JP2021038380A - Compound, dye composition, aluminum anodic oxide coloring agent and coloring method, and production method of that compound - Google Patents

Abstract

To provide a compound capable of forming, on a surface of aluminum, aluminum oxide or aluminum alloy, an anodic oxide coating excellent in light fastness and heat resistance and free of heavy metal such as chromium; a dye composition; an aluminum anodic oxide coloring agent and coloring method; and a production method of the compound.SOLUTION: The compound is represented by the general formula (I) in the figure. [In the formula (1), A represents an optionally substituted alkyl group or the like; R1 represents -COO- or -COOH; R2 to R6 independently represent respective various groups such as -H, -OH, -COO-, -COOH, -NO2, -NO, -CN, -SO3-, -SO3H, -SH, an amino group, and an alkyl group, where neighboring groups of R2 to R5 may be linked to each other to form a ring; X represents a non-coloring cation; and k represents an integer from 1 to 6.]SELECTED DRAWING: None

Description

The present invention relates to compounds, dye compositions and colorants for anodized aluminum. The present invention also relates to a method for coloring aluminum anodized using the compound and a dye composition, and a method for producing the compound.

Conventionally, as a method of coloring the surface of aluminum (including its oxide or alloy), aluminum is energized (anodized) as an anode in an electrolytic solution containing water and an appropriate acid, and a porous aluminum oxide film (anodic oxide) is applied to the surface. After forming an alumite film), a dyeing method is used in which the surface is colored using an organic dye as a colorant (Patent Documents 1 to 4).

In order to meet the demand for a wide variety of colored aluminum products in recent years, a dyeing method (Patent Document 4) capable of dealing with dyes of various colors has been developed.

Japanese Unexamined Patent Publication No. 9-302256 Japanese Unexamined Patent Publication No. 60-235867 Special Table 2002-522617 Special Table 2013-506053

For example, a reddish yellow to orange alumite film dye is preferably used as a gold color, but conventional dyes have insufficient light resistance and do not require color mixing and are single. As a dye, a dye having good light resistance is required.

Chromium-containing dyes for alumite films (Patent Documents 1 to 3 and the like) have excellent light resistance and heat resistance and have been used for general purposes. However, in recent years, they do not contain heavy metals such as chromium from the environmental point of view. , Dyes having various hues are required.

The problem to be solved by the present invention is a compound having excellent light resistance and heat resistance and capable of forming an anodized film containing no heavy metal such as chromium on the surface of aluminum, aluminum oxide or aluminum alloy. It is an object of the present invention to provide a dye composition containing the above, a colorant and a coloring method for anodized aluminum comprising the dye composition, and a method for producing the compound.

In order to solve the above problems, the inventors have diligently studied a dye (dye) for aluminum anodic oxidation, and as a result, anodized by using a compound having a specific structure (azo dye) as a colorant for aluminum anodic oxide. It has been found that a film having excellent light resistance and heat resistance can be formed on aluminum. That is, the present invention is composed of, for example, the following contents.

［式（１）中、Ａは置換基を有していてよいアルキル基、置換基を有していてよいシクロアルキル基、又は下記式（Ｉａ）で表される基を表し、

Ｒ^１は―ＣＯＯ⁻または―ＣＯＯＨを表し、
Ｒ^２〜Ｒ^１１はそれぞれ独立に、―Ｈ、―ＯＨ、―ＣＯＯ⁻、―ＣＯＯＨ、―ＮＯ_２、―ＮＯ、―ＣＮ、―ＳＯ_３ ⁻、―ＳＯ_３Ｈ、―ＳＨ、
置換基を有していてもよい炭素原子数０〜２０のアミノ基、
置換基を有していてもよい炭素原子数０〜２０のスルホニル基、
置換基を有していてもよい炭素原子数１〜２０の直鎖状もしくは分岐状のアルキル基、
置換基を有していてもよい炭素原子数３〜２０のシクロアルキル基、
置換基を有していてもよい炭素原子数１〜２０の直鎖状もしくは分岐状のアルコキシ基、
置換基を有していてもよい炭素原子数３〜２０のシクロアルコキシ基、
置換基を有していてもよい炭素原子数２〜２０の直鎖状もしくは分岐状のアルケニル基、
置換基を有していてもよい炭素原子数１〜２０のアシル基、
置換基を有していてもよい炭素原子数６〜３０の芳香族炭化水素基、または
置換基を有していてもよい環形成原子数５〜３０の複素環基を表し、
Ｒ^２〜Ｒ^５、Ｒ^７〜Ｒ^１１は、隣り合う基同士で互いに結合して環を形成していてもよく、
Ｘは非発色カチオンを表し、ｋは１〜６の整数を表す。］ [1] A compound represented by the following general formula (I).

