KR20120116341A - Compound - Google Patents

Abstract

PURPOSE: A compound for dye is provided to enhance solubility for organic solvents. CONSTITUTION: A compound for dye is represented by chemical formula(1). In the chemical formula(1), L1 indicates a short-chain, an alkandiyl group having 1-8 carbons, -SO2-, -O-, -CO- or -CO-O-. The hydrogen atom included in the alkandiyl group can be substituted with halogen atom. The -CH2- included in the alkanediyl group can be substituted with -O- or -CO-. R1 and R2 independently indicate the alkyl group with 1-8 carbons or the hydrogen atom. A1 and A2 indicate benzene ring, naphthalene ring or quinoline ring which can independently have substituent. The dye contains a compound of chemical formula(1) as a main component. The coloring composite includes the dye of the chemical formula(1).

Description

Compound {COMPOUND}

The present invention relates to compounds useful as dyes.

Dye is used for color display using reflected light or transmitted light, for example in the field of a fiber material, a liquid crystal display device, an inkjet, etc.

As such a dye, for example, Quinophthalone dye C.I. Acid Yellow 3 is widely known.

[Non-Patent Document 1] Masao Yokote, Fukumatsu Shibamiya, Synthetic Dye, First Edition, Nikkan Kogyo Shimbun, April 1978, 128 pages

The compounds known in the art have not been sufficiently satisfactory for their solubility in organic solvents.

The present invention provides the following [1] to [10].

[1] Formula (１)

In the formula ^(1), L 1 represents a single bond, having from 1 to 8 alkanediyl _{group, -SO 2 -?, -O-,} -CO- , or represents -CO-O-, contained in the alkanediyl group The hydrogen atom may be substituted with the halogen atom, and -CH ₂ -contained in the alkanediyl group may be substituted with -O- or -CO-.

R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

A ¹ and A ² each independently represent a benzene ring which may have a substituent, a naphthalene ring which may have a substituent, or a quinoline ring which may have a substituent.

m and n represent the integer of 0-5 independently of each other. However, m + n is an integer of 1-8. When m + n is an integer of 2 or more, a plurality of -SO ₂ NR ¹ R ² are the same as or different from each other].

[2] The compound according to [1], wherein A ¹ is a benzene ring which may have a substituent.

[3] The compound as described in [1] or [2], wherein A ¹ is an unsubstituted benzene ring or a benzene ring having a halogeno group.

[4] The compound according to any one of [1] to [3], wherein A ¹ and A ² are each independently a benzene ring which may have a substituent.

[5] The compound according to any one of [1] to [4], wherein A ¹ and A ² are each independently an unsubstituted benzene ring or a benzene ring having a halogeno group.

[6] The compound according to any one of [1] to [5], wherein R ¹ and R ² are each independently a hydrogen atom or a branched alkyl group having 1 to 8 carbon atoms.

[7] The compound according to any one of [1] to [6], wherein L ¹ is a single bond or -SO _2- .

[Vi] The compound as described in any one of [1]-[7] whose m + n is an integer of 1-5.

[Iii] A dye containing the compound according to any one of [1] and [VII] as a main component.

The coloring composition containing the dye as described in [IX].

The compound of the present invention is excellent in solubility in organic solvents.

 The compound of the present invention is a compound represented by the formula (1) hereinafter referred to as "compound (1)".

In the formula ^(1), L 1 represents a single bond, having from 1 to 8 alkanediyl _{group, -SO 2 -?, -O-,} -CO- , or represents -CO-O-, contained in the alkanediyl group The hydrogen atom may be substituted with the halogen atom, and -CH ₂ -contained in the alkanediyl group may be substituted with -O- or -CO-.

R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

A ¹ and A ² each independently represent a benzene ring which may have a substituent, a naphthalene ring which may have a substituent, or a quinoline ring which may have a substituent.

m and n represent the integer of 0-5 independently of each other. However, m + n is an integer of 1-8. when m + n is an integer of 2 or more, a plurality of -SO ₂ NR ¹ R ² are the same as or different from each other].

L ¹ represents a single bond, an alkanediyl group having 1 to 8 carbon atoms, -SO _2- , -O-, -CO-, or -CO-O-. L ¹ is preferably a single bond or -SO ₂ -from the viewpoint of heat resistance.

Examples of the alkanediyl group having 1 to 8 carbon atoms include methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, propane-2,2-diyl group, butane-1, 4-diyl group, butane-1,3-diyl group, butane-2,2-diyl group, pentane-1,5-diyl group, pentane-2,2-diyl group, 2-methylbutane-3,3- Diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, etc. are mentioned.

As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned.

As a group in which the hydrogen atom contained in a C1-C8 alkanediyl group is substituted by the halogen atom, it is a 1,1,1,3,3,3-hexafluoropropane-2,2-diyl group, 2, 2-difluoropropane-1,3-diyl group, 2,2-dichloropropane-1,3-diyl group, etc. are mentioned.

? Having 1 to 8 alkanediyl -CH ₂ contained in the diary - as a group which is substituted with -O- or -CO-, for example, the following groups represented by the following formula, and the like. In the following formulae, * represents a bonding hand.

