TW201942257A - Complex salt compound, dye composition, coloring agent and coloring method for anodized aluminum, and method for producing said compound - Google Patents

Abstract

The present invention relates to a compound represented by general formula (1) [wherein R1 to R10 independently represent -H, -SO3-, an amino group which has 0 to 20 carbon atoms and may have a -NO2 substituent, or the like; M represents a Cr atom or the like; X represents a non-chromogenic cation; k represents an integer of 1 to 8; and Y represents -O- or -O-(C=O)-], wherein R5 represents -NH2 or NHCOR5a, and R5a represents an alkyl group, R6 represents -NHCO-Ph, R9 represents -SO3- and/or R2 or R3 represents -CH3.

Description

Staggered salt compound, dye composition, coloring agent and coloring method for anodized aluminum, and method for producing the same

The present invention relates to a staggered salt compound, a dye composition containing the compound, a coloring agent for anodized aluminum containing the dye composition, a method for coloring anodized aluminum using the dye composition, and a method for manufacturing the compound.

Previously, as a method of coloring the surface of aluminum (also including aluminum oxide or aluminum alloy), electricity was applied to the aluminum as an anode in an electrolytic solution containing water and a suitable acid to make the aluminum surface a porous alumina layer. (Oxidized film, commonly referred to as alumina film) after treatment (hereinafter referred to as anodizing or anodizing treatment, alumina film treatment, etc.), then use: electrolytic coloring method using inorganic compounds or metal compounds; using inorganic dyes, Dyeing method of organic dyes (azo dyes, mixed salt compound dyes such as dye molecules and metal atoms, acid dyes, direct dyes, etc.) as colorants (see Patent Documents 1 to 14).

Those who use dyes as colorants have the problem of poor light resistance. In order to improve the light resistance of colored aluminum, various dyes with different salt compounds have been developed, but most of these colors are black or gray (for example, Patent Documents 1 to 6). In order to meet the needs of various colored aluminums in recent years, dyeing methods capable of coping with various colors of dyes have been developed (for example, Patent Documents 7 to 10). In addition, the development of additives for improving light resistance when using organic dyes is also being promoted (for example, refer to Patent Document 8).

On the other hand, a method of coloring anodized aluminum to blue, green, yellow, and red colors by using an electrolytic solution containing an organic acid or an inorganic acid and changing the voltage condition of anodization without using ordinary dyes has also been developed. (Patent Documents 11 to 13 and the like), but there are restrictions on the types of colors.

In addition, the anodized aluminum coloring film using dyes has not previously developed into the blue-green, green, or yellow-green monochrome dyes that are bright and light-resistant as expected by the market. Therefore, blue and yellow colorants are used (for example, TAC Green GM (1) and TAC Green SBM (2) are manufactured by Ao Ye Pharmaceutical Industry Co., Ltd.). However, in terms of color stability (no chromatic aberration, discoloration), it is required to use a monochrome dye to develop a coloring agent to a desired color. For example, an anthraquinone-based green azo dye (Patent Document 9) or a phthalocyanine green pigment (Patent Document 14) has been proposed as a colorant for anodized aluminum. Properties, light resistance have not yet reached the performance expected by the market.
[Prior technical literature]
[Patent Literature]

[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 Publication No. 2002-522617
[Patent Document 7] Japanese Patent Publication No. 2013-506053
[Patent Document 8] Japanese Patent Laid-Open No. 2009-91622
[Patent Document 9] Japanese Patent 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

[Problems to be solved by the invention]

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

In order to solve the above-mentioned problems, the inventors have made intensive studies on pigments (dyestuffs) for anodizing aluminum, and as a result, have found that by using a salt compound (azo dye) having a specific structure as a colorant for anodized aluminum, It is possible to form a film colored in blue, blue, green, and other blue-green colors with a monochromatic dye and excellent light resistance on anodized aluminum. That is, the present invention relates to the following inventions.

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

[In formula (1),
R ¹ ~ R ¹⁰ each independently represent _{^{-H, -SO 3 -, -NO 2}} , -NO, -CN, -OH, -COO -, -COOH, -SH, -F,
It may have an amino group having 0 to 20 carbon atoms,
It may also have a sulfofluorenyl group having 0 to 20 carbon atoms,
It may have a linear or branched alkyl group having 1 to 20 carbon atoms,
It may have a cycloalkyl group having 3 to 20 carbon atoms,
It may have a linear or branched alkoxy group having 1 to 20 carbon atoms in a substituent,
Cycloalkoxy having 3 to 20 carbon atoms, which may have a substituent,
It may have a linear or branched alkenyl group having 2 to 20 carbon atoms in a substituent,
It may have a substituent having 1 to 20 carbon atoms,
An aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent, or a heterocyclic group having 5 to 30 ring atoms which may have a substituent,
R ¹ to R ¹⁰ may also be bonded to each other to form a ring.
M represents a Cr, Fe, Co, Si or Al atom,
X is a non-chromogenic cation, k is an integer from 1 to 8,
Y means -O- or -O- (C = O)-]
As shown, 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 .
Compound [2] [1], the general formula in which ^{(1), R 1 ~ R} 4 are independently _{^{-H, -SO 3 -, -NO 2}} , also having 0 carbon atom of the substituent group An amine group of ~ 10, a linear or branched alkyl group having 1 to 10 carbon atoms that may have a substituent, or a linear or branched chain having 2 to 10 carbon atoms that may have a substituent Alkenyl or fluorenyl 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 have a substituent, and R ⁶ is -H, -SO ₃ ^- or may be substituent group having a carbon number of atoms of 0 to 10, any one of ¹⁰ R ⁷ ~ R is one or two -SO ₃ ^-.
[4] A dye composition containing the compound according to any one of [1] to [3].
[5] A coloring agent for anodized aluminum, which contains the dye composition as described in [4].
[6] A coloring method of anodized aluminum oxide, 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 Thing.
[7] a manufacturing method,
It is a method for producing a compound according to any one of [1] to [3], and includes making the following general formula (I):
[Chemical 2]