[In the formula (1), A represents an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, or a group represented by the following formula (Ia).

R ¹ is -COO ^- represents or -COOH,
The R ² to R ¹¹ are each _{^{independently, -H, -OH, -COO -,}} -COOH, -NO 2, -NO, -CN, -SO 3 -, -SO 3 H, -SH,
An amino group having 0 to 20 carbon atoms, which may have a substituent,
A sulfonyl group having 0 to 20 carbon atoms, which may have a substituent,
A linear or branched alkyl group having 1 to 20 carbon atoms, which may have a substituent,
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,
A cycloalkoxy group having 3 to 20 carbon atoms, which may have a substituent,
A linear or branched alkenyl group having 2 to 20 carbon atoms, which may have a substituent,
Acyl groups having 1 to 20 carbon atoms, which may have substituents,
It represents an aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent, or a heterocyclic group having 5 to 30 ring-forming atoms which may have a substituent.
^{R 2 ~R 5, R 7 ~R} 11 is bonded together with the adjacent group together may form a ring,
X represents a non-coloring cation and k represents an integer of 1-6. ]

[2] The compound according to [1], which is represented by the following general formula (1).

[In formula (1), R ^{1 to} R ¹¹ , X and k have the same meaning as the above definitions. ]

[3] The general formula (I), independently ^{of R 4} and ^{R 5} are _{^{each, -H, -COO -, -COOH,}} -NO 2, -SO 3 -, -SO 3 H, or, a substituent The compound according to [1] or [2], which is a linear or branched alkyl group having 1 to 10 carbon atoms which may be possessed.

[4] In the general formula (I), R ⁶ has —COO ⁻ , —COOH, an amino group having 0 to 10 carbon atoms which may have a substituent, or a substituent. The compound according to any one of [1] to [3], which is a linear or branched alkyl group having 1 to 10 carbon atoms.

In [5] the general formula ^{(1), R} 7 ~R ¹¹ are each ^{_{independently, -H, -NO 2, -SO 3}} -, a _-SO 3 H or _{-SO 2 NH 2,, [1} ] The compound according to any one of [4].

[6] A dye composition containing the compound according to any one of [1] to [5].

[7] A colorant for anodized aluminum containing the dye composition according to [6].

[8] A method for coloring aluminum anodized aluminum or an aluminum anodized alloy, which comprises using a dye composition containing 0.02 to 10% by mass of the compound according to any one of [1] to [5]. ..

[9] In the method for producing the compound according to any one of [1] to [5], the compound represented by the general formula (I) is a compound represented by the following general formula (II). A production method obtained by a diazo coupling reaction between a diazodized product obtained by diazotization and a compound represented by the following general formula (III) and / or a salt thereof.

[In formulas (II) and (III), A and R ^{1 to} R ¹¹ have the same meaning as the above definitions. ]

[10] A method for producing a compound represented by the general formula (1), wherein the compound represented by the general formula (1) is obtained by diazotizing a compound represented by the following general formula (2). A production method obtained by a diazo coupling reaction between a diazo product obtained from the above and a compound represented by the following general formula (3) and / or a salt thereof.

[In formulas (2) and (3), R ^{1 to} R ¹¹ have the same meaning as the above definitions. ]

According to the present invention, a compound capable of forming an anodized film having excellent light resistance and heat resistance and not containing heavy metals such as chromium on the surface of aluminum, aluminum oxide or aluminum alloy, and a dye composition containing the compound. , A colorant for aluminum anoxide and a coloring method comprising the dye composition, and a method for producing the compound can be provided.

