TWI809069B - Aluminum complex, dye composition, coloring agent for anodized aluminum, coloring method, and method for producing the compound - Google Patents

Abstract

The present invention relates to a kind of compound, it is by following general formula (1): [In formula (1), R ¹ to R ¹⁰ independently represent -H, -SO ₃ ^- , -NO ₂ and may have substituents such as amino groups with 0 to 20 carbon atoms, M represents Cr atoms, etc., X represents a non-color-forming cation, k represents an integer from 1 to 8, Y represents -O- or -O-(C=O)-], and R ⁵ is -NH ₂ or NHCOR ^5a and R ^5a is an alkyl group , R ⁶ is -NHCO-Ph, R ⁹ is -SO ₃ ^- , and/or R ² or R ³ is -CH ₃ .

Description

Aluminum complex, dye composition, coloring agent for anodized aluminum, coloring method, and method for producing the compound

The present invention relates to a zirconium salt compound, a dye composition containing the compound, a colorant for anodized aluminum containing the dye composition, a coloring method for anodized aluminum using the dye composition, and a method for producing the compound.

Previously, as a method of coloring the surface of aluminum (including aluminum oxide or aluminum alloy, etc.), electricity was applied to aluminum as an anode in an electrolyte solution containing water and an appropriate acid to make the aluminum surface a porous aluminum oxide layer. (Oxide film, commonly referred to as aluminum oxide film) treatment (hereinafter referred to as anodic oxidation or anodic oxidation treatment, aluminum oxide film treatment, etc.), use: electrolytic coloring method using inorganic compounds or metal compounds; use inorganic dyes, Dyeing method in which organic dyes (azo dyes, complex dyes of dye molecules and metal atoms, acid dyes, direct dyes, etc.) are used as colorants (see Patent Documents 1 to 14).

Those who use dyes as coloring agents have the problem of poor light fastness. In order to improve the light fastness of colored aluminum, etc., various dyes of zirconium salt compounds have been developed, but their colors are mostly black or gray (such as patent documents 1~6 etc.), in order to cope with various colored aluminum demands in recent years, a dyeing method capable of dealing with dyes of various colors has been developed (for example, patent documents 7 to 10, etc.). Moreover, the development of the additive for improving the light fastness in the case of using an organic dye is advancing (for example, refer patent document 8 etc.).

On the other hand, there is also a method of coloring anodized aluminum into blue, green, yellow, red and other colors by using an electrolyte solution containing organic acid or inorganic acid and changing the voltage conditions of anodization without using common dyes. (Patent Documents 11~13, etc.), but there are restrictions on the types of colors.

In addition, the anodized aluminum coloring film using dyes has not been able to develop the bright blue-green, green or yellow-green monochromatic dyes that the market expects and has good light fastness. Therefore, blue and yellow coloring agents are prepared and used (such as TAC Green GM (1), TAC Green SBM (2), both manufactured by Okuno Pharmaceutical Co., Ltd.). However, in terms of color stability (no color difference, fading), it is required to use a coloring agent that develops a desired color with a monochromatic dye. For example, a colorant for anodized aluminum using an anthraquinone-based green azo dye (Patent Document 9) or a phthalocyanine green pigment (Patent Document 14) has been proposed, but there are few types of colors, and the dyeing of aluminum Sexuality and light resistance have not yet reached the performance expected by the market. [Prior Art Literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 55-60562 [Patent Document 2] Japanese Patent Laid-Open No. 55-97492 [Patent Document 3] Japanese Patent Laid-Open No. 9-302256 [Patent Document 4] Japanese Patent Laid-Open No. 60-235867 [Patent Document 5] Japanese Patent Laid-Open No. 6-93195 [Patent Document 6] Japanese Patent Application Publication No. 2002-522617 [Patent Document 7] Japanese Patent Application Publication No. 2013-506053 [Patent Document 8] Japanese Patent Laid-Open No. 2009-91622 [Patent Document 9] Japanese Patent Application Publication No. 2003-504426 [Patent Document 10] Japanese Patent Laid-Open No. 2000-290524 [Patent Document 11] Japanese Patent Laid-Open No. 59-6397 [Patent Document 12] Japanese Patent Laid-Open No. 10-158890 [Patent Document 13] Japanese Patent Laid-Open No. 2000-96293 [Patent Document 14] Japanese Patent Laid-Open No. 2016-216803

[Problem to be solved by the invention]

An object of an aspect of the present invention is to provide a zirconium salt compound with a novel structure capable of forming an anodized film with excellent light resistance and a blue-green color in a single color on the surface of aluminum, aluminum oxide, or aluminum alloy. Another aspect of the present invention aims to provide a dye composition containing the above-mentioned zirconium salt compound, a colorant and coloring method for anodized aluminum using the dye composition, and a method for producing the above-mentioned zirconium salt compound. [Technical means to solve the problem]

In order to solve the above-mentioned problems, the inventors have diligently studied pigments (dye) for anodizing aluminum, and found that by using an alum salt compound (azo dye) with a specific structure as a colorant for anodizing aluminum, It is possible to form a film on anodized aluminum that is colored with a single-color dye in a blue-green color system such as blue, blue-green, and green, and has excellent light resistance. That is, the present invention relates to the following inventions.