R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. As a C1-C8 alkyl group in R <^1> and R <^2> , a methyl group, an ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-jade Straight chain alkyl groups such as a methyl 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-ethyl Butyl, 1-methylhexyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 1-ethylpentyl, 2-ethylpentyl, 3-ethylpentyl , 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, 5-methylheptyl group, 6-methylheptyl group, 1-ethylhexyl group, 2-ethylhexyl group, 3-ethylhexyl group, 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-dimethyl Butyl 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-dimethylpentyl 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 Real 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-methyl moiety Methyl group, 1-propyl-2-methylbutyl group, 1-propyl-3-methylbutyl group, 1- (1-methylethyl) -1-methylbutyl group, 1- (1-methylethyl) -2-methylbutyl And branched alkyl groups such as groups, 1- (1-methylethyl) -3-methylbutyl group, 1,1-diethylbutyl group and 1,2-diethylbutyl group.

Among these, R ¹ and R ² are each independently a branched alkyl group having 3 to 8 carbon atoms, more preferably a branched alkyl group having 6 to 8 carbon atoms, even more preferably a branched alkyl group having 8 carbon atoms, It is further more preferable that it is a 2-ethylhexyl group.

Examples of —SO ₂ NR ¹ R ² include an unsubstituted sulfamoyl group, an N-1 substituted sulfamoyl group, and an N, N-2 substituted sulfamoyl group.

As an N-1 substituted sulfamoyl group, For example, N-methyl sulfamoyl group, N-ethyl sulfamoyl group, N-propyl sulfamoyl group, N-isopropyl sulfamoyl group, N-butyl sulfamoyl group, N Isobutyl sulfamoyl group, N-sec-butyl sulfamoyl group, N-tert-butyl sulfamoyl group, N-pentyl sulfamoyl group, N- (1-ethylpropyl) sulfamoyl group, N- (1,1 -Dimethylpropyl) sulfamoyl group, N- (1,2-dimethylpropyl) sulfamoyl group, N- (2,2-dimethylpropyl) sulfamoyl group, N- (1-methylbutyl) sulfamoyl group, N- (2-methylbutyl) sulfamoyl group, N- (3-methylbutyl) sulfamoyl group, N-cyclopentylsulfamoyl group, N-hexyl sulfamoyl group, N- (1,3-dimethylbutyl) sulfamoyl group , N- (3,3-dimethylbutyl) sulfamoyl group, N-heptylsulfamoyl group, N- (1-methylhexyl) sulfamoyl group, N- (1,4-dimethylpentyl) sulfamoyl group, N- Octyl sulfamoyl group, N- (2-ethylhexyl) sulfamoyl group, N- (1,5-dimethyl) hexyl sulfamoyl group, N- (1,1,2,2-tetramethylbutyl) sulfamoyl group Can be mentioned.

Examples of the N, N-2 substituted sulfamoyl group include, for example, N, N-dimethylsulfamoyl group, N, N-ethylmethylsulfamoyl group, N, N-diethylsulfamoyl group, and N, N-propylmethyl Sulfamoyl group, N, N-isopropylmethylsulfamoyl group, N, N-tert-butylmethylsulfamoyl group, N, N-butylethylsulfamoyl group, N, N-bis (1-methylpropyl) sulfamo A diary, N, N-heptylmethyl sulfamoyl group, etc. are mentioned.

m and n represent the integer of 0-5 independently of each other. However, m + n is an integer of 1-8, Preferably it is an integer of 1-5. Moreover, it is preferable that m and n are 0 or 1 independently of each other, and m + n is 1 further.

-SO ^₂ NR ¹ R ₂ if present, a plurality of preferably they are the same type of group to each other.

A <^1> and A <^2> represent the benzene ring which may have a substituent independently, the naphthalene goli which may have a substituent, or the quinoline ring which may have a substituent independently of each other. As such a substituent, -R ^3- , -OR ^3- , -COR ^3- , -O-COR ³ , a C1-C8 fluorinated alkyl group, a halogeno group, a hydroxyl group, a sulfanyl group, a carboxyl group, a nitro group, a formyl group , -NHR ³ , -NR ³ R ⁴ , and the like. Here, R <^3> and R <^4> represent a C1-C8 alkyl group, and the group similar to what was mentioned above is mentioned as said alkyl group.

As a C1-C8 fluorinated alkyl group, a fluoromethyl group, a trifluoromethyl group, a fluoroethyl group, pentafluoroethyl group, a perfluoro propyl group, a perfluoro butyl group, a perfluoro pentyl group, perfluoro, for example A rohexyl group, a perfluoroheptyl group, a perfluorooctyl group, etc. are mentioned.

Examples of -OR ³ include a methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group and the like.

Examples of -COR ³ include an acetyl group, propionyl group, butyryl group, valeryl group, pivaloyl group and the like.

Examples of -O-COR ³ include an acetyloxy group, propionyloxy group, butyryloxy group, valeryloxy group, pivaloyloxy group, and the like.

Examples of -NHR ³ include N-methylamino group, N-ethylamino group, N-propylamino group, N-butylamino group, N-pentylamino group, N-octylamino group, and the like.