[In formula (I), R ¹ to R ¹⁰ and Y represent the same meaning as the above definition]
A step in which the compound shown is reacted with a compound containing a Cr, Fe, Co, Si or Al atom to obtain a compound represented by the general formula (1).
[8] The production method according to [7], wherein the compound represented by the general formula (I) is a diazide obtained by diazotizing a 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,
[Chemical 3]

[In the formulae (II) and (III), R ¹ to R ¹⁰ and Y have the same meanings as defined above].
[Effect of the invention]

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

Hereinafter, embodiments of the present invention will be described in detail. The present invention is not limited to the following embodiments, and various changes can be made within the scope of the gist thereof. A part in the square brackets [] in the compound represented by the general formula (1) is an anion and forms a complex with a non-color-developing cation represented by X in the general formula (1).

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

Formula (1), R ¹ ~ R ¹⁰ each independently represent _{^{-H, -SO 3 -, -NO 2}} , -NO, -CN, -OH, -COO -, -COOH, -SH, -F, also It may have an amino group having 0 to 20 carbon atoms in a substituent, a sulfofluorenyl group having 0 to 20 carbon atoms in a substituent, or a linear or branched chain having 1 to 20 carbon atoms in a substituent. A chain alkyl group, a cycloalkyl group having 3 to 20 carbon atoms which may have a substituent, a linear or branched alkoxy group having 1 to 20 carbon atoms which may have a substituent, or A cycloalkoxy group having 3 to 20 carbon atoms having a substituent, a linear or branched alkenyl group having 2 to 20 carbon atoms having a substituent, or 1 carbon atom having a substituent A fluorenyl group of ~ 20, an aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent, or a heterocyclic group of 5 to 30 ring atoms which may also have a substituent, R ¹ to R ¹⁰ may also be Adjacent radicals are bonded to each other to form a ring, M represents Cr, Fe, Co, Si or Al atom, X represents non-chromic cation, k represents an integer of 1 to 8, and Y represents -O- or -O- (C = O)-.

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

Hereinafter, the compound (1) will be specifically described, but the present invention is not limited to these. The anion part may have one kind of structure in the range of the general formula (1), or plural kinds of structures different from each other, and preferably one kind of structure. That is, the plurality of R ¹ to R ¹⁰ and Y may be the same type or different types, respectively. The non-color-developing cationic portion may be one type or a mixture of plural types, and one type is preferred. That is, when k is 2 to 8, the plurality of Xs existing may be the same type or different types.

In the present specification, examples of the "amino group having 0 to 20 carbon atoms which may have a substituent" include an unsubstituted amine group (-NH ₂ ), a mono-substituted amine group, and a di-substituted amine group. The number of carbon atoms in the mono-substituted amino group or the di-substituted amino group is, for example, 1 to 20, may be 1 to 10, and may be 2 to 6. The amine group having 0 to 20 carbon atoms which may have a substituent may be an aromatic hydrocarbon group having 6 to 30 carbon atoms or a heterocyclic ring having 5 to 30 ring atoms through -NH- Base of base. Examples of the mono-substituted amino group include an ethylamino group, an ethylamino group, and a phenylamino group. Examples of the di-substituted amino group include a diethylamino group, a diphenylamino group, and an ethylaminophenylamino group. The mono-substituted amino group may be a group represented by -NHCOR ^5a . The substituent R ^5a is an alkyl group.

In the present specification, "a sulfofluorenyl group which may have a substituent having 0 to 20 carbon atoms" means a substituent having -SO ₂ -R ¹⁰⁰ (or -S (= O) ₂ -R ¹⁰⁰ ) R ¹⁰⁰ is sulfofluorenyl. The substituent R ¹⁰⁰ may be a group containing a carbon atom or a group containing no carbon atom. When the substituent R ¹⁰⁰ is a group containing a carbon atom, the carbon number of the substituent R ¹⁰⁰ is 1 to 20, may be 1 to 10, and may be 1 to 7. Specific examples of the sulfofluorenyl group which may have a substituent having 0 to 20 carbon atoms include, for example, a sulfonamido group (-S (= O) ₂ -NH ₂ ), a methanesulfonyl group, and a tosylsulfonyl group .

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

In the present specification, as the "cycloalkyl group having 3 to 20 carbon atoms" in the "cycloalkyl group having 3 to 20 carbon atoms which may have a substituent", specific examples include cyclopropyl and cyclobutyl. Base, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclododecyl, and the like.

In the present specification, the term "linear or branched alkoxy group having 1 to 20 carbon atoms which may have a substituent" as "linear or branched chain having 1 to 20 carbon atoms" "Alkoxy" specifically includes methoxy, ethoxy, propoxy, n-butoxy, n-pentoxy, n-hexyloxy, heptyloxy, octyloxy, nonyloxy, and decyl Linear alkoxy groups such as oxy groups; branched chain alkoxy groups such as isopropoxy, isobutoxy, second butoxy, third butoxy, isooctyloxy, and third octyloxy base.