Hereinafter, embodiments of the present invention will be described in detail. The present invention is not limited to the following embodiments, and can be variously modified and implemented within the scope of the gist thereof. Hereinafter, the compound represented by the general formula (I) and the compound represented by the general formula (1) will be specifically described, but the present invention is not limited thereto. The part in square brackets [] in the compound represented by the general formula (I) and the compound represented by the general formula (1) is an anion, and the non-coloring cation represented by X in the general formula (1). To form a complex with. In the general formula (I) and the general formula (1), the anion portion may have one kind of structure or may have a plurality of kinds of structures different from each other, and one kind of structure is preferable. That is, a plurality of R ^{1 to} R ¹¹ existing may be of the same type or different types, respectively. Further, X may be one type or a mixture of a plurality of types, and is preferably one type. When k is an integer of 2 to 6, a plurality of Xs may be of the same type or different types.

The compound according to this embodiment is the compound represented by the above-mentioned general formula (I). A represents an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, or a group represented by the following formula (Ia).

The alkyl group represented by A, which may have a substituent, is, for example, "a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent" described later. It may be there. Specific examples of the alkyl group which may have a substituent represented by A include a methyl group. The cycloalkyl group which may have a substituent represented by A may be, for example, "a cycloalkyl group having 3 to 20 carbon atoms which may have a substituent" which will be described later. Specific examples of the cycloalkyl group which may have a substituent represented by A include a cyclohexyl group.

The compound represented by the general formula (I) may be a compound represented by the above general formula (1) in which A is a group represented by the formula (Ia). In this case, it becomes easier to form an anodized film which is a single color and exhibits a yellowish-orange reddish yellow color.

Examples of the "amino group having 0 to 20 carbon atoms which may have a substituent" represented by R ^{2 to} R ¹¹ _{include an unsubstituted amino group (-NH 2} ), a monosubstituted amino group and a disubstituted amino. The group etc. can be mentioned. The number of carbon atoms in the mono- or di-substituted amino group is, for example, 1 to 20, may be 1 to 10, and may be 2 to 6. The amino group having 0 to 20 carbon atoms which may have a substituent is an aromatic hydrocarbon group having 6 to 20 carbon atoms (for example, an aromatic group described later) via -NH- or -N <. It may be a group to which a hydrocarbon group), an acyl group having 1 to 20 carbon atoms, and a heterocyclic group having 5 to 20 ring-forming atoms are bonded. Examples of the monosubstituted amino group include an ethylamino group, an acetylamino group, a phenylamino group and a benzoylamino group. Examples of the disubstituted amino group include a dimethylamino group, a diethylamino group, a diphenylamino group, an acetylphenylamino group and the like.

"Good sulfonyl group which may have a substituent group having a carbon number of 0 to 20" is represented by _{^{R 2 ~R 11, -SO 2 -R}} 100 ( or ^{_{-S (= O) 2 -R 100}} ) means a sulfonyl group having a substituent group R ¹⁰⁰ represented in. ^{However, R 100} is, -OH and O ^- is other than. R ¹⁰⁰ may be a group containing a carbon atom or a group not containing a carbon atom. When R ¹⁰⁰ is a carbon-containing group, the ^{number of carbon atoms of R 100} is 1 to 20, may be 1 to 10, and may be 1 to 7. Examples of the sulfonyl group which may have a substituent having 0 to 20 carbon atoms include a sulfonamide group (-S (= O) _2- NH ₂ ), a mesyl group and a tosyl group.

The carbon of the "linear or branched alkyl group" in the "linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent" represented by ^{R 2 to} R ^11. The number of atoms is 1 to 20, may be 1 to 10, may be 1 to 6, and may be 1 to 4. "Linear or branched alkyl group having 1 to 20 carbon atoms" in "linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent" represented by R ^{2 to} R ^11. Specific examples of the "alkyl group" include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, and an n-. Linear alkyl groups such as nonyl group and n-decyl group; branched alkyl groups such as isopropyl group, isobutyl group, s-butyl group, t-butyl group, isooctyl group and t-octyl group can be mentioned.