As —NR ³ R ⁴ , for example, N, N-dimethylamino group, N, N-diethylamino group, N, N-dipropylamino group, N, N-dibutylamino group, N-butyl-N-methylamino group, N, N-dioctylamino group etc. are mentioned.

As a halogeno group, a fluoro group, a chloro group, a bromo group, an iodine group, etc. are mentioned, Preferably it is a chloro group.

Among the, A ¹ is more preferably a benzene ring preferably a benzene ring which may have a substituent group, and, A ¹ is to have a non-substituted benzene ring, or a halo group. In this form, it is preferable that the halogeno group is a chloro group.

In addition, A ¹ and A ² are independently preferably a benzene ring which may have a substituent group, and, A ¹ and A ² is more preferably a benzene ring independently to the non-substituted benzene ring or a halo with the group with one another . In this form, it is preferable that the halogeno group is a chloro group.

In addition, A ¹ and A ² are each independently an unsubstituted benzene ring or a benzene ring having a halogeno group, R ¹ and R ² are each independently a hydrogen atom or a branched alkyl group having 8 carbon atoms, and L ¹ is bond or -SO ₂ -, and a is 0 or 1 and m and n independently from each other, and it is preferable that m + n is 1. In this form, it is preferable that the halogeno group is a chloro group.

Moreover, A <^1> and A <^2> are the same, and they are the unsubstituted benzene ring or the benzene ring which has a halogeno group, R <^1> and R <^2> are the same and are a hydrogen atom or a C8 branched alkyl group, L <^1> is a single bond or -SO ₂ -, m and n are independently 0 or 1 to each other, and it is more preferred that m + n is 1. In this form, it is preferable that the halogeno group is a chloro group.

In compound (1)

또는

or

As group represented by these, the group etc. which are represented by following formula (VII-1) -formula (VII-46) are mentioned. Among these, formula (V1), formula (V1-4), formula (V2-4), formula (V2-2), formula (V3), formula (V3), formula (V3) ), Formulas (V3) and formulas (V3) are preferred, and the formulas (V1), (V1-4), (2-2), (3) and (3) Group represented by? 38) is more preferable. In the following formula, x represents m or n.

Since the preparation of compound (1) is easy,

와

는 동일한 구조인 것이 바람직하다.

Wow

Is preferably the same structure.

As compound (1), a compound (1-1)-a compound (1-40) etc. are mentioned, for example. Moreover, Q ¹

를 나타내고, Q²는

And Q ² is

를 나타낸다. 표 1에서, Q¹란 및 Q²란은 상기에 예시한 기의 식의 번호를 기재한다.

Indicates. In Table 1, the Q ¹ column and the Q ² column describe the numbers of the formulas of the groups exemplified above.

Compound (1) can be manufactured by introducing a sulfo group into the compound represented by Formula (i) and then sulfonating the sulfo group.

[Wherein L ¹ , A ¹ and A ² represent the same meaning as described above]

The compound represented by Formula (VII) [hereinafter, referred to as "compound (VII)") is produced by reacting the compound represented by Formula (VII), the compound represented by Formula (VII) and the compound represented by Formula (VII) in an organic solvent. can do.

[L <^1> , A <^1> and A <^2> show the same meaning as the above in Formula (VII), Formula (XI1), and Formula (VII2).

Organic solvents used for the reaction include N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, sulfolane, N, N-dimethylformamide, N, N-dimethylacetamide and mixed solvents thereof Can be mentioned. Although the usage-amount of an organic solvent changes with kinds of solvent, it is 3-50 mass parts with respect to 1 mass part of compounds represented by Formula (i), Preferably it is 5-20 mass parts.

2-8 mol is preferable with respect to 1 mol of usage-amounts of the compound represented by Formula (Xi), and, as for the total usage-amount of the compound represented by Formula (X1) and Formula (X2), 3-5 mol is more preferable.

150-250 degreeC is preferable and 180-220 degreeC of reaction temperature is more preferable. 5-72 hours are preferable and, as for reaction time, 8-24 hours are more preferable.

After completion | finish of reaction, a reaction liquid can be obtained by mixing with a poor solvent of a compound, and filtering a precipitate. As a poor solvent, acetonitrile, ethyl acetate, tetrahydrofuran, diethyl ether, etc. are mentioned, for example.

The use amount of the poor solvent is preferably 1 to 50 parts by mass, and more preferably 5 to 20 parts by mass with respect to 1 part by mass of the reaction liquid.

The precipitate obtained by filtration is preferably washed with an alcohol solvent or the like and then dried. Moreover, you may refine | purify further by well-known methods, such as recrystallization as needed. Methanol, ethanol, isopropyl alcohol, etc. are mentioned as an alcohol solvent used for washing | cleaning.

Subsequently, the compound (i) is sulfonated to introduce a sulfo group. Sulfonation can be performed by a well-known method, Preferably there is a method of sulfonating directly using a sulfonating agent in a compound (i). By bringing a compound and a sulfonating agent into contact and reacting both, the compound which introduce | transduced the sulfo group into the compound (henceforth "sulfonic acid compound (VII)") can be produced.