In the present specification, the "cycloalkoxy group having 3 to 20 carbon atoms" in the "cycloalkoxy group having 3 to 20 carbon atoms which may have a substituent", specifically, a cyclopropoxy group is exemplified. , Cyclobutoxy, cyclopentyloxy, cyclohexyloxy and the like.

In the present specification, a "straight-chain or branched-chain olefin having 2 to 20 carbon atoms" as a "straight-chain or branched-chain alkenyl group having 2 to 20 carbon atoms which may have a substituent" "Specifically," a vinyl group, an allyl group, an isopropenyl group, a 2-butenyl group, a 1-hexenyl group, or a linear or branched chain in which a plurality of these alkenyl groups are bonded may be listed. The base.

In the present specification, the "fluorenyl 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 a carbon atom or a group containing no carbon atom. When the substituent R ¹⁰¹ is a group containing a carbon atom, the number of carbon atoms of the substituent R ¹⁰¹ may be, for example, 1 to 20 and may be 1 to 10. The fluorenyl group having 1 to 20 carbon atoms which may have a substituent may be an aromatic hydrocarbon group having the following 6 to 30 carbon atoms or a heterocyclic group having 5 to 30 ring atoms via a fluorenyl group. The base. 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 "fluorenyl group having 1 to 20 carbon atoms" in the "fluorenyl group having 1 to 20 carbon atoms which may have a substituent" include, specifically, methylamino, ethylfluorenyl, propionyl, and propylene Fluorenyl, benzamidine and the like.

In the present 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, phenyl, naphthyl, Biphenyl, anthryl, phenanthryl, fluorenyl, bitriphenyl, indenyl, fluorenyl and the like. The "aromatic hydrocarbon group" in this specification refers to an aromatic hydrocarbon group and a condensed polycyclic aromatic group. Among these, a phenyl group or a naphthyl group is preferred.

In the present specification, the "heterocyclic group having 5 to 30 ring atoms" in the "heterocyclic group having 5 to 30 ring atoms which may have a substituent", specifically, pyridyl and pyrimidine Base, triazinyl, pyrrolyl, imidazolyl, pyrazolyl, triazolyl, quinolinyl, isoquinolinyl, naphthyridinyl, indolyl, benzimidazolyl, carbazolyl, carbolinyl, Acridinyl, morpholinyl, hydantoinyl, furanyl, benzofuranyl, dibenzofuranyl, thienyl, benzothienyl, dibenzothienyl, oxazolyl, benzoxazole Group, thiazolyl, benzothiazolyl, and the like.

In the present specification, "an amino group having 0 to 20 carbon atoms having a substituent", "sulfofluorenyl group having 0 to 20 carbon atoms having a substituent", and "a carbon atom having 1 to 20 carbon atoms having a substituent""Straight or branched alkyl", "Cycloalkyl having 3 to 20 carbon atoms having substituents", "Straight or branched alkane having 1 to 20 carbon atoms having substituents""Oxy","cycloalkoxy having 3 to 20 carbon atoms having a substituent", "straight or branched alkenyl having 2 to 20 carbon atoms having a substituent", "having a substituent "Substituted fluorenyl groups having 1 to 20 carbon atoms", "Aromatic hydrocarbon groups having 6 to 30 carbon atoms having substituents" or "Substituting heterocyclic groups having 5 to 30 ring atoms having substituents" group "specifically include: -SO ₃ ^-, nitro (-NO _2), nitroso (-NO2), cyano (-CN), hydroxyl (-OH), ^- COO -, carboxyl (- COOH), thiol group (-SH),
Unsubstituted amino groups; methylamino, dimethylamino, diethylamino, ethylmethylamino, methylpropylamino, di-thirdbutylamino, phenylamino Diphenylamino group, such as a linear or branched alkyl group having 1 to 17 carbon atoms or one of substituted or disubstituted amino groups having 6 to 24 carbon atoms;
A group having a sulfofluorenyl group (-S (= O) _2- ) such as a sulfonamido (-S (= O) ₂ -NH ₂ ) group, a methanesulfonyl group, a tosylsulfonyl group;
Methyl, ethyl, n-propyl, isopropyl, n-butyl, second butyl, third butyl, pentyl, n-hexyl, isohexyl, heptyl, n-octyl, third octyl, iso Linear or branched alkyl groups having 1 to 17 carbon atoms, such as octyl, nonyl, and decyl;
Cycloalkyl groups having 3 to 17 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, and cyclododecyl;
Linear or branched alkoxy groups having 1 to 17 carbon atoms, such as methoxy, ethoxy, propoxy, third butoxy, n-pentoxy, and n-hexyloxy;
Cycloalkoxy groups having 3 to 17 carbon atoms such as cyclopropoxy, cyclobutoxy, cyclopentyloxy, and cyclohexyloxy;
Vinyl, 1-propenyl, allyl, 1-butenyl, 2-butenyl, 1-pentenyl, 1-hexenyl, isopropenyl, isobutenyl, or such alkenyl bonds A plurality of straight or branched alkenyl groups having 2 to 19 carbon atoms;
Formamyl, ethenyl, propionyl, propenyl, benzyl and the like;
Aromatic hydrocarbon groups having 6 to 24 carbon atoms, such as phenyl, naphthyl, anthryl, phenanthryl, fluorenyl, bitriphenyl, indenyl, and fluorenyl;
Pyridyl, pyrimidinyl, triazinyl, pyrrolyl, imidazolyl, pyrazolyl, triazolyl, pyryl, daphyl, piperidinyl, piperazinyl, quinolinyl, isoquinolinyl, naphthyridinyl , Indolyl, benzimidazolyl, carbazolyl, carbolinyl, acridinyl, morpholinyl, morphinyl, hydantoinyl, furanyl, benzofuranyl, dibenzofuranyl, Pyranyl, coumarin, isobenzofuranyl, Base, oxanthranyl, pyranyl, thienyl, thienyl, benzothienyl, dibenzothienyl, 9-oxothio Hexyl, oxazolyl, benzoxazolyl, morpholinyl, thiazolyl, benzothiazolyl and other heterocyclic groups having 5 to 24 ring atoms;
Cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, (1,3- or 1,4-) cyclohexadienyl, 1,5-cyclooctadienyl Equivalent cyclic olefin groups with 3 to 24 carbon atoms, etc. These "substituents" may contain only one or a plurality of them, and when there are a plurality of them, they may be the same or different. These "substituents" may have the substituents exemplified above, and further, these substituents may 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 may be -H, for example. R ² can be, for example, ^{_{-H, -SO 3 -, -CN,}} -NO, -NO 2, also having a number of carbon atoms of the substituent group having 1 to 20 (or 1 to 10 carbon atoms) of linear or branched the alkyl chain (e.g., -CH _3), may also have a substituent group of carbon number 1 to 20 (or 1 to 10 carbon atoms) of the straight-chain or branched alkoxy group (e.g., - OCH ₃ ), or a linear or branched alkenyl group having 2 to 20 carbon atoms (or 2 to 10 carbon atoms) which may have a substituent (for example, -CH = CH-CH ₃ ), or It can be -NO ₂ or CH ₃ . R ³ may be, for example, -H, -NO ₂ , a cycloalkoxy group having 3 to 20 carbon atoms that may have a substituent, or 1 to 20 carbon atoms (or 1 to 10 carbon atoms) that may have a substituent. ), A linear or branched alkoxy group, or a linear or branched alkyl group having 1 to 20 carbon atoms (or 1 to 10 carbon atoms) which may have a substituent (for example, -CH ₃ ), or -H. R ⁴ may 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, R ¹ , R ³ and R ⁴ may be -H, respectively. When R ³ is -CH ₃ , R ¹ , R ² and R ⁴ may be -H, respectively.