Specifically, the "cycloalkyl group having 3 to 20 carbon atoms" in the "cycloalkyl group having 3 to 20 carbon atoms which may have a substituent" represented by R ^{2 to} R ^{11 is specifically defined.} Examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group and a cyclododecyl group.

In the "linear or branched alkoxy group having 1 to 20 carbon atoms which may have a substituent" represented by ^{R 2 to} R ^{11, "linear or branched having 1 to 20 carbon atoms".} Specific examples of the "alkoxy group in the form" include a methoxy group, an ethoxy group, a propoxy group, an n-butoxy group, an n-pentyloxy group, an n-hexyloxy group, an n-heptyloxy group, and an n-octyloxy group. Linear alkoxy groups such as n-nonyloxy group and n-decyloxy group; branched such as isopropoxy group, isobutoxy group, s-butoxy group, t-butoxy group, isooctyloxy group and t-octyloxy group. Alkoxy groups can be mentioned.

As "cycloalkoxy group having 3 to 20 carbon atoms" in the "cycloalkoxy group which may having 3 to 20 carbon atoms which may have a substituent" represented by R ² to R ¹¹ are, specifically, Cyclopropoxy group, cyclobutoxy group, cyclopentyloxy group, cyclohexyloxy group and the like can be mentioned.

"Linear or branched alkenyl group having 2 to 20 carbon atoms" in "linear or branched alkenyl group having 2 to 20 carbon atoms which may have a substituent" represented by R ^{2 to} R ^11. Specific examples of the "formal alkenyl group" include a vinyl group, an allyl group, an isopropenyl group, a 2-butenyl group, a 1-hexenyl group, or a linear or branched group in which a plurality of these alkenyl groups are bonded. Can be given.

The "acyl group having 1 to 20 carbon atoms which may have a substituent" represented by ^{R 2 to} R ¹¹ is a group represented ^{by-(C = O) -R 101.} The number of carbon atoms in the acyl group is the total number of carbon atoms of the acyl group and the substituent R ^101. The substituent R ¹⁰¹ may be a group containing a carbon atom or a group not containing a 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 acyl group having 1 to 20 carbon atoms which may have a substituent is a group having an aromatic hydrocarbon group described later bonded via the acyl group and having a total carbon atom number of 1 to 20. , A heterocyclic group having 5 to 20 ring-forming atoms, which will be described later, may be bonded to the group via an acyl group, and the total number of carbon atoms may be 1 to 20. Examples of the substituent R ¹⁰¹ include -H, -CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH = CH ₂ , and -C ₆ H ₅ (phenyl group). 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 a formyl group, an acetyl group, a propionyl group, and an acryloyl group. (Acrylyl group), benzoyl group and the like.

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" represented by ^{R 2 to} R ^{11 includes} Specific examples thereof include a phenyl group, a benzoyl group, a naphthyl group, a biphenyl group, an anthryl group, a phenanthryl group, a pyrenyl group, a triphenylenyl group, an indenyl group and a fluorenyl group. Here, the "aromatic hydrocarbon group" in the present invention represents an aromatic hydrocarbon group and a condensed polycyclic aromatic group, and among these, a phenyl group or a naphthyl group is preferable.

Specific examples of the "heterocyclic group having 5 to 30 ring-forming atoms" in the "heterocyclic group having 5 to 30 ring-forming atoms which may have a substituent" represented by R ^{2 to} R ^{11 are specific.} In addition, piperazinyl group, pyridyl group, pyrimidinyl group, triazinyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, triazolyl group, quinolyl group, isoquinolyl group, naphthyldinyl group, indolyl group, benzoimidazolyl group, carbazonyl group, carbolinyl group, acridinyl group, Examples thereof include a phenanthrolinyl group, a hydantin group, a furanyl group, a benzofuranyl group, a dibenzofuranyl group, a thienyl group, a benzothienyl group, a dibenzothienyl group, an oxazolyl group, a benzoxazolyl group, a thiazolyl group and a benzothiazolyl group.