Examples of the sulfonating agent include chlorosulfonic acid, sulfuryl chloride, sulfuric acid, fuming sulfuric acid, sulfur trioxide, and the like, and chlorosulfonic acid is preferable. As for the usage-amount of a sulfonating agent, 1-20 mass parts is preferable with respect to 1 mass part of compound (X), and 5-10 mass parts is more preferable.

50-150 degreeC is preferable and 70-100 degreeC of reaction temperature is more preferable. 2-15 hours are preferable and, as for reaction time, 4-8 hours are more preferable.

The produced sulfonic acid compound (X1) may be extracted by a known method, or the mixed solution after the sulfonation reaction may be used as it is for the next sulfonation reaction.

Subsequently, the sulfonic acid compound (XI1) is sulfonated. Compound (1) can be obtained by halogenating the sulfo group which has a sulfonic acid compound (X1) to produce the sulfonyl halide compound (X2), and then reacting the sulfonyl halide compound (X2) with an amine compound.

The sulfonic acid compound (X1) can be halogenated, for example, using a halogenated thionyl compound. As a halogenated thionyl compound, thionyl chloride is mentioned, for example. As for the usage-amount of the halogenated thionyl compound, 1-10 mol is preferable with respect to 1 mol of sulfonic acid compounds (X1). However, when water is brought into the reaction system, such as when the water content of the sulfonic acid compound (X1) to be used is large, it is preferable to decompose water using an excess amount.

The reaction may be carried out without solvent or in a solvent. As said solvent, For example, ethers, such as tetrahydrofuran and a 1, 4- dioxane; Halogenated hydrocarbons such as chloroform, methylene chloride, 1,2-dichloroethane, tetrachloroethylene, dichloropropane, amyl chloride and 1,2-dibromoethane; Nitriles such as acetonitrile; Amides, such as N-methyl- 2-pyrrolidone, etc. are mentioned. Among these, chloroform, acetonitrile and N-methyl-2-pyrrolidone are preferable.

3-10 mass is preferable with respect to 1 mass part of sulfonic acid compounds (X1), and, as for the usage-amount of a solvent, 5-8 mass is more preferable.

0-100 degreeC is preferable and 50-80 degreeC of reaction temperature is more preferable. The reaction time is 0.5 to 10 hours, preferably 1 to 5 hours.

The produced sulfonyl halide compound (X2) may be extracted by a known method, or the reaction mixture may be used for reaction with an amine compound as it is.

As a method of extracting a sulfonyl halide compound (X2), the sulfonyl halide compound (X2) can be obtained by mixing the reaction liquid after completion | finish of reaction with ice water, and filtering a precipitate. The amount of ice water used is preferably 3 to 20 parts by mass, and more preferably 5 to 12 parts by mass with respect to 1 part by mass of the reaction mixture. It is preferable that the precipitate obtained by filtration reduces the residual of a halogenated thionyl compound by water washing etc.

Reaction of a sulfonyl halide compound (X2) and an amine compound can be performed by mixing in a solvent. As a solvent used for reaction, amides, such as N-methyl- 2-pyrrolidone, are mentioned, for example. The reaction may be carried out in the presence of a basic catalyst. After mixing a sulfonyl halide compound (X2) with a solvent, it is preferable to add dropwise an amine compound.

Examples of the amine compound include n-propylamine, n-butylamine, n-hexylamine, 1,5-dimethylhexylamine, 1,1,3,3-tetramethylbutylamine, 2-ethylhexylamine, 3 -Amino-1-phenylbutane, isopropoxypropylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, etc. are mentioned. You may use these individually or in combination of 2 or more types.

As for the usage-amount of an amine compound, 3-10 mol is preferable with respect to 1 mol of sulfonyl halide compounds (X2), and 3-7 mol is more preferable.

As a basic catalyst, tertiary amines, such as triethylamine, triethanolamine, pyridine, are preferable, for example. The use amount of basic catalyst is 1.1-2 mol with respect to 1 mol of amine compounds. A basic catalyst may be added dropwise simultaneously with an amine compound, and may be added separately from an amine compound.

0-50 degreeC is preferable, 0-30 degreeC is more preferable, and 5-20 degreeC is more preferable. The reaction time is preferably 1 to 25 hours.

Compound (1) can be obtained by filtering a precipitate in the reaction liquid after completion | finish of reaction with an amine compound. You may mix alcohol solvent and / or acidic aqueous solution, such as methanol, ethanol, and isopropyl alcohol, with the said reaction liquid, and after filtering a product, you may filter out. The amount of the alcohol solvent used is preferably 10 to 100 parts by mass, more preferably 20 to 50 parts by mass with respect to 1 part by mass of the reaction solution. As the acidic aqueous solution, an aqueous solution of an acidic substance can be used. PH = 0-6 is preferable and, as for the hydrogen ion concentration of an acidic aqueous solution, 1-5 are more preferable. Although it does not specifically limit as an acidic substance, For example, ammonium chloride, oxalic acid, acetic acid, hydrochloric acid, a sulfuric acid, etc. are mentioned. The use amount of the acidic aqueous solution is preferably 1 to 10 parts by mass, more preferably 2 to 5 parts by mass with respect to 1 part by mass of the reaction solution.