[1] A compound comprising the following general formula (1): [Chemical 1] [In formula (1), R ¹ to R ¹⁰ independently represent -H, -SO ₃ ^- , -NO ₂ , -NO, -CN, -OH, -COO ^- , -COOH, -SH, -F, An amino group with 0 to 20 carbon atoms that may also have a substituent, a sulfonyl group with 0 to 20 carbon atoms that may also have a substituent, a straight chain with 1 to 20 carbon atoms that may also have a substituent, or A branched alkyl group, a cycloalkyl group with 3 to 20 carbon atoms that may have a substituent, a linear or branched alkoxy group with a carbon number of 1 to 20 substituents, and A cycloalkoxy group with 3 to 20 carbon atoms that may have a substituent, a linear or branched alkenyl group with 2 to 20 carbon atoms that may have a substituent, and a carbon number that may have a substituent An acyl group of 1 to 20, an aromatic hydrocarbon group with 6 to 30 carbon atoms that may also have a substituent, or a heterocyclic group with 5 to 30 ring atoms that may also have a substituent, R ¹ to R ¹⁰ are also acceptable Adjacent bases are bonded to each other to form a ring, M represents Cr, Fe, Co, Si or Al atoms, X represents a non-coloring cation, k represents an integer from 1 to 8, Y represents -O- or -O-( C=O)-], and R ⁵ is -NH ₂ or NHCOR ^5a and R ^5a is alkyl, R ⁶ is -NHCO-Ph, R ⁹ is -SO ₃ ^- , and/or R ² or R ³ is -CH ₃ . [2] The compound as described in [1], wherein in the general formula (1), R ¹ to R ⁴ are each independently -H, -SO ₃ ^- , -NO ₂ , and the number of carbon atoms that may have a substituent is 0 Amino group with ~10 carbon atoms, straight chain or branched chain alkyl group with 1 to 10 carbon atoms that may have substituents, straight chain or branched chain with 2 to 10 carbon atoms that may also have substituents an alkenyl group, or an acyl group having 1 to 10 carbon atoms which may have a substituent. [3] The compound according to [1] or [2], wherein R ⁵ is -H or an amino group having 0 to 10 carbon atoms which may also have a substituent, and R ⁶ is -H, -SO ₃ ^- or An amino group having a substituent having 0 to 10 carbon atoms, one or both of R ⁷ to R ¹⁰ is -SO ₃ ^- . [4] A dye composition containing the compound according to any one of [1] to [3]. [5] A colorant for anodized aluminum comprising the dye composition according to [4]. [6] A coloring method of anodized aluminum, anodized aluminum oxide, or anodized aluminum alloy, characterized in that a dye combination containing 0.02 to 10% by mass of the compound according to any one of [1] to [3] is used things. [7] A production method, which is a production method of the compound according to any one of [1] to [3], comprising making the following general formula (I): [Chem. 2] [In formula (I), R ¹ ~ R ¹⁰ , and Y represent the same meanings as defined above] The compound shown is reacted with a compound containing Cr, Fe, Co, Si or Al atoms to obtain the general formula (1) Steps for the indicated compounds. [8] The production method according to [7], wherein the compound represented by the general formula (I) is obtained by diazotizing the compound represented by the following formula (II) and the following formula ( III) obtained by the diazo coupling reaction of the compound and/or its salt, [Chem. 3] [In formulas (II) and (III), R ¹ to R ¹⁰ and Y represent the same meanings as defined above]. [Effect of Invention]

According to the present invention, it is possible to provide a zirconium salt compound of a novel structure capable of forming an anodized film having excellent light resistance and a single-color bluish-green color on the surface of aluminum, aluminum oxide, or aluminum alloy. According to the dye composition containing the compound of the present invention, it is possible to obtain a colorant for anodized aluminum capable of forming a monochromatic colored film of blue, cyan, green, and other blue-green systems with excellent light resistance. Moreover, by using this coloring agent, the anodized aluminum coating film excellent in light resistance which is colored in blue-green system, such as blue, blue-green, green, can be obtained. According to the dye composition containing the compound of this invention, the anodized aluminum film excellent in heat resistance in addition to light resistance can be formed.

Embodiments of the present invention will be described in detail below. In addition, this invention is not limited to the following embodiment, Various changes can be implemented within the range of the summary. The part in the square brackets [] in the compound represented by the general formula (1) is an anion, which forms a complex with the non-color-developing cation represented by X in the general formula (1).

The compound of the present embodiment is a compound represented by the following general formula (1) (hereinafter also referred to as "compound (1)"). [chemical 4]

In formula (1), R ¹ ~ R ¹⁰ independently represent -H, -SO ₃ ^- , -NO ₂ , -NO, -CN, -OH, -COO ^- , -COOH, -SH, -F, and Amino group with 0 to 20 carbon atoms which may have substituents, sulfonyl group with 0 to 20 carbon atoms which may also have substituents, straight chain or branched with 1 to 20 carbon atoms which may also have substituents A chained alkyl group, a cycloalkyl group with 3 to 20 carbon atoms that may have a substituent, a straight-chain or branched alkoxy group with 1 to 20 carbon atoms that may have a substituent, Cycloalkoxy group with 3 to 20 carbon atoms which may have a substituent, straight-chain or branched alkenyl group with 2 to 20 carbon atoms which may also have a substituent, or carbon number 1 which may also have a substituent An acyl group with ~20 carbon atoms, an aromatic hydrocarbon group with 6 to 30 carbon atoms that may also have substituents, or a heterocyclic group with 5 to 30 ring atoms that may also have substituents, R ¹ ~R ¹⁰ may also be the same Adjacent groups are bonded to each other to form a ring, M represents Cr, Fe, Co, Si or Al atoms, X represents a non-coloring cation, k represents an integer from 1 to 8, Y represents -O- or -O-(C =O)-.

In compound (1), R ⁵ is -NH ₂ or NHCOR ^5a and R ^5a is alkyl, R ⁶ is -NHCO-Ph, R ⁹ is -SO ₃ ^- , and/or R ² or R ³ is -CH ₃ .

Hereinafter, although compound (1) is demonstrated concretely, this invention is not limited to these. The anion portion may be one type of structure within the range of the general formula (1), or may be a plurality of different structures, preferably one type of structure. That is, a plurality of R ¹ to R ¹⁰ and Y present may be of the same type or different types. Moreover, the non-color-developing cation part may be 1 type or what mixed several types, Preferably it is 1 type. That is, when k is 2-8, the X which exists in plural may be the same type or different types.

In this specification, examples of "amino group having 0 to 20 carbon atoms which may have a substituent" include unsubstituted amino group (-NH ₂ ), monosubstituted amino group, disubstituted amino group, and the like. The number of carbon atoms in the mono-substituted amino group or the di-substituted amino group is, for example, 1-20, may be 1-10, may be 2-6. An amino group with 0 to 20 carbon atoms that may have a substituent may also be bonded to the following aromatic hydrocarbon group with 6 to 30 carbon atoms or a heterocyclic ring with 5 to 30 ring atoms via -NH- The foundation of the foundation. Examples of the monosubstituted amino group include ethylamino group, acetylamino group, phenylamino group and the like. Examples of the disubstituted amino group include a diethylamino group, a diphenylamino group, an acetylphenylamino group, and the like. A substituted amino group can also be a group represented by -NHCOR ^5a . The substituent R ^5a is an alkyl group.

