): Compound synthesized in Example 3 20 parts (B-1) Resin: Methacrylic acid / benzyl methacrylate copolymer (molar ratio; 30/70; weight average molecular weight 10700, Acid value 70 mg KOH / g) 50 parts (C-1) polymerizable compound: dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) 50 parts (D-1) polymerization initiator: Irgacure OXE01 (oxime compound; manufactured by BASF Japan) ) 15 parts (E-1) Solvent: 680 parts of N, N′-dimethylformamide are mixed to obtain a colored photosensitive resin composition.

Example 8
[Preparation of colored photosensitive resin composition]
(A) Colorant: Compound (I-95): Compound synthesized in Example 4 20 parts (B-1) Resin: Methacrylic acid / benzyl methacrylate copolymer (molar ratio; 30/70; weight average molecular weight 10700, Acid value 70 mg KOH / g) 50 parts (C-1) polymerizable compound: dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) 50 parts (D-1) polymerization initiator: Irgacure OXE01 (oxime compound; manufactured by BASF Japan) ) 15 parts (E-1) Solvent: 680 parts of N, N′-dimethylformamide are mixed to obtain a colored photosensitive resin composition.

[Production of color filters]
On the glass, the colored photosensitive resin composition obtained above is applied by a spin coating method to volatilize volatile components. After cooling, light irradiation is performed using a quartz glass photomask having a pattern and an exposure machine. After light irradiation, development is performed with an aqueous potassium hydroxide solution, and the color filter is obtained by heating to 200 ° C. in an oven.

  From the results in Table 2, it can be seen that the compounds of Examples have a large molar extinction coefficient. Moreover, it turns out that the high solubility with respect to the organic solvent is shown from the result of Table 3. From this, it can be said that it is useful as a dye used for a color filter of a display device.

  The compound of the present invention has a large molar extinction coefficient.

Claims (6)

A compound represented by formula (I).

[In Formula (I), R ¹ represents a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, and —CH ₂ — contained in the aliphatic hydrocarbon group is —O— or It may be replaced by -CO-.
R ² represents a hydrogen atom, a cyano group or a carbamoyl group.
R ³ represents an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom contained in the alkyl group may be substituted with a halogen atom.
R ^{4 to} R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxyalkyl group having 2 to 8 carbon atoms, a hydroxy group, a cyano group, or a nitro group. or an -SO ₃ ^M, at least one of R 4 to R ⁸ is a nitro group, at least one represents -SO ₃ M.
M represents a hydrogen atom or an alkali metal atom. ] The compound of Claim 1 represented by a formula (II).

[In formula (II), R ¹ , R ² , R ³ and M each have the same meaning as described above. ] The compound according to claim 1 or 2, wherein R ¹ is -L ¹ -X ¹ -R ⁹ .
[L ¹ represents an alkanediyl group having 1 to 8 carbon atoms. X ¹ represents —CO—O—. R ⁹ represents a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 17 carbon atoms, and —CH ₂ — contained in the aliphatic hydrocarbon group is replaced by —O— or —CO—. Also good. ] The compound according to claim 3, wherein X ¹ is * -O-CO-.
[* Represents a bond to ^{L 1.} ]   The dye which uses the compound in any one of Claims 1-4 as an active ingredient.   A colored photosensitive resin composition comprising the dye, resin and solvent according to claim 5.