It is preferable that the compound (1) obtained by filtration is washed with an alcohol solvent or the like. Methanol, ethanol, isopropyl alcohol, etc. are mentioned as an alcohol solvent used for washing | cleaning. It is preferable to dry after washing | cleaning.

Since the compound of this invention obtained in this way has high heat resistance, it is especially useful as dye used for the color filter of display apparatuses, such as a liquid crystal display device.

It is preferable that the coloring composition of this invention contains the compound of this invention as a coloring agent (henceforth "coloring agent (A)"), and contains resin further. It is further more preferable that the coloring composition of this invention contains 1 or more types chosen from the group which consists of a polymeric compound (C), a polymerization initiator (D), and a solvent (E).

In addition to the compound of this invention, a coloring agent (A) may contain the pigment and / or dye (however different from the compound of this invention).

Examples of the dye include Solvent, Acid, Basic, Reactive, Direct, and Disperse in the Color Index (Published by The Society of Dyers and Colourists). Or dyes classified as bats. More specifically, dyes having the following color index (C.I.) numbers may be mentioned, but are not limited thereto. Among these, organic solvent soluble dye is preferable.

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. Dispulse 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.

As said pigment, the organic pigment or inorganic pigment normally used for a pigment dispersion registry is mentioned. Examples of the inorganic pigments include metal compounds such as metal oxides and metal complex salts. Specifically, oxides or complex metal oxides of metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc and antimony Can be mentioned. Moreover, as an organic pigment and an inorganic pigment, the compound specifically classified by Pigment in the Color Index (The Society of Dyers and Colourists) is mentioned. More specifically, the pigment of the following color index (C.I.) number is mentioned, It 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;

Content of a coloring agent (A) becomes like this. Preferably it is 5-60 mass% with respect to solid content in a coloring composition. Here, solid content means the sum total of the component except the solvent in a coloring composition.

Content of the compound of this invention contained in a coloring agent (A) becomes like this. Preferably it is 3-100 mass%.

You may use these dyes and pigments individually or in combination of 2 or more types like the compound of this invention.

It does not specifically limit as resin, You may use any resin. It is preferable that resin (i) is alkali-soluble resin, and it is still more preferable that it is resin containing the structural unit guide | induced from (meth) acrylic acid. Here, (meth) acrylic acid represents acrylic acid and / or methacrylic acid.

Specific examples of the resin 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, etc. are mentioned.

As for the polystyrene conversion weight average molecular weight of resin, 5,000-35,000 are preferable, More preferably, it is 6,000-30,000.

As for the acid value of resin, 50-150 are preferable, More preferably, it is 60-135. Content of resin is preferably 7-65 mass% with respect to solid content of a coloring composition, More preferably, it is 13-60 mass%.

A polymerizable compound (C) will not be specifically limited if it is a compound which can superpose | polymerize with the active radical, the acid, etc. which generate | occur | produced in the polymerization initiator (D). For example, the compound etc. which have a polymerizable ethylenically unsaturated bond are mentioned.

As said polymeric compound (C), it is preferable that it is a polymeric compound which has 3 or more of polymeric groups. As a polymeric compound which has three or more polymerizable groups, for example, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerytate Lithol hexaacrylate, dipentaerythritol hexamethacrylate, etc. are mentioned. You may use these polymeric compounds individually or in combination of 2 or more types.

It is preferable that content of a polymeric compound (C) is 5-65 mass% with respect to solid content of a coloring composition, More preferably, it is 10-60 mass%.

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, oxime compounds, and the like.

As said alkylphenone compound, 2-methyl-2- morpholino-1- (4-methylsulfanylphenyl) propane-1-one, 2-hydroxy-2-methyl-1-phenyl propane-, for example 1-one, benzyl dimethyl ketal, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexylphenyl ketone, etc. are mentioned. have.

As said thioxanthone compound, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, 1-chloro-, for example 4-propoxy city oxanthone etc. are mentioned.

As said triazine compound, it is 2, 4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1, 3, 5- triazine, 2, 4-bis (trichloromethyl), for example. -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-tri Azine, 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 etc. are mentioned.

Examples of the oxime compound include O-acyl oxime compounds, and specific examples thereof include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine and N- Benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine, N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-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, etc. are mentioned.

As the active radical generator, for example, 2,4,6-trimethylbenzoyl diphenylphosphine 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, phenylglyoxylate, titanocene compound, etc. May be used.

As said acid generator, 4-hydroxyphenyl dimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyl dimethylsulfonium hexafluoro antimonate, 4-acetoxyphenyl dimethylsulfonium p-toluene, for example Sulfonate, 4-acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfo Onium salts such as nate and diphenyl iodonium hexafluoroantimonate, nitrobenzyl tosylates, benzointosylates and the like.

You may use these polymerization initiators individually or in combination of 2 or more types.

Content of a polymerization initiator (D) becomes like this. Preferably it is 0.1-30 mass parts with respect to 100 mass parts of total amounts of resin (K) and a polymeric compound (C), More preferably, it is 1-20 mass parts. When content of a polymerization initiator exists in the said range, since it becomes high sensitivity and shortens an exposure time and improves productivity, it is preferable.