In this specification, "a sulfonyl group having 0 to 20 carbon atoms which may also have a substituent" means having a substituent represented by -SO ₂ -R ¹⁰⁰ (or -S(=O) ₂ -R ¹⁰⁰ ) The sulfonyl group of R ¹⁰⁰ . The substituent R ¹⁰⁰ may be a group containing carbon atoms or a group not containing carbon atoms. When the substituent R ¹⁰⁰ is a group containing carbon atoms, the number of carbon atoms in the substituent R ¹⁰⁰ is 1-20, may be 1-10, may be 1-7. Specific examples of a sulfonyl group that may have a substituent having 0 to 20 carbon atoms include, for example, a sulfonylamino group (-S(=O) ₂ -NH ₂ ), a methylsulfonyl group, and a toluenesulfonyl group. .

In this specification, as "a linear or branched alkyl group having 1 to 20 carbon atoms" in "a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent" "Alkyl", specifically, straight-chain alkyl groups such as methyl, ethyl, n-propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, etc.; isopropyl, Branched-chain alkyl groups such as isobutyl, second-butyl, third-butyl, isooctyl, and third-octyl.

In the present specification, examples of the "cycloalkyl group having 3 to 20 carbon atoms" in the "cycloalkyl group having 3 to 20 carbon atoms which may have substituents" specifically include cyclopropyl, cyclobutyl Cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclododecyl, etc.

In this specification, as "straight-chain or branched alkoxy group having 1-20 carbon atoms which may have a substituent" "Alkoxy", specifically: methoxy, ethoxy, propoxy, n-butoxy, n-pentyloxy, n-hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy Linear alkoxy such as oxy; branched alkoxy such as isopropoxy, isobutoxy, second butoxy, third butoxy, isooctyloxy, third octyloxy base.

In this specification, examples of the "cycloalkoxy group having 3 to 20 carbon atoms" in the "cycloalkoxy group having 3 to 20 carbon atoms which may have substituents" specifically include cyclopropoxy , cyclobutoxy, cyclopentyloxy, cyclohexyloxy, etc.

In this specification, "straight-chain or branched alkenyl having 2 to 20 carbon atoms" in "straight-chain or branched alkenyl group having 2 to 20 carbon atoms which may have substituents" "group", specifically vinyl, allyl, isopropenyl, 2-butenyl, 1-hexenyl, or linear or branched chains in which multiple alkenyl groups are bonded. foundation.

In this specification, "acyl group having 1 to 20 carbon atoms which may have a substituent" is a group represented by -C=OR ¹⁰¹ . The substituent R ¹⁰¹ may be a group containing carbon atoms or a group not containing carbon atoms. When the substituent R ¹⁰¹ is a group containing carbon atoms, the number of carbon atoms in the substituent R ¹⁰¹ may be, for example, 1-20, or 1-10. The acyl group with 1 to 20 carbon atoms that may also have a substituent may also be bonded to the following aromatic hydrocarbon group with 6 to 30 carbon atoms or a heterocyclic group with 5 to 30 ring atoms via the acyl group foundation. Examples of the substituent R ¹⁰¹ include -H, -CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH=CH ₂ , and -C ₆ H ₅ (-Ph). Specific examples of the "acyl group having 1 to 20 carbon atoms" in the "acyl group having 1 to 20 carbon atoms which may have a substituent" include formyl, acetyl, acyl, and acryl groups. Acyl, benzoyl, etc.

In this specification, the "aromatic hydrocarbon group having 6 to 30 carbon atoms" in the "aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent" specifically includes phenyl, naphthyl, Biphenyl, anthracenyl, phenanthrenyl, pyrenyl, terphenyl, indenyl, fenyl, etc. The "aromatic hydrocarbon group" in this specification refers to an aromatic hydrocarbon group and a condensed polycyclic aromatic group, and among them, phenyl or naphthyl is preferable.

In the present specification, the "heterocyclic group having 5 to 30 ring atoms" in the "heterocyclic group having 5 to 30 ring atoms that may have a substituent" specifically includes pyridyl, pyrimidine Base, triazinyl, pyrrolyl, imidazolyl, pyrazolyl, triazolyl, quinolinyl, isoquinolyl, naphthyridinyl, indolyl, benzimidazolyl, carbazolyl, carbalinyl, Acridyl, phenanthrinyl, hydantoylureidyl, furyl, benzofuryl, dibenzofuryl, thienyl, benzothienyl, dibenzothienyl, oxazolyl, benzoxazole base, thiazolyl, benzothiazolyl, etc.

In this specification, "amino group having a substituent having 0 to 20 carbon atoms", "a sulfonyl group having a substituting group having 0 to 20 carbon atoms", "a group having a substituent having 0 to 20 carbon atoms" Linear or branched alkyl", "cycloalkyl with 3 to 20 carbon atoms with substituents", "straight or branched alkyl with 1 to 20 carbon atoms with substituents"Oxygen","cycloalkoxy with 3 to 20 carbon atoms with substituents", "linear or branched alkenyl with 2 to 20 carbon atoms with substituents", "substituent "acyl group with 1 to 20 carbon atoms", "aromatic hydrocarbon group with 6 to 30 carbon atoms with substituents" or "heterocyclic group with 5 to 30 ring atoms with substituents"", specifically: -SO ₃ ^- , nitro (-NO ₂ ), nitroso (-NO), cyano (-CN), hydroxyl (-OH), -COO ^- , carboxyl (- COOH), thiol (-SH), unsubstituted amine; methylamine, dimethylamine, diethylamine, ethylmethylamine, methylpropylamine, di- One of tertiary butylamino, phenylamino, diphenylamino, etc. is substituted with a linear or branched alkyl group with 1 to 17 carbon atoms or an aryl group with 6 to 24 carbon atoms or Disubstituted amino group; sulfonamide (-S(=O) ₂ -NH ₂ ) group, methylsulfonyl group, toluenesulfonyl group and other groups with sulfonyl group (-S(=O) ₂ -); methyl Base, ethyl, n-propyl, isopropyl, n-butyl, second butyl, third butyl, pentyl, n-hexyl, isohexyl, heptyl, n-octyl, third octyl, isooctyl straight-chain or branched-chain alkyl groups with 1 to 17 carbon atoms, such as radical, nonyl, and decyl; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclo Decyl, cyclododecyl and other cycloalkyl groups with 3 to 17 carbon atoms; 1-17 linear or branched alkoxy; Cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy and other cycloalkoxy with 3-17 carbon atoms; Vinyl , 1-propenyl, allyl, 1-butenyl, 2-butenyl, 1-pentenyl, 1-hexenyl, isopropenyl, isobutenyl, or a plurality of these alkenyl groups A linear or branched alkenyl group with 2 to 19 carbon atoms; acyl groups such as formyl, acetyl, propionyl, acryl, benzoyl, etc.; phenyl, naphthyl , anthracenyl, phenanthrenyl, pyrenyl, terphenyl, indenyl, fenyl and other aromatic hydrocarbon groups with 6 to 24 carbon atoms; pyridyl, pyrimidyl, triazinyl, pyrrolyl, imidazolyl, pyrazole Base, Triazolyl, Pyroxyl, Pyridyl, Piperidyl, Piperazinyl, Quinolinyl, Isoquinolyl, Naphthyridyl, Indolyl, Benzimidazolyl, Carbazolyl, Carboline Base, acridinyl, phenanthroline, phenanthridinyl, hydantoinyl, furyl, benzofuryl, dibenzofuryl, pyranyl, coumarinyl, isobenzofuryl, 𠮿 Base, Xanthenyl, Pyranyl, Thienyl, Thienyl, Benzothienyl, Dibenzothienyl, 9-Oxythiol Heterocyclic group with 5-24 ring atoms such as oxazolyl, benzoxazolyl, morpholinyl, thiazolyl, benzothiazolyl; cyclopropenyl, cyclobutenyl, cyclopentenyl, Cyclohexenyl, cycloheptenyl, (1,3- or 1,4-) cyclohexadienyl, 1,5-cyclooctadienyl and other cyclic alkenyl groups with 3 to 24 carbon atoms, etc. These "substituents" may contain only one or plural, and when plural are contained, they may be the same or different. These "substituents" may also have the substituents exemplified above, and further, these substituents may also be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring. .