Represented by R ² to R ^11,
"Amino group having 0 to 20 carbon atoms having a substituent",
"Sulfonyl group having 0 to 20 carbon atoms having a substituent",
"Linear or branched alkyl group having 1 to 20 carbon atoms having a substituent",
"Cycloalkyl group having 3 to 20 carbon atoms having a substituent",
"Linear or branched alkoxy group having 1 to 20 carbon atoms having a substituent",
"Cycloalkoxy group having 3 to 20 carbon atoms having a substituent",
"Linear or branched alkenyl group having 2 to 20 carbon atoms having a substituent",
"Acyl group having 1 to 20 carbon atoms having a substituent",
The "substituent" in the "aromatic hydrocarbon group having 6 to 30 carbon atoms having a substituent" or the "heterocyclic group having 5 to 30 ring-forming atoms having a substituent"
Specifically, a hydroxyl group (-OH), ^- COO -, a carboxyl group (-COOH), a nitro group _(-NO 2), nitroso group (-NO), a cyano group ^{_{(-CN), - SO 3 -}} , sulfonic acid group _(-SO 3 H), thiol group (-SH),
An unsubstituted amino group; a monosubstituted amino group in which a group having 0 to 20 carbon atoms is bonded via -NH-; a disubstituted amino group in which a group having 0 to 20 carbon atoms is bonded via -N <;
Group having - sulfonamide _{(-S (= O) 2 -NH} 2) group, mesyl group, a sulfonyl group such as tosyl group _{(-S (= O) 2)} ;
Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, t-butyl group, pentyl group, n-hexyl group, isohexyl group, heptyl group, n-octyl group, t- Linear or branched alkyl groups such as octyl group, isooctyl group, nonyl group, decyl group;
Cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecyl group, cyclododecyl group;
Linear or branched alkoxy groups such as methoxy group, ethoxy group, propoxy group, t-butoxy group, n-pentyloxy group, n-hexyloxy group;
Cycloalkoxy groups such as cyclopropoxy group, cyclobutoxy group, cyclopentyloxy group, cyclohexyloxy group;
Vinyl group, 1-propenyl group, allyl group, 1-butenyl group, 2-butenyl group, 1-pentenyl group, 1-hexenyl group, isopropenyl group, isobutenyl group, or linear chain in which a plurality of alkenyl groups thereof are bonded. Or a branched alkenyl group;
Acyl groups such as formyl group, acetyl group, propionyl group, acryloyl group (acryloyl group), benzoyl group;
Aromatic hydrocarbon groups such as phenyl group, naphthyl group, anthryl group, phenanthryl group, pyrenyl group, triphenylenyl group, indenyl group, fluorenyl group;
Pyridyl group, pyrimidinyl group, triazinyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, triazolyl group, pyrazinyl group, pyridadinyl group, piperidinyl group, piperazinyl group, quinolyl group, isoquinolyl group, naphthyldinyl group, indrill group, benzoimidazolyl group, carbazonyl group. , Carbolinyl group, acridinyl group, phenanthrolinyl group, phenanthridinyl group, hydantoin group, flanyl group, benzofuranyl group, dibenzofuranyl group, pyranyl group, cummarinyl group, isobenzofuranyl group, xanthenyl group, oxanthrenyl group , Pyranonyl group, thienyl group, thiopyranyl group, benzothienyl group, dibenzothienyl group, thioxanthenyl group, oxazolyl group, benzoxazolyl group, morpholinyl group, thiazolyl group, benzothiazolyl group and other heterocyclic groups;
Cyclic olefin groups such as cyclopropenyl group, cyclobutenyl group, cyclopentenyl group, cyclohexenyl group, cycloheptenyl group, (1,3- or 1,4-) cyclohexadienyl group, 1,5-cyclooctadienyl group; etc. Can be given.
Only one of these "substituents" may be contained, a plurality of these "substituents" may be contained, and when a plurality of these "substituents" are contained, they may be the same or different from each other. Moreover, these "substituents" may have the above-exemplified substituents. When the "substituent" contains a carbon atom, the carbon atom is the above-mentioned "carbon atom number 0 to 20", "carbon atom number 1 to 20", "carbon atom number 2 to 20", "carbon atom number 2 to 20". It is included in "number 3 to 20" and "number of carbon atoms 6 to 30". Similarly, when the "substituent" contains a ring-forming atom, the ring-forming atom is included in "the number of ring-forming atoms 5 to 30". 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 is -COO ^- is or -COOH. R ^{2 _{is, -H, -COO -, -COOH,}} -NO 2, -SO 3 -, -SO 3 H or, a good 1 to 10 carbon atoms which may have a substituent group linear or, It is preferably a branched alkyl group. R ³ is preferably an amino group having —H, —NO ₂ , and optionally having a substituent and having 0 to 10 carbon atoms, and more preferably —H. R ⁴ and ^{R 5} are each _{^{independently, -H, -COO -, -COOH,}} -NO 2, -SO 3 -, -SO 3 H or, optionally carbon atoms which may have a substituent 1, preferably 10 a linear or branched alkyl group, ^{R 4} is _{^{-COO -, -COOH, -NO 2,}} -SO 3 -, -SO 3 H or a _-SO 2 NH _2, Is more preferable.