The solvent (E) is not particularly limited as long as the compound of the present invention can be dissolved, and examples thereof include ethers, aromatic hydrocarbons, ketones, alcohols, esters, amides, and the like.

Examples of the ethers include tetrahydrofuran, tetrahydropyran, 1,4-dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether and 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, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol And the like can be furnace-butyl ether acetate.

As said aromatic hydrocarbons, benzene, toluene, xylene, mesitylene, etc. are mentioned, for example.

As said ketones, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, 4-hydroxy-4-methyl-2-, for example Pentanone, cyclopentanone, cyclohexanone, etc. are mentioned.

As said alcohol, methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin, etc. are mentioned, for example.

As said ester, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, lactic acid, for example Methyl, ethyl lactate, butyl lactate, methoxyacetic acid methyl, methoxyacetic acid ethyl, methoxyacetic acid butyl, ethoxyacetic acid methyl, ethoxyacetic acid ethyl, 3-methoxypropionate methyl, 3-methoxypropionate ethyl 3- Methyl oxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionic acid, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-methoxy Methyl 2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, acetoacetic acid Methyl, ethyl acetoacetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, (gamma) -butyrolactone, etc. are mentioned.

As said amides, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, etc. are mentioned, for example.

You may use these solvents individually or in combination of 2 or more types.

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

The coloring composition of this invention may contain various additives, such as surfactant, a filler, other polymeric compounds, adhesion promoter, antioxidant, an ultraviolet absorber, a light stabilizer, a chain transfer agent, as needed.

Since the compound of this invention shows high heat resistance, it is especially useful as a coloring agent used for color filters of display apparatuses, such as a liquid crystal display device.

Moreover, the coloring composition of this invention relates to various colored images, such as a display apparatus (for example, a well-known liquid crystal display device, an organic electroluminescent apparatus, etc.), a solid-state image sensor, etc. which comprise a color filter as a part of its component parts. It can be used in a form known in the device.

[Example]

Next, an Example is given and this invention is demonstrated further more concretely. In the examples,% and parts indicating content to amount of use are based on mass unless otherwise specified.

In the following examples, the structure of the compound is elemental analysis [VARIO-EL; (Made by Elemental Co., Ltd.) and elemental analysis (LC; 1200 by Agilent, MASS; LC / MSD by Agilent).

Example 1

53.26 parts of sulfolane was added to 7.00 parts of the compound (manufactured by Tokyo Kasei Co., Ltd.) represented by the formula (VII-1), and then heated to dissolve at 180 ° C. After confirming the dissolution, 11.19 parts of quinaldine (manufactured by Tokyo Kasei Co., Ltd.) was added, and the mixture was refluxed at 200 ° C. for 9 hours to react. After the reaction was completed, the reaction solution was poured into 500 parts of acetonitrile and the precipitate was filtered off. The obtained precipitate was pulped twice with 500 parts of ethanol and twice with 500 parts of dimethyl sulfoxide, to obtain a yellow solid. The said yellow solid was dried at 60 degreeC under reduced pressure, and 4.5 parts of compounds which are represented by a formula (VII-1) were obtained.

Identification of the compound represented by formula (XI-1);

(Elemental Analysis) C 70.84 H 3.28 N 4.75 S 5.09

Subsequently, 7.0 parts of compounds represented by Formula (VII-1) were added to 67.0 parts of chlorosulfonic acid, and it stirred at 70 degreeC for 4 hours. After stirring, 10.95 parts of thionyl chloride was added dropwise to the reaction solution, the mixture was stirred at 80 ° C for 2 hours, cooled to 15 ° C, and stirring was continued for 14 hours as it was. After the completion of the reaction, the mixture was slowly added to 556 parts of ice water, and stirred and filtered. The obtained residue was combined with 200 parts of N-methyl-2-pyrrolidone, and 29.73 parts of 2-ethylhexylamine were added dropwise thereto, and the mixture was kept at 20 to 30 ° C. and stirred for 18 hours, followed by filtration. Got water. The residue was added to 800 parts of 20% aqueous acetic acid solution, stirred for 2 hours, and then obtained by filtration. The residue was added to 400 parts of acetonitrile and after stirring for 2 hours, a yellow solid was obtained by filtration. 4.93 parts of compounds represented by Formula (I-5) were obtained by drying the said yellow solid at 60 degreeC under reduced pressure for 15 hours.

Identification of the compound represented by formula (I? 5)

(Mass spectrometry) ionization mode = ESI +: m / z = 780.3 [Ｍ] ⁺

Exact Mass: 799.2

From the above results, it was confirmed that m + n was one.

[Example 2]

53.26 parts of sulfolane was added to 7.00 parts of the compound represented by the formula (VII-1), and then heated to 18 ° C to dissolve it. After dissolution was confirmed, 13.88 parts of 8-chloroquinaldine was added and refluxed at 200 ° C. for 9 hours. After the reaction was completed, the reaction solution was poured into 500 parts of acetonitrile and the precipitate was filtered off. The obtained precipitate was pulped twice with 500 parts of ethanol and twice with 500 parts of dimethyl sulfoxide, to obtain a yellow solid. The said yellow solid was dried at 60 degreeC under reduced pressure, and 8.15 parts of compounds which are represented by a formula (VII-2) were obtained.