R ¹ can be -H, for example. R ² can be, for example, -H, -SO ₃ ^- , -CN, -NO, -NO ₂ , or a linear or branched chain with 1 to 20 carbon atoms (or 1 to 10 carbon atoms) that may have substituents. A chained alkyl group (for example, -CH ₃ ), a straight-chain or branched alkoxy group with a carbon number of 1 to 20 (or a carbon number of 1 to 10) that may also have a substituent (for example, - OCH ₃ ), or a linear or branched alkenyl group with 2 to 20 carbon atoms (or 2 to 10 carbon atoms) that may also have substituents (for example, -CH=CH-CH ₃ ), and Can be -NO ₂ or CH ₃ . R ³ can be, for example, -H, -NO ₂ , a cycloalkoxy group with 3 to 20 carbon atoms that may have a substituent, or a cycloalkoxy group with 1 to 20 carbon atoms (or 1 to 10 carbon atoms) that may have a substituent. ) straight-chain or branched-chain alkoxy group, or a straight-chain or branched-chain alkyl group with 1 to 20 carbon atoms (or 1 to 10 carbon atoms) that may also have substituents (for example, -CH ₃ ), can also be -H. R ⁴ can be -H, -NO ₂ , or F, for example.

In the general formula (1), R ² or R ³ may be -CH ₃ . When R ² is -CH ₃ , for example, each of R ¹ , R ³ and R ⁴ can be -H. When R ³ is -CH ₃ , R ¹ , R ² and R ⁴ can each be -H.

In the general formula (1), R ¹ ~ R ⁴ represent the above-mentioned substituents, but adjacent groups may be connected to each other through a single bond, or through a bond of an oxygen atom (-O-) or through a bond of a sulfur atom. Bonds (-S-) are bonded to each other to form a ring.

In the general formula (1), "M" represents a chromium atom (Cr), an iron atom (Fe), a cobalt atom (Co), a silicon atom (Si) or an aluminum atom (Al), preferably a Cr atom or a Co atom , more preferably a Cr atom.

In the general formula (1), "X" is a non-color-forming cation, specifically hydrogen ions (H ⁺ ), lithium ions (Li ⁺ ), sodium ions (Na ⁺ ), potassium ions (K ⁺ ), etc. Alkali metal ions, cations including organic compounds, etc. Among these, alkali metal ions are more preferred, and K ⁺ or Na ⁺ is particularly preferred.

k represents the number of non-color-forming cations "X", and represents an integer of 1-8, preferably an integer of 3-7. k becomes a value which becomes neutral as a whole like general formula (1).

In the general formula (1), "Y" represents "-O-" or "-O-(C=O)-", and when representing "-O-(C=O)-", it is preferably Bond like "M" and "M-O-(C=O)-".

R ⁵ is preferably -H or an amino group having 0 to 10 carbon atoms which may have a substituent, more preferably -H or -NH ₂ . R ⁶ is preferably -H, -SO ₃ ^- or an amino group having 0 to 10 carbon atoms which may have a substituent. Any one or two of R ⁷ ~ R ¹⁰ is preferably -SO ₃ ^- , when any two of R ⁷ ~ R ¹⁰ are -SO ₃ ^- , R ⁷ and R ¹⁰ are more preferably -SO ₃ ^- .

In compound (1), R ⁵ may be -NH ₂ or NHCOR ^5a . The substituent R ^5a may be, for example, the group exemplified above as the linear or branched alkyl group having 1 to 20 carbon atoms, and may be a methyl group. In general formula (1), when R ⁵ is -NH ₂ or NHCOR ^5a , for example, R ⁶ can be -H or SO ₃ ^- , R ⁷ can be -H, -SO ₃ ^- , R ⁸ can be -H, -SO ₃ ^- , -COO ^- , R ⁹ may be -H, a cycloalkyl group with 3 to 20 carbon atoms that may have a substituent, or a cycloalkyl group with 6 to 30 carbon atoms that may also have a substituent In the aromatic hydrocarbon group, R ¹⁰ may be -H, -SO ₃ ^- or an acyl group with 1 to 20 carbon atoms which may also have a substituent.

In compound (1), R ⁶ may be -NHCO-Ph. "Ph" in this specification means phenyl. When R ⁶ is -NHCO-Ph, for example, R ⁵ , R ⁸ and R ⁹ can each be -H, and R ¹⁰ can be -SO ₃ ^- .

In compound (1), R ⁹ may be -SO ₃ ^- . When R ⁹ is -SO ₃ ^- , for example, R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ¹⁰ can each be -H.