In the general formula (1), R ¹ to R ⁴ represent the substituents as described above, but adjacent groups may be bonded to each other through a single bond or a bond through an oxygen atom (-O-) or a sulfur atom. The 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-developing cation, and specific examples thereof include hydrogen ion (H ⁺ ), lithium ion (Li ⁺ ), sodium ion (Na ⁺ ), potassium ion (K ⁺ ), and the like. Alkali metal ions, cations containing organic compounds, etc. Among these, an alkali metal ion is more preferable, and K ⁺ or Na ^{+ is more} preferable.

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

In the general formula (1), "Y" means "-O-" or "-O- (C = O)-", and in the case of "-O- (C = O)-", it is preferably Bonding is performed like "M" and "MO- (C = O)-".

R ^{5 is} preferably -H or an amino group having 0 to 10 carbon atoms which may have a substituent, and more preferably -H or -NH ₂ . R ^{6 is} preferably -H, -SO ₃ ^- or an amine group having 0 to 10 carbon atoms which may have a substituent. R ⁷ ~ R ¹⁰ of any one or two preferred is -SO ₃ ^-, in any of the two R ⁷ ~ R ¹⁰ is -SO ₃ ^- when the situation, R ⁷ and R ¹⁰ is 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 as the above-mentioned linear or branched alkyl group having 1 to 20 carbon atoms, and may be a methyl group. In the general formula (1), in the case when R ⁵ is -NH ₂ or NHCOR ^5a of, for example, R ⁶ may be -H or SO ₃ ^-, R ⁷ can be -H, -SO ₃ ^-, R ⁸ may be is _{^{-H, -SO 3 -, -COO -}} , R 9 may be -H, a substituent may also have a number of carbon atoms of a cycloalkyl group having 3 to 20, or may have a substituent group having a carbon number of 6 to 30 atoms As the aromatic hydrocarbon group, R ¹⁰ may be -H, -SO ₃ ^- or a fluorenyl group having 1 to 20 carbon atoms which may have a substituent.

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

The compound (1), R ⁹ may be -SO ₃ ^-. To R ⁹ is -SO ₃ ^- of the case when, for ^{example, R 5, R 6, R} 7, R 8 and R ¹⁰ may be -H.

The compound of the present invention represented by the general formula (1) includes all possible stereoisomers, and any of the isomers 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 with respect to the compound of the general formula (1), the compound of the present invention includes the general formula (1) and the general formula (1-a) The compound may be a mixture of two or more kinds 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 formulas, but the present invention is not limited to these. In addition, in the exemplified compounds, the entire charge of the anion portion in the square brackets [] of the general formula (1) is described, and a part of the hydrogen atom is omitted in the structural formula.
[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]

[Chemical 21]

[Chemical 22]

[Chemical 23]

[Chemical 24]

[Chemical 25]

[Chemical 26]

[Chemical 27]

[Chemical 28]

[Chemical 29]

The compound (1) may be a compound represented by the formulae (A-1) to (A-24), and may be a formula (A-3) from the viewpoint that light resistance is further superior and heat resistance is further superior. Or a compound represented by (A-4).