Identification of the compound represented by formula (X2);

(Elemental Analysis) C 63.3 H 2.8 N 3.8 Cl 10.2 S 5.0

Next, 3.0 parts of compounds represented by Formula (X2) were added to 25.8 parts of chlorosulfonic acid, and it stirred at 70 degreeC for 4 hours. After stirring, 4.21 parts of thionyl chloride was added dropwise to the reaction solution, stirred at 80 ° C. for 2 hours, cooled to 15 ° C. or less, and continued stirring for 14 hours as it was. After the completion of the reaction, the mixture was slowly added to 556 parts of ice water, and stirred and filtered. The obtained residue was combined with 100 parts of N-methyl-2-pyrrolidone, and 5.72 parts of 2-ethylhexylamine were added dropwise thereto, and the mixture was kept at 20 to 30 ° C and stirred for 18 hours, followed by filtration. Got water. The residue was added to 400 parts of 20% acetic acid aqueous solution, stirred for 2 hours, and then obtained by filtration. The residue was added to 400 parts of acetonitrile and after stirring for 2 hours, a yellow solid was obtained by filtration. 2.93 parts of compounds represented by Formula (II-20) were obtained by drying the said yellow solid at 60 degreeC under reduced pressure for 15 hours.

Identification of the compound represented by formula (II-20)

(Mass spectrometry) ionization mode = ESI +: m / z = 868.3 [M] ⁺

Exact Mass: 867.1

In the above result, it was confirmed that m + n is 1.

[Example 3]

92.65 parts of sulfolane was added to 10.0 parts of compounds (manufactured by Tokyo Kasei Co., Ltd.) represented by the formula (VII-2), and then heated to dissolve at 180 ° C. After confirming dissolution, 24.15 parts of quinaldine was added and refluxed at 200 ° C. for 9 hours. After the reaction was completed, the reaction solution was poured into 500 parts of acetonitrile and the precipitate was filtered off. The obtained precipitate was pulped twice with 500 parts of ethanol and twice with 500 parts of dimethyl sulfoxide, to obtain a yellow solid. The said yellow solid was dried at 60 degreeC under reduced pressure, and 13.5 parts of compounds which are represented by a formula (VII-3) were obtained.

Identification of the compound represented by formula (VIII);

(Elemental Analysis) C 79.97 H 3.68 N 5.31

Next, 5.0 parts of compounds represented by Formula (VIII) were added to 53.5 parts of chlorosulfonic acid, and it stirred at 70 degreeC for 4 hours. After stirring, 8.74 parts of thionyl chloride was added dropwise to the reaction solution, stirred at 80 ° C. for 2 hours, cooled to 15 ° C., and stirring was continued for 14 hours as it was. After the completion of the reaction, the mixture was slowly added to 556 parts of ice water, and stirred and filtered. The obtained residue was combined with 200 parts of N-methyl-2-pyrrolidone, and 11.87 parts of 2-ethylhexylamine were added dropwise thereto, and the mixture was kept at 20 to 30 ° C, stirred for 18 hours, and then remained by filtration. Got water. The residue was added to 800 parts of 20% aqueous acetic acid solution, stirred for 2 hours, and then obtained by filtration. The residue was added to 400 parts of acetonitrile and after stirring for 2 hours, a yellow solid was obtained by filtration. The yellow solid was dried at 60 ° C. under reduced pressure for 15 hours to obtain 4.93 parts of the compound represented by formula (II-50).

Identification of the compound represented by formula (I-50)

(Mass spectrometry) ionization mode = ESI +: m / z = 736.3 [M] ⁺

Exact Mass: 735.2

In the above result, it was confirmed that m + n is 1.

Example 4

After adding 64.86 parts of sulfolane to 7.0 parts of the compound represented by the formula (X2), it was heated to dissolve at 180 ° C. After confirming dissolution, 16.90 parts of 8-chloroquinaldine was added and refluxed at 200 ° C. for 9 hours. After the reaction was completed, the reaction solution was poured into 500 parts of acetonitrile and the precipitate was filtered off. The obtained precipitate was pulped twice with 500 parts of ethanol and twice with 500 parts of dimethyl sulfoxide, to obtain a yellow solid. The said yellow solid was dried at 60 degreeC under reduced pressure, and 9.0 parts of compounds which are represented by a formula (V4) were obtained.

Identification of the compound represented by formula (V4);

(Elemental Analysis) C 68.5 H 3.0 N 3.6 Cl 10.4

Subsequently, 5.0 parts of compounds represented by Formula (IV-4) were added to 47.5 parts of chlorosulfonic acid, and it stirred at 70 degreeC for 4 hours. After stirring, 7.76 parts of thionyl chloride was added dropwise to the reaction solution, stirred at 80 ° C. for 2 hours, cooled to 15 ° C., and stirring was continued for 14 hours as it was. After the completion of the reaction, the mixture was slowly added to 556 parts of ice water, and stirred and filtered. The obtained residue was combined with 200 parts of N-methyl-2-pyrrolidone, and 5.27 parts of 2-ethylhexylamine were added dropwise thereto, and the mixture was kept at 20 to 30 ° C. and stirred for 18 hours, followed by filtration. Got water. The residue was added to 800 parts of 20% aqueous acetic acid solution, stirred for 2 hours, and then obtained by filtration. The residue was added to 400 parts of acetonitrile and after stirring for 2 hours, a yellow solid was obtained by filtration. The yellow solid was dried at 60 ° C. under reduced pressure for 15 hours to obtain 4.93 parts of the compound represented by formula (I-6).