The compound of the present invention represented by the general formula (1) includes all possible stereoisomers, and any isomer can be preferably used as the compound of the present invention. For example, when the compound represented by the following general formula (1-a) exists relative to the compound of the general formula (1), the compound of the present invention includes the compounds represented by the general formula (1) and the general formula (1-a) The compound can also be a mixture of two or more selected from these stereoisomers. [chemical 5]

Specific examples of the compound (compound (1)) of the present invention represented by the general formula (1) are shown in the following formula, but the present invention is not limited thereto. Furthermore, in the exemplified compounds, the charge of the entire anion portion within the square brackets [ ] of the general formula (1) is described, and in the structural formula, a part of the hydrogen atom is omitted. [chemical 6] [chemical 7] [chemical 8] [chemical 9] [chemical 10] [chemical 11] [chemical 12] [chemical 13] [chemical 14] [chemical 15] [chemical 16] [chemical 17] [chemical 18] [chemical 19] [chemical 20] [chem 21] [chem 22] [chem 23] [chem 24] [chem 25] [chem 26] [chem 27] [chem 28] [chem 29]

Compound (1) may be a compound represented by formulas (A-1) to (A-24), and may be a compound represented by formula (A-3) from the viewpoint of further excellent light resistance and further excellent heat resistance Or the compound represented by (A-4).

An example of the production method of the compound represented by general formula (1) is shown below, but it is not limited to this method. Specifically, first, by making the following general formula (II): [Chem. 30] [In the formula (II), R ¹ ~ R ⁴ and Y represent the same meanings as defined above] and the aromatic amine derivatives and/or their salts with appropriate substituents are mixed in aqueous acid solutions such as hydrochloric acid and sulfuric acid The alkaline aqueous solution prepared by using sodium nitrite etc. is reacted at an appropriate temperature to obtain the following general formula (IV): [Chemical 31] [In formula (IV), R ¹ to R ⁴ and Y represent the same meanings as defined above] The compound and/or its salt (diazo component). By making the following general formula (III): [Chem. 32] The compound shown is dissolved in an aqueous solution of sodium hydroxide or the like and reacted to obtain the following formula (IIIa): [Chem. 33] [In formula (IIIa), R ¹ to R ⁴ and Y represent the same meaning as defined above, and n represents 0, 1 or 2] The compound (coupling component) represented. Next, an azo compound (azo dye) represented by the following general formula (I) is obtained by reacting the above-mentioned diazo component and the above-mentioned coupling component (diazo coupling reaction). [chem 34] [In formula (II), R ¹ to R ⁴ and Y represent the same meanings as defined above].

Then, prepare the reaction solution containing the azo compound represented by the above general formula (I) and the aqueous solution containing the compound containing the atom represented by M in the manner of atom (M): azo dye = 1:2 and make it Compound (1) can be produced in the form of a 1:2 type zirconium salt compound by performing zigzag saltation and salting out by such reactions. The compound containing an atom represented by M is a compound containing Cr, Fe, Co, Si, or Al atoms, and one type of compound may be used alone, or two or more types of compounds may be used in combination. As a specific example of the compound containing the atom represented by M, chromium acetate is mentioned, for example.

That is, the production method of the compound (1) of one embodiment has the following general formula (I): [Chemical 35] [In formula (I), R ¹ ~ R ¹⁰ , and Y represent the same meanings as above] The step of reacting the compound (compound (I)) shown with a compound containing Cr, Fe, Co, Si or Al atoms . As mentioned above, the compound (I) can be a diazonium compound (compound (IV)) obtained by diazotizing the compound (compound (II)) represented by the following formula (II) and the following formula (III ) obtained by the diazo coupling reaction of the compound represented by (compound (III)) and/or its salt. [chem 36] [chem 37]

Compound (1) can be purified by the following known methods: purification by column chromatography; adsorption purification by silica gel, activated carbon, activated clay, etc.; recrystallization and crystallization by solvent. Compounds can be identified and evaluated using ultraviolet-visible light absorption spectroscopy (UV-Vis), thermogravimetry-differential thermal analysis (TG-DTA), gas chromatography analysis (GC), nuclear magnetic resonance analysis (NMR) analysis, etc. And proceed.

Compound (1) can be used as a component of a dye composition. Even if the compound (1) is used alone, it can color aluminum, fibers, and the like. That is, the compound (1) can be preferably used as a pigment compound for coloring aluminum, fiber, and the like using one kind of monochromatic dye alone. Compound (1) may be used in combination of two or more to obtain various colors by color mixing. The dye composition may also contain other components for optimal dyeing (coloring using a dye). Specifically, liquids (solvents) such as water, alcohols, and solvents; additives such as surfactants; and the like. As a solvent, water is preferable. Compound (1) can also be used in combination with other dyes as a component of a dye composition. Other compounds, pigments, dyes, and the like other than the pigment compound (1), specifically, ruthenium complexes, coumarin-based pigments, anthocyanin-based pigments, merocyanine-based pigments, and rhodocyanine-based pigments Pigments, phthalocyanine pigments, porphyrin pigments, 𠮿 Department of pigments and so on. When the compound (1) is used in combination with other components, the usage-amount of the other components is preferably 10 to 200% by mass, more preferably 20 to 100% by mass, based on the compound (1).

The dye composition of this embodiment can be used as a coloring agent for anodized aluminum. When compound (1) is used as a coloring agent such as anodized aluminum, in its coloring (dyeing) method, the concentration of compound (1) in the dye composition containing compound (1) is relative to the total amount of the dye composition, Preferably it is 0.02-10 mass %, More preferably, it is 0.05-1 mass %.

Here, the term "anodized aluminum" refers to aluminum treated to form an oxide layer having fine pores on the surface of an electrolytically treated aluminum in an electrolytic solution such as an acid aqueous solution. The colorant for anodized aluminum refers to a coloring agent capable of coloring (dyeing) by adsorbing the compound (1) into the pores of the aluminum surface having pores using a dye composition containing the compound (1). Usually, in order to improve the durability and light resistance of the colored aluminum surface, a sealing treatment for blocking pores is performed after coloring.

Examples of aluminum in anodized aluminum include aluminum, aluminum oxide, or aluminum alloys with other metals, metals or metal compounds containing aluminum, and the like.