Although an example of the manufacturing method of the compound represented by General formula (1) is shown below, it is not limited to this method. Specifically, first, by making the following general formula (II):
[Chemical 30]

[In formula (II), R ¹ to R ⁴ and Y have the same meanings as defined above]
The aromatic amine derivative and / or its salt shown and having an appropriate substituent are reacted in an acid aqueous solution such as hydrochloric acid and sulfuric acid with a basic aqueous solution prepared using sodium nitrite and the like at an appropriate temperature to obtain the following general formula. Formula (IV):
[Chemical 31]

[In formula (IV), R ¹ to R ⁴ and Y have the same meanings as defined above]
The compound shown and / or its salt (diazo component).
By making the following general formula (III):
[Chemical 32]

The compound shown is dissolved in an aqueous solution such as sodium hydroxide and reacted to obtain the following formula (IIIa):
[Chemical 33]

[In formula (IIIa), R ¹ to R ⁴ and Y represent the same meanings as defined above, and n represents 0, 1 or 2]
Compounds shown (couplings).
Next, the diazo component and the coupling component are reacted (diazo coupling reaction) to obtain an azo compound (azo dye) represented by the following general formula (I).
[Chem 34]

[In formula (II), R ¹ to R ⁴ and Y have the same meanings as defined above].

Then, a reaction solution containing an azo compound represented by the above-mentioned general formula (I) and an aqueous solution containing a compound containing an atom represented by M were prepared such that the atom (M): azo dye = 1: 2, and allowed to react. The compound (1) can be produced in the form of a 1: 2 type complex salt compound by performing cross-salting and salting out by waiting for the reaction. The compound containing an atom represented by M is a compound containing Cr, Fe, Co, Si, or Al atoms, and may be used alone or in combination of two or more kinds. Specific examples of the compound containing an atom represented by M include, for example, chromium acetate.

That is, the manufacturing method of the compound (1) of one Embodiment is provided with the following general formula (I):
[Chemical 35]

[In formula (I), R ¹ to R ¹⁰ and Y represent the same meanings as described above]
The step of reacting the shown compound (compound (I)) with a compound containing Cr, Fe, Co, Si or Al atom. As described above, the compound (I) may be a diazide (compound (IV)) obtained by diazotizing a compound (compound (II)) represented by the following formula (II) and the following formula (III) It is obtained by the diazo coupling reaction of the compound (compound (III)) and / or its salt represented by).
[Chemical 36]

[Chemical 37]

Compound (1) can be purified by known methods such as: purification by column chromatography; adsorption purification by silica gel, activated carbon, activated clay, etc .; recrystallization and crystallization by solvent. Compound identification and physical property evaluation can use UV-Vis, thermogravimetry-differential thermal analysis (TG-DTA), gas chromatography (GC), nuclear magnetic resonance analysis (NMR) analysis, etc. And proceed.

The compound (1) can be used as a component of a dye composition. Even if the compound (1) is used alone, aluminum, fibers, and the like can be colored. That is, the compound (1) can be preferably used as a pigment compound for coloring aluminum, fibers, and the like by using a single monochrome dye alone. The compound (1) may be used in combination of two or more kinds to obtain a plurality of colors by color mixing. The dye composition may be mixed with other ingredients for optimal dyeing (coloring using a dye). Specific examples include liquids (solvents) such as water, alcohols, and solvents; and additives such as surfactants. The solvent is preferably water. The compound (1) may be used in combination with other dyes as a component of a dye composition. Other compounds, pigments, and dyes other than the pigment-based compound (1), specifically, ruthenium complexes, coumarin-based pigments, anthocyanins-based pigments, merocyanine-based pigments, and rhodocyanine-based compounds Pigment, phthalocyanine pigment, porphyrin pigment, Department of pigments and so on. In the case where the compound (1) is used in combination with other components, the use amount of the other components with respect to the compound (1) is preferably 10 to 200% by mass, and more preferably 20 to 100% by mass.

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, the concentration of compound (1) in the dye composition containing compound (1) in the coloring (dyeing) method is relative to the total amount of the dye composition, It is preferably 0.02 to 10% by mass, and more preferably 0.05 to 1% by mass.

Here, the anodized aluminum refers to aluminum in which an electrolytically treated aluminum surface is treated to form an oxide layer having pores in an electrolytic solution such as an acid aqueous solution. The coloring agent for anodized aluminum refers to a coloring (staining) by which the compound (1) can be adsorbed into the pores by using a dye composition containing the compound (1) on the aluminum surface having the pores. Generally, in order to improve the durability and light resistance of the colored aluminum surface, a sealing process for blocking the pores is performed after the coloring.

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

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

First, an aluminum plate is degreased with an acid aqueous solution such as sulfuric acid, oxalic acid, chromic acid, and sulfonic acid, and washed with water. Next, the degreased aluminum plate is used as an anode, and an acidic aqueous solution is used as an electrolyte for electrolysis. On the surface of the aluminum anode, an anodic oxide film (alumina film) having a large number of pores is formed (anodized), and then Washed. Then, after surface adjustment, water washing, and the like are appropriately performed, it is immersed in an aqueous solution of a coloring agent for anodized aluminum containing a dye composition containing the compound of the present invention, and the dye is adsorbed (dyed, electrolytically colored) into the pores, and aluminum is used. The oxide hydrate and the like can seal the pores on the surface to form a sealing substance, whereby coloring can be performed.
When the dye composition of the present invention is used in combination of two or more kinds, or when the dye composition of the present invention is used in combination with other dyes, a mixed solution of all the dyes to be used may be prepared and anodized aluminum may be impregnated therein. Alternatively, each pigment solution can be separately prepared and sequentially immersed in each solution.