Identification of the compound represented by formula (I-665)

(Mass spectrometry) ionization mode = ESI +: m / z = 804.3 [Ｍ] ⁺

Exact Mass: 803.2

In the above result, it was confirmed that m + n is 1.

Solubility Assessment

About the compound obtained in Examples 1-4 and the compound of Comparative Example 1, propylene glycol monomethyl ether (hereinafter abbreviated as PGME), propylene glycol monomethyl ether acetate (hereinafter abbreviated as PGMEA), cyclohexanone ( Hereinafter, solubility in CHN) and N-methylpyrrolidone (hereinafter abbreviated as NMP) was obtained as follows.

In a 50 mL sample tube, 0.1 g of the compound and 1 g of the solvent were mixed in the following proportions, after which the sample tube was sealed and vibrated with an ultrasonic vibrator for 3 minutes at 30 ° C. Subsequently, it was left at room temperature for 30 minutes and then filtered to observe the residue thereof. When insoluble matters could not be determined, it was determined that the solubility was good, and it was described as ○ in Table 2, and when insoluble matters were determined, the solubility was considered poor, and it was described as × in Table 2.

In Table 2, the compound (R? 1) is C.I. Acid Yellow 3 [Tokyo Kasei Co., Ltd. product].

[Example 5]

[Preparation of coloring composition]

(A) Colorant: Compound (I? 5): 20 parts of the compound synthesized in Example 1

(Iii) Resin: methacrylic acid / benzyl methacrylate copolymer (molar ratio; 30/70, weight average molecular weight; 10700, acid value; 70 mgKOH / g) 70 parts

(C? 1) Polymerizable compound: 30 parts of dipentaerythritol hexaacrylate (manufactured by Nihon Kayaku Co., Ltd.)

(D? 1) Photoinitiator: 15 parts of benzyl dimethyl ketal (a monocure 651; BASF Corporation make)

(E? 1) Solvent: 680 parts of propylene glycol monomethyl ether

It mixed and obtained the coloring composition.

[Production of color filter]

The coloring composition obtained above is apply | coated by the spin coating method on glass, and a volatile component is volatilized. After cooling, light irradiation is performed using a quartz glass photomask and an exposure machine. After light irradiation, it develops with aqueous potassium hydroxide solution and heats to 200 degreeC in oven, and obtains a color filter.

[Example 6]

The coloring composition and the color filter were obtained like Example 5 except having replaced the compound (I-5) synthesize | combined in Example 1 with the compound (II-20) synthesize | combined in Example 2.

[Example 7]

The coloring composition and the color filter were obtained like Example 5 except having replaced the compound (I-5) synthesize | combined in Example 1 with the compound (1-50) synthesize | combined in Example 3.

[Example 8]

The coloring composition and the color filter were obtained like Example 5 except having replaced the compound (I-5) synthesize | combined in Example 1 with the compound (1-6) synthesize | combined in Example 4.

From the results in Table 2, it was found that the compounds of the present invention exhibit high solubility in organic solvents. Moreover, the coloring composition containing the said compound has little generation | occurrence | production of a foreign material, and it is possible to manufacture a high quality color filter.

The compound of the present invention is excellent in solubility in organic solvents.

Claims (10)

Formula (1)

In the formula ^(1), L 1 represents a single bond, having from 1 to 8 alkanediyl _{group, -SO 2 -?, -O-,} -CO- , or represents -CO-O-, contained in the alkanediyl group The hydrogen atom may be substituted with the halogen atom, and -CH ₂ -contained in the alkanediyl group may be substituted with -O- or -CO-.
R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
A ¹ and A ² each independently represent a benzene ring which may have a substituent, a naphthalene ring which may have a substituent, or a quinoline ring which may have a substituent.
m and n represent the integer of 0-5 independently of each other. However, m + n is an integer of 1-8. When m + n is an integer of 2 or more, a plurality of -SO ₂ NR ¹ R ² are the same as or different from each other]. The method of claim 1,
A compound wherein the benzene ring A ¹ is which may have a substituent. The method of claim 1,
The said A ¹ is an unsubstituted benzene ring or the benzene ring which has a halogeno group. The method of claim 1,
The said A ¹ and A ² are the benzene rings which may have a substituent independently of each other. The method of claim 1,
Wherein A ¹ and A ² are independently an unsubstituted benzene ring or a benzene ring having a halogeno group. The method of claim 1,
R ¹ and R ² are each independently a hydrogen atom or a branched alkyl group having 1 to 8 carbon atoms. The method of claim 1,
L ¹ is a single bond or —SO ₂ —. The method of claim 1,
M + n is an integer of 1-5. A dye containing the compound according to claim 1 as a main component. The coloring composition containing the dye of Claim 9.