As a method of coloring aluminum using a colorant for anodized aluminum, a method known as an aluminum oxide film dyeing method can be used. For example, methods described in Japanese Industrial Standards (JIS H 8601: 1999 "Anodic Oxide Films of Aluminum and Aluminum Alloys"), Patent Documents 1 to 3, and 8 can be used. The coloring method of aluminum is not particularly limited, but an example is shown below.

First, the aluminum plate is degreased and washed with aqueous acid such as sulfuric acid, oxalic acid, chromic acid, or sulfonic acid. Secondly, use the degreased aluminum plate as the anode, and use the acid solution as the electrolyte for electrolysis, on the surface of the aluminum anode, an anodic oxide film (aluminum oxide film) with a large number of pores is formed (anodizing treatment), and carry out wash. Then, after performing surface adjustment, washing with water, etc. as appropriate, dip in an aqueous colorant solution for anodized aluminum containing a dye composition containing the compound of the present invention, etc., to adsorb the dye (dyeing, electrolytic coloring) into the pores, and use aluminum Oxide hydrate or the like seals the pores on the surface to form a sealing substance, thereby enabling coloring. When two or more dye compositions of the present invention are used in combination or when the dye composition of the present invention is used in combination with other pigments, a mixed solution of all the pigments to be used can be prepared and anodized aluminum can be dipped in it, and then , each pigment solution can also be prepared separately and the anodized aluminum is immersed in each solution sequentially.

The electrolysis conditions during coloring can be DC electrolysis or AC electrolysis, preferably DC electrolysis. The current density is preferably 0.1~10 A/dm ² , more preferably 0.5~3 A/dm ² . The electrification time is preferably 10 seconds to 60 minutes. The thickness of the anodized film is preferably 2-20 μm.

The treatment temperature of the above steps is preferably an appropriate temperature for each, and the temperature during anodic oxidation is preferably 0-80°C. The temperature during dyeing is preferably 10°C~70°C. Other treatment temperatures are preferably 10-80°C.

The dye composition of the present embodiment can also be used similarly for anodic oxides using metals other than aluminum. For example, magnesium, zinc, titanium, zirconium, etc. can also be used for non-metals such as conductive plastics, as long as they are capable of adsorbing dyes in the anodized pores.

The coloring agent for anodized aluminum of this embodiment can be evaluated by measuring the hue, light resistance, heat resistance, etc. about the characteristic of the sample which colored aluminum. Regarding the hue, the hue and uniformity can be evaluated visually, and can also be measured in the form of density (K/Sd), hue (L ^* , a ^* , b ^* ) and color difference (ΔE ^* ) with a color difference meter.

According to the coloring agent for anodized aluminum of this embodiment, it is possible to display green, blue, purple, and those light colors (light green, etc.) or dark colors (black green, etc.) with different shades. The colorant for anodized aluminum according to this embodiment can also display a color obtained by mixing the above-mentioned compound with other pigments (intermediate colors such as yellow-green, dark blue, black, gray, and brown). As an intermediate color, black and gray are preferable.

The light resistance test of aluminum colored by using the colorant for anodized aluminum of this embodiment can also use a testing machine that simulates sunlight including ultraviolet light, etc., to irradiate the sample with light for a fixed time, and use a color difference meter to measure the test. Evaluate the change in hue of colored aluminum before and after. Regarding the judgment of light fastness, the hue of colored aluminum can also be judged by visual inspection using gray scale according to the method stipulated in Japanese Industrial Standards (Gray scale for discoloration and fading, JIS L 0804).

The heat resistance test of aluminum colored by using the colorant for anodized aluminum of this embodiment can be, for example, heated in a thermostat in the temperature range of 50 to 300°C or in a hot air dryer for 30 minutes to 50 hours. A method of evaluating the change in hue before and after the test in the same way as the lightfastness test, such as the method of fixed time.

Colored aluminum using the colorant for anodized aluminum of this embodiment is used for various aluminum sheet materials, aluminum exteriors, and the like. [Example]

Hereafter, although an Example demonstrates this invention concretely, it is not limited to the following Example.