The electrolysis conditions during coloring can be either direct current electrolysis or alternating current electrolysis, preferably direct current electrolysis. The current density is preferably 0.1 to 10 A / dm ² , and more preferably 0.5 to 3 A / dm ² . The power-on time is preferably 10 seconds to 60 minutes. The thickness of the anodized film is preferably 2 to 20 μm.

The processing temperature of each of the above steps is preferably an appropriate temperature, and the temperature during anodization is preferably 0 to 80 ° C. The temperature during dyeing is preferably 10 ° C to 70 ° C. Other processing temperatures are preferably 10 to 80 ° C.

The dye composition of this embodiment can also be used similarly to an anodic oxide using a metal 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 can adsorb dyes to anodic pores.

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

According to the coloring agent for anodized aluminum according to this embodiment, it is possible to display green, blue, purple, and other light (light green, etc.) or dark (black green, etc.) different shades. According to the coloring agent for anodized aluminum according to this embodiment, it is also possible to display a color mixture (yellow green, dark blue, black, gray, brown, etc.) by mixing the above-mentioned compound with other dyes in combination. As the intermediate color, black and gray are preferable.

The light resistance test of colored aluminum using the coloring agent for anodized aluminum oxide of this embodiment can also use a test 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. The change of hue of colored aluminum before and after was evaluated. Regarding the determination of light resistance, the fastness of dyeing aluminum can also be determined by visual inspection using gray scale in accordance with the method specified in Japanese Industrial Standards (gradation for discoloration, JIS L 0804).

The heat resistance test of the colored aluminum using the coloring agent for anodized aluminum in this embodiment may be, for example, heating in a thermostat or a hot-air dryer in a temperature range of 50 to 300 ° C for 30 minutes to 50 hours, as appropriate. The method of evaluating the change in hue before and after the test in the same manner as the light resistance test, such as the method of fixing time.

The colored aluminum using the coloring agent for anodized aluminum according to this embodiment is used for various aluminum plate materials, aluminum exteriors, and the like.
[Example]

Hereinafter, the present invention will be specifically described by way of examples, but it is not limited to the following examples.

[Synthesis Example 1: Synthesis of Compound (A-1)]
(Preparation of diazo component)
In a reaction vessel, 20 g of 2-amino-4-nitrophenol, 140 mL of water, and 11 g of 35% hydrochloric acid were placed. While the obtained reaction solution was stirred at 10 ° C., 23 g of a 40% by weight sodium nitrite aqueous solution was added dropwise, and then reacted for 1 hour. Thus, a diazo component liquid was obtained.
(Preparation of even fractions)
In a reaction vessel, 30 g of 8-amino-1-hydroxynaphthalene-3,6-disulfonic acid, 200 mL of water, and 18.9 g of a 24% by weight aqueous sodium hydroxide solution were placed. The obtained reaction solution was stirred at 10 ° C. for 1 hour to obtain a coupling liquid.
(Diazo coupling reaction)
A diazo component liquid was placed in the coupled coupling liquid while stirring, and stirred for 1 hour to carry out a 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) and the retention time peak positions and areas obtained by observing typical azo dyes.
(Wrong salting)
A 48% by weight chromium acetate aqueous solution was put into the reaction solution after the coupling was completed, and the mixture was stirred at a range of 80 to 100 ° C. The completion of the reaction was confirmed by TLC. After the reaction, the obtained reaction solution was cooled to 25 ° C. Sodium chloride was added, and the precipitated solid was collected by filtration. The solid was dried under reduced pressure, and compound (A-1) was obtained as a solid powder (15.3 g, yield: 31.1%).
[Synthesis Example 2: Synthesis of Compound (A-2)]
Compound (A-2) was obtained in the same manner as in Synthesis Example 1 except that 2-amino-5-nitrophenol was used instead of 2-amino-4-nitrophenol.
[Synthesis Example 3: Synthesis of Compound (A-3)]
Compound (A-3) was obtained in the same manner as in Synthesis Example 1 except that 2-amino-4,6-dinitrophenol was used instead of 2-amino-4-nitrophenol.
[Synthesis Example 4: Synthesis of Compound (A-4)]
Use picrinic acid (2-amino-4,6-dinitrophenol) instead of 2-amino-4-nitrophenol and 1-amino-8-naphthol-4-sulfonic acid instead of 8-amine A compound (A-4) was synthesized in the same manner as in Synthesis Example 1 except that the compound was substituted with 1-hydroxyl-naphthalene-3,6-disulfonic acid. Compound (A-4) is obtained as a solid powder.
[Synthesis Example 5: Synthesis of Compound (A-5)]
Use picric acid (2-amino-4,6-dinitrophenol) instead of 2-amino-4-nitrophenol and 1-amino-8-naphthol-2,4-disulfonic acid instead A compound (A-5) was synthesized in the same manner as in Synthesis Example 1 except for 8-amino-1-hydroxynaphthalene-3,6-disulfonic acid.
[Synthesis Example 6: Synthesis of Compound (A-6)]
Use picrinic acid (2-amino-4,6-dinitrophenol) instead of 2-amino-4-nitrophenol and 1-ethylamido-8-naphthol-3,6-di Compound (A-6) was synthesized in the same manner as in Synthesis Example 1 except that sulfonic acid was used instead of 8-amino-1-hydroxynaphthalene-3,6-disulfonic acid.
[Synthesis Example 7: Synthesis of Compound (A-7)]
Compound (A-7) was obtained in the same manner as in Synthesis Example 1 except that 2-amino-4-methylphenol was used instead of 2-amino-4-nitrophenol.
[Synthesis Example 8: Synthesis of Compound (A-8)]
Use picrinic acid (2-amino-4,6-dinitrophenol) instead of 2-amino-4-nitrophenol and 6-benzylideneamino-4-hydroxy-2-naphthalenesulfonic acid A compound (A-8) was synthesized in the same manner as in Synthesis Example 1 except that 8-amino-1-hydroxynaphthalene-3,6-disulfonic acid was replaced.
[Comparative example]
As a compound for comparison, the dye index (CI) of acid green 1, acid green 9, acid green 25, acid green 28, acid green 73, acid green 104, and acid green 111 are prepared as green alumina film dyes Of compounds.
[Chemical 38]