[Synthesis Example 1: Synthesis of Compound (A-1)] (Preparation of Diazo Component) In a reaction vessel, put 20 g of 2-amino-4-nitrophenol, 140 mL of water, and 35% hydrochloric acid 11 g. While stirring the obtained reaction liquid at 10° C., 23 g of a 40% by weight sodium nitrite aqueous solution was added dropwise, and then reacted for 1 hour. Thereby, a diazo component liquid is obtained. (Preparation of Coupling Components) 30 g of 8-amino-1-hydroxynaphthalene-3,6-disulfonic acid, 200 mL of water, and 18.9 g of a 24% by weight sodium hydroxide aqueous solution were placed in a reaction container. The obtained reaction solution was stirred at 10° C. for 1 hour to obtain a coupling component liquid. (Diazo Coupling Reaction) The diazo component liquid was put into the coupling component liquid being stirred, and stirred for 1 hour to carry out the diazo coupling reaction. The completion of the reaction was confirmed by shallow layer chromatography (TLC). The purity of the product was confirmed by high-speed liquid chromatography (HPLC) by observing the retention time peak position and area obtained by typical azo dyes. (Baloxalization) Put 48% by weight of chromium acetate aqueous solution into the reaction liquid after the coupling, and stir in the range of 80~100°C. The completion of the reaction was confirmed by TLC. After the reaction, the obtained reaction liquid was cooled to 25°C. Add sodium chloride, and collect the precipitated solid by filtration. The solid was dried under reduced pressure to obtain compound (A-1) (15.3 g, yield: 31.1%) as a solid powder. [Synthesis Example 2: Synthesis of Compound (A-2)] In the same manner as in Synthesis Example 1, except that 2-amino-5-nitrophenol was used instead of 2-amino-4-nitrophenol to obtain compound (A-2). [Synthesis Example 3: Synthesis of Compound (A-3)] Using 2-amino-4,6-dinitrophenol instead of 2-amino-4-nitrophenol, in the same manner as in Synthesis Example Compound (A-3) was obtained in the same manner as in 1. [Synthesis Example 4: Synthesis of Compound (A-4)] Using picric acid (2-amino-4,6-dinitrophenol) instead of 2-amino-4-nitrophenol, 1-amine Base-8-naphthol-4-sulfonic acid instead of 8-amino-1-hydroxynaphthalene-3,6-disulfonic acid, except that, compound (A-4) was synthesized in the same manner as in Synthesis Example 1 . Compound (A-4) is obtained in the form of solid powder. [Synthesis Example 5: Synthesis of Compound (A-5)] Using picric acid (2-amino-4,6-dinitrophenol) instead of 2-amino-4-nitrophenol, 1-amine Base-8-naphthol-2,4-disulfonic acid instead of 8-amino-1-hydroxynaphthalene-3,6-disulfonic acid, except that, compound (A -5). [Synthesis Example 6: Synthesis of Compound (A-6)] Using picric acid (2-amino-4,6-dinitrophenol) instead of 2-amino-4-nitrophenol, 1-ethyl Acylamino-8-naphthol-3,6-disulfonic acid was replaced by 8-amino-1-hydroxynaphthalene-3,6-disulfonic acid, except that it was synthesized in the same way as in Synthesis Example 1 Compound (A-6). [Synthesis Example 7: Synthesis of Compound (A-7)] In the same manner as in Synthesis Example 1, except that 2-amino-4-methylphenol was used instead of 2-amino-4-nitrophenol to obtain compound (A-7). [Synthesis Example 8: Synthesis of Compound (A-8)] Using picric acid (2-amino-4,6-dinitrophenol) instead of 2-amino-4-nitrophenol, 6-benzene Formylamino-4-hydroxyl-2-naphthalenesulfonic acid replaces 8-amino-1-hydroxynaphthalene-3,6-disulfonic acid, except that the compound is synthesized in the same manner as in Synthetic Example 1 ( A-8). [Comparative example] As a compound for comparison, dye index (CI) Acid Green (Acid Green) 1, Acid Green 9, Acid Green 25, Acid Green 28, Acid Green 73, Acid Green 104 were prepared as green aluminum oxide film dyes , Compounds of Acid Green 111. [chem 38] REFERENCE EXAMPLE Compounds (Q-1) and (Q-2) represented by the following formulas were prepared as black aluminum oxide film dyes. [chem 39] <Evaluation of Hue and Light Fastness Test> [Example 1] Anodizing treatment was performed on an aluminum substrate in the following procedure to produce colored aluminum. Furthermore, in the steps of anodizing and dyeing, two kinds of dyeing conditions were set in which the treatment time and the concentration of the dye compound were changed. (Degreasing) In a container, mix 150 mL of a degreasing agent (TOP ADD-100 manufactured by Okuno Pharmaceutical Co., Ltd.), 70 mL of 98% sulfuric acid, and 1000 mL of water to prepare a degreasing solution, and cut the dyed The aluminum substrate was immersed therein, subjected to degreasing treatment at 60° C. for 3 minutes, and washed with water after the treatment. (Anodic oxidation) Use 98% sulfuric acid to prepare 180 g/L electrolyte, connect the aluminum substrate to the electrode of the electrolysis device, and immerse it in the electrolyte tank at a temperature of 20±1°C and a current density of 1.0 A/ ^dm2 or less The anodic oxidation is carried out under the conditions of the energization time, and the anodic oxide film with the following thickness is obtained. After oxidation, washing with water is performed. Dyeing condition (1): energized for 15 minutes Anodized film thickness: 5 μm Stained condition (2): energized for 45 minutes Anodized film thickness: 15 μm (Surface adjustment) Surface conditioner (manufactured by Okuno Pharmaceutical Co., Ltd., TAC) was used SORMAL 121) and water, prepare a surface adjustment solution with a concentration of 50 mL/L, and immerse the aluminum substrate in it at 45°C for 1 minute. After dipping, the aluminum substrate was washed with water. (Dyeing) Using the compound (A-1) obtained in Synthesis Example 1 as the pigment, the aqueous solution for dyeing containing the pigment of the following concentration was prepared respectively as the dye composition of the present invention, and dipped according to the following dyeing time. Dyeing was carried out at a temperature of 55°C. After dyeing, the aluminum substrate was washed with water. Dyeing condition (1): 0.1% by weight of pigment concentration Dyeing time: 30 seconds Dyeing condition (2): 0.2% by weight of pigment concentration Dyeing time: 5 minutes (sealing) using a sealing agent (manufactured by Okuno Pharmaceutical Co., Ltd., TOP Seal H-298) and water to prepare a 40 mL/L sealing solution, and seal at about 90°C for 15 minutes. After sealing, dry with warm air.

(Hue evaluation) The hue of the colored aluminum plate colored using the compound (A-1) was visually evaluated. Table 1 shows the evaluation results.

(Light resistance test) The light resistance test was performed by the following method about the colored aluminum plate colored using the compound (A-1). Using a xenon attenuation meter/ATLAS Ci3000+Xenon Weather Ometer (manufactured by Atlas Corporation), under irradiance: 300~400 nm, 60 W/m ² , temperature in the test tank: 38°C, humidity: 50%, black panel (BP) Temperature: Under the condition of 63°C, irradiate the colored aluminum plate for 50 hours. Based on the obtained results, use the gray scale to visually judge the color fastness (gray scale for color change and fading, JIS L 0804). Level 5 is the highest and level 1 is the lowest. The higher the level, the darker the color and the hue before irradiation will be maintained. In the evaluation method of the present invention, the judgment results of the number of stages were divided into three grades, and the evaluation was performed according to the following judgment criteria, and the results are summarized in Table 1. Criterion for judging gray scale: Correspondence between the number of grades and the evaluation (A, B, C) in the present invention Grade 5~4: A (extra good light fastness) Grade 3: B (normal light fastness) below grade 2 : C (lower light resistance) [Examples 2-8, Comparative Examples and Reference Examples] The compounds shown in Table 1 were used instead of Compound (A-1), and prepared in the same manner as in Example 1 Color the aluminum plate, and evaluate the hue and light fastness. The measurement results are summarized in Table 1.