[Reference example]
Compounds (Q-1) and (Q-2) represented by the following formulas were prepared as black alumina film dyes.
[Chemical 39]

＜ Evaluation of hue and light resistance test ＞
[Example 1]
Anodizing was performed on an aluminum substrate in the following procedure to produce colored aluminum. Furthermore, in the steps of anodizing and dyeing, two dyeing conditions are set which change the treatment time and the concentration of the dye compound.
(Degreasing) In a container, 150 mL of degreasing agent (TOP ADD-100, manufactured by Okuno Pharmaceutical Industry Co., Ltd.), 70 mL of 98% sulfuric acid, and 1000 mL of water are mixed to prepare a degreasing solution, which is cut into dyes of an appropriate size. The aluminum substrate was immersed therein, and degreased at 60 ° C for 3 minutes, and then washed with water.
(Anodic oxidation) Use 180% sulfuric acid to prepare 180 g / L electrolyte, connect the aluminum substrate to the electrode of the electrolytic device, and immerse it in the electrolyte tank at a temperature of 20 ± 1 ℃ and a current density of 1.0 A / dm ² or less Anodizing was performed under the conditions of the energization time to obtain an anodized film having the following thickness. After oxidation, washing with water was performed.
Dyeing condition (1): 15 minutes after anodizing. Film thickness: 5 μm
Dyeing conditions (2): Anodized film thickness for 45 minutes after application of electricity: 15 μm
(Surface adjustment) A surface adjustment solution (manufactured by Okuno Pharmaceutical Industry Co., Ltd., TAC SORMAL 121) and water was used to prepare a surface adjustment solution having a concentration of 50 mL / L, and the aluminum substrate was immersed therein at 45 ° C for 1 minute. After immersion, the aluminum substrate was washed with water.
(Dyeing) Using the compound (A-1) obtained in Synthesis Example 1 as a dye, a dyeing aqueous solution containing a dye having the following concentration was prepared as the dye composition of the present invention, and dipped for the following dyeing time, all in Dyeing was performed at a temperature of 55 ° C. After dyeing, the aluminum substrate was washed with water.
Dyeing condition (1): Pigment concentration of 0.1% by weight Dyeing time: 30 seconds Dyeing condition (2): Pigment concentration of 0.2% by weight Dyeing time: 5 minutes
(Sealing) A 40 mL / L sealing solution was prepared using a sealing agent (TOP Seal H-298, manufactured by Okano Pharmaceutical Industry Co., Ltd.) and water, and sealing was performed at about 90 ° C for 15 minutes. After the sealing process, drying is performed with warm air.

(Hue evaluation) The hue of a colored aluminum plate colored with the compound (A-1) was visually evaluated. The evaluation results are shown in Table 1.

(Light resistance test) The light resistance test was performed with the following method about the colored aluminum plate coloring using the compound (A-1). Xenon attenuator / ATLAS Ci3000 + Xenon Weather Ometer (manufactured by Atlas), radiation intensity: 300 ~ 400 nm, 60 W / m ² , temperature in test tank: 38 ° C, humidity: 50%, black panel (BP) Temperature: 63 ° C, the colored aluminum plate was irradiated for 50 hours, and based on the obtained results, the fastness of dyeing was determined visually by using the number of gray levels (gray for discoloration, JIS L 0804). The number of stages is the highest at level 5 and the lowest at level 1. The higher the level, the stronger the color and the hue before irradiation. In the evaluation method of the present invention, the determination result of the number of levels is divided into three levels, and the evaluation is performed according to the following determination criteria. The results are summarized in Table 1.
Gray scale judgment criterion: Correspondence between the number of levels and the evaluation (A, B, C) in the present invention
Levels 5 to 4: A (especially good light resistance)
Level 3: B (normal level of light resistance)
Below level 2: C (low light resistance)
[Examples 2 to 8, Comparative Examples and Reference Examples]
A colored aluminum plate was produced in the same manner as in Example 1 except that the compounds shown in Table 1 were used instead of the compound (A-1), and the hue and light resistance were evaluated. The measurement results are summarized in Table 1.

[Table 1]

According to the results in Table 1, by using an anodized aluminum colorant containing the dye composition containing the compound of the present invention, blue, blue-green, light green, green, black green, light blue, blue, and ink can be formed on aluminum. Blue, black and green blue-green film with high light resistance. The light resistance obtained by using the compounds of the examples is not inferior to that of a film made using a conventional black pigment (Q-1) or (Q-2). On the other hand, those obtained using the pigment of the comparative example had poor light resistance.
＜ Heat resistance test ＞
[Example 3]
With respect to the colored aluminum plate which was colored under the dyeing condition (2) of the above example using the compound (A-3), a heat resistance test was performed by the following method. Using a constant temperature dryer (manufactured by AS ONE Co., Ltd., model: 87L EOP-450V), the samples were heated under the following exposure conditions.
Temperature and heating time in the dryer: 200 ° C-5 hours, or 250 ° C-3 hours. The method for evaluating heat resistance of the present invention is to measure the color difference of colored aluminum samples before and after heating by using the following color difference meter and judge according to the following The benchmark was evaluated visually. The results are shown in Table 2.
Device: Color Difference Meter (Konica Minolta Spectrophotometer, Model: CM-3700A)
Color difference calculation formula: ΔE ^* _ab (L ^* a ^* b ^* , CIE 1976) and ΔE ^* ₀₀ (CIE DE2000)
Viewing angle: 10 °
Criteria for determining heat resistance:
A: Good heat resistance (no discoloration or discoloration)
B: Normal level heat resistance (no discoloration 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 Compound (A-4) was used. When heated at 250 ° C, it becomes a greenish color with a slight black tone, but it is generally heat-resistant. The results are summarized in Table 2.
[Comparative and Reference Examples]
A heat resistance test was performed in the same manner as in Example 3 except that Acid Green 9, 28, 104, or TAC Green SBM (2), which was previously used as a green pigment, was used. The results are summarized in Table 2.

A heat resistance test was performed in the same manner as in Example 3 except that the compounds (Q-1) and (Q-1) using the previous black pigment were used. The results are summarized in Table 2.
[Table 2]

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

According to the dye composition containing the compound of the present invention, a coloring agent for anodized aluminum having excellent light resistance and capable of forming a blue-green colored film in a single color can be obtained. By using the coloring agent of the present invention, it is possible to obtain an anodized aluminum oxide film having excellent light resistance in a blue-green color by monochromatic coloration. The colored film obtained by using the dye composition containing the compound of the present invention is also excellent in heat resistance.

Claims (8)

A compound, It is represented by the following general formula (1): [Chemical 1] [In formula (1), R¹ ~ R¹⁰ Represents -H and -SO independently₃ ^- , -NO₂ , -NO, -CN, -OH, -COO^- , -COOH, -SH, -F, It may have an amino group having 0 to 20 carbon atoms, It may also have a sulfofluorenyl group having 0 to 20 carbon atoms, It may have a linear or branched alkyl group having 1 to 20 carbon atoms, It may have a cycloalkyl group having 3 to 20 carbon atoms, It may have a linear or branched alkoxy group having 1 to 20 carbon atoms in a substituent, Cycloalkoxy having 3 to 20 carbon atoms, which may have a substituent, It may have a linear or branched alkenyl group having 2 to 20 carbon atoms in a substituent, It may have a substituent having 1 to 20 carbon atoms, It may have an aromatic hydrocarbon group having 6 to 30 carbon atoms as a substituent, or It may also have a heterocyclic group having 5 to 30 ring atoms having a substituent, R¹ ~ R¹⁰ Adjacent bases can also be bonded to each other to form a ring. M represents a Cr, Fe, Co, Si or Al atom, X is a non-chromogenic cation, k is an integer from 1 to 8, Y means -O- or -O- (C = O)-] As shown, and R⁵ For -NH₂ Or NHCOR^5a And R^5a Is alkyl, R⁶ -NHCO-Ph, R⁹ For -SO₃ ^- , And / or R² Or R³ For -CH₃ . The compound of the requested item 1, wherein in the above general formula (1), R ¹ ~ R ⁴ are independently _{^{-H, -SO 3 -, -NO 2}} , may also have substituent groups of carbon atoms from 0 to 10 An amine group, a linear or branched alkyl group having 1 to 10 carbon atoms that may have a substituent, or a linear or branched chain olefin having 2 to 10 carbon atoms that may have a substituent Or a fluorenyl group having 1 to 10 carbon atoms which may have a substituent. For example, the compound of claim 1 or 2, wherein R ⁵ is -H or an amino group having 0 to 10 carbon atoms which may have a substituent, and R ⁶ is -H, -SO ₃ ^- or a carbon which may also have a substituent. 0 to 10 atoms of the group, any one of ¹⁰ R ⁷ ~ R is one or two -SO ₃ ^-. A dye composition containing the compound according to any one of claims 1 to 3. A coloring agent for anodized aluminum, which contains the dye composition according to claim 4. A coloring method of anodized aluminum oxide, anodized aluminum oxide, or anodized aluminum alloy, characterized in that a dye composition containing 0.02 to 10% by mass of the compound according to any one of claims 1 to 3 is used. A manufacturing method, which is a method for manufacturing a compound according to any one of claims 1 to 3, and includes the following general formula (I): [化 2] [In the formula (I), R ¹ to R ¹⁰ and Y represent the same meaning as the above definition] The compound shown is reacted with a compound containing a Cr, Fe, Co, Si, or Al atom to obtain the general formula (1 ) For the compound shown. The production method according to claim 7, wherein the compound represented by the general formula (I) is a diazonium compound obtained by diazotizing a compound represented by the following formula (II) and the following formula (III) Obtained from the diazo coupling reaction of the shown compound and / or its salt, [Chem. 3] [In the formulae (II) and (III), R ¹ to R ¹⁰ and Y have the same meanings as defined above].