[Table 1]

According to the results in Table 1, blue, cyan, light green, green, dark green, light blue, blue, ink can be formed on aluminum by using an anodized aluminum colorant containing a dye composition comprising the compound of the present invention. Blue, black and green and other blue-green films with high light resistance. The light resistance obtained by using the compound of the example is not inferior to that of the film produced by using the previous black pigment (Q-1) or (Q-2). On the other hand, those obtained by using the dyes of Comparative Examples were poor in light resistance. <Heat resistance test> [Example 3] The heat resistance test was performed by the following method about the colored aluminum plate colored under the dyeing condition (2) of the said Example using a compound (A-3). Using a constant temperature dryer (manufactured by AS ONE Co., Ltd., model: 87L EOP-450V), the sample was heated under the following exposure conditions. Temperature and heating time in the dryer: 200°C-5 hours, or 250°C-3 hours The heat resistance evaluation method of the present invention is to use the following color difference meter to measure the color difference of the colored aluminum sample before and after heating and judge according to the following The benchmarks were evaluated visually. The results are shown in Table 2. Device: Color difference meter (Spectrocolor difference meter manufactured by Konica Minolta Co., Ltd., model: CM-3700A) Color difference calculation formula: ΔE ^* _ab (L ^* a ^* b ^* , CIE 1976) and ΔE ^* ₀₀ (CIE DE2000 ) Angle of view: 10° Heat resistance criteria: A: Good heat resistance (no discoloration or fading) B: Normal level of heat resistance (no fading but slight discoloration) C: Low heat resistance (fading and discoloration) [ Example 4] A heat resistance test was performed in the same manner as in Example 3 except that the compound (A-4) was used. After heating at 250°C, it turns green with a black tint, but it has the usual level of heat resistance. The results are summarized in Table 2. COMPARATIVE EXAMPLES AND REFERENCE EXAMPLES The heat resistance test was performed by the method similar to Example 3 except having used Acid Green 9, 28, 104 or TAC Green SBM (2) which were green pigments previously. The results are summarized in Table 2.

The heat resistance test was performed by the method similar to Example 3 except having used the compound (Q-1) and (Q-1) which used the previous black-type dye. The results are summarized in Table 2. [Table 2]

According to the results in Table 2, by using the anodized aluminum colorant containing the dye composition containing the compound of the present invention, a green film with high heat resistance can be formed on aluminum. The heat resistance of the film using the pigment of the example is better than that of the previous green-based pigment, and is not inferior to that of the previous black-based pigment. [Industrial availability]

According to the dye composition containing the compound of the present invention, it is possible to obtain a colorant for anodized aluminum that is excellent in light resistance and can form a cyan colored film in one color. By using the coloring agent of the present invention, an anodized aluminum film excellent in light resistance that is monochromaticly colored in blue-green color can be obtained. The colored film obtained by using the dye composition containing the compound of the present invention is also excellent in heat resistance.

Claims (6)

A compound represented by the following general formula (1):

M represents a Cr, Fe, Co, Si or Al atom, X represents a non-color cation, and the above-mentioned non-color cation is a hydrogen ion or an alkali metal ion, k represents an integer from 1 to 8, Y represents -O-, and is the following Any one of (a)~(h): (a) In the above general formula (1), R ¹ is -H, R ² is -NO ₂ , R ³ is -H, R ⁴ is -H, R ⁵ is -NH ₂ , R ⁶ is -H, R ⁷ is -SO ₃ ^- , R ⁸ is -H, R ⁹ is -H, R ¹⁰ is -SO ₃ ^- ; (b) in the above general formula (1) , R ¹ is -H, R ² is -H, R ³ is -NO ₂ , R ⁴ is -H, R ⁵ is -NH ₂ , R ⁶ is -H, R ⁷ is -SO ₃ ^- , R ⁸ is -H, R ⁹ is -H, R ¹⁰ is -SO ₃ ^- ; (c) In the above general formula (1), R ¹ is -H, R ² is -NO ₂ , R ³ is -H, R ⁴ is -NO ₂ , R ⁵ is -NH ₂ , R ⁶ is -H, R ⁷ is -SO ₃ ^- , R ⁸ is -H, R ⁹ is -H, R ¹⁰ is -SO ₃ ^- ; (d) the above-mentioned general In formula (1), R ¹ is -H, R ² is -NO ₂ , R ³ is -H, R ⁴ is -NO ₂ , R ⁵ is -NH ₂ , R ⁶ is -H, R ⁷ is -H , R ⁸ is -SO ₃ ^- , R ⁹ is -H, R ¹⁰ is -H; (e) In the above general formula (1), R ¹ is -H, R ² is -NO ₂ , R ³ is -H , R ⁴ is -NO ₂ , R ⁵ is -NH ₂ , R ⁶ is -SO ₃ ^- , R ⁷ is -H, R ⁸ is -SO ₃ ^- , R ⁹ is -H, R ¹⁰ is -H; ( f) In the above general formula (1), R ¹ is -H, R ² is -NO ₂ , R ³ is -H, R ⁴ is -NO ₂ , R ⁵ is -NHCOCH ₃ , R ⁶ is -H, R ⁷ is -SO ₃ ^- , R ⁸ is -H, R ⁹ is -H, R ¹⁰ is -SO ₃ ^- ; (g) In the above general formula (1), R ¹ is -H, R ² is -CH ₃ , R ³ is -H, R ⁴ is -H, R ⁵ is -NH ₂ , R ⁶ is -H, R ⁷ is -SO ₃ ^- , R ⁸ is -H, R ⁹ is -H, R ¹⁰ is - SO ₃ ^- ; (h) In the above general formula (1), R ¹ is -H, R ² is -NO ₂ , R ³ is -H, R ⁴ is -NO ₂ , R ⁵ is -H, R ⁶ is -NHCO-Ph, R ⁷ is -H, R ⁸ is -H, R ⁹ is -H, R ¹⁰ is -SO ₃ ^- . A dye composition, which contains the compound as claimed in claim 1. A coloring agent for anodized aluminum, which contains the dye composition according to claim 2. A coloring method for anodized aluminum, anodized aluminum oxide, or anodized aluminum alloy, characterized in that a dye composition containing 0.02-10% by mass of the compound according to claim 1 is used. A kind of production method, it is the production method of the compound as claim item 1, and comprises making following general formula (I):

[In formula (I), R ¹ ~ R ¹⁰ , and Y represent the same meaning as defined in claim item 1] The compound shown is reacted with a compound containing Cr, Fe, Co, Si or Al atoms to obtain the above-mentioned The steps of the compound represented by the general formula (1). The production method according to claim 5, wherein the compound represented by the above general formula (I) is obtained by diazotizing the compound represented by the following formula (II) and the following formula (III) The one obtained by the diazo coupling reaction of the indicated compound and/or its salt,

[In formulas (II) and (III), R ¹ to R ¹⁰ and Y represent the same meanings as defined in Claim 1].