R ⁶ is —COO ⁻ , —COOH, an amino group having 0 to 10 carbon atoms which may have a substituent, or a linear chain having 1 to 10 carbon atoms which may have a substituent. Alternatively, it is preferably a branched alkyl group.

R ^{7 to} R ¹¹ are each independently preferably _{-H, -NO 2} , -SO ₃ ^- , -SO ₃ H, or -SO ₂ NH ₂ , and at least one of ^{R 7 to} R ^{11 is -SO.} ₃ ^- or more preferably -SO ₃ H.

Although ^{R 2 ~R 5, R 7 ~R} 11 represents a substituent as described above, with adjacent groups together, via a bond (-O-) or a sulfur atom through a single bond, or an oxygen atom They may be bonded to each other to form a ring by the resulting bond (—S—). For example, R ^{2 to} R ⁵ may be bonded to each other to form a benzene ring, or R ⁴ and R ⁵ may be bonded to each other to form a benzene ring.

"X" is a non-coloring cation. Non-coloring cations are cations that do not have a chromophore (eg, nitro group, azo group, carbonyl group). Specific examples of non-coloring cations include ^{alkali metal ions such as hydrogen ion (H +} ), lithium ion (Li ⁺ ), sodium ion (Na ⁺ ), and potassium ion (K ⁺ ); ammonium ion (NH ₄ ⁺ ), Examples thereof include cations containing a nitrogen atom such as a substituted ammonium ion (aminium ion). Specific examples of the cation containing a nitrogen atom include ammonium ions represented by ^{R 12} R ¹³ R ¹⁴ R ¹⁵ N ^{+ , and R 12 to} R ¹⁵ independently have −H and a substituent. It represents a linear or branched alkyl group having 1 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, and is bonded to each other. A ring may be formed. In the formula, ^{"substituents" in R 12 to} R ¹⁵ , "linear or branched alkyl groups having 1 to 20 carbon atoms" and "aromatic hydrocarbon groups having 6 to 20 carbon atoms" for more information, the same as ^R 2 ^{to R 11} in the general formula (1) is applied. Among these cations, alkali metal ions are more preferable as X, and K ⁺ or Na ⁺ is particularly preferable.

k represents the number of non-coloring cations “X”, represents an integer of 1 to 6, and is preferably an integer of 1 to 4.

The compounds represented by the general formulas described above shall include all possible stereoisomers. Specific examples of the compound of the present invention represented by the above-mentioned general formula are shown in the following formulas, but the present invention is not limited thereto. In the exemplified compound, the charge of the entire anion portion in square brackets [] is described, and a hydrogen atom is partially omitted in the structural formula.

The compound represented by the general formula (I) includes, for example, a diazodide obtained by diazotizing a compound represented by the following general formula (II), a compound represented by the following general formula (II), and / or a compound thereof. It can be obtained by a method including a step of diazo coupling reaction with a salt (coupling step). That is, the compound represented by the general formula (I1) is a diazodide obtained by diazotizing the compound represented by the general formula (II), and the compound represented by the following general formula (III) and / or a salt thereof. It may be obtained by a diazo coupling reaction with.

The method for producing the compound represented by the general formula (I) may further include, for example, a step of diazotizing the compound represented by the general formula (II) before the coupling step.

An example of a method for producing the compound of the present invention represented by the general formula (1) is shown below, but the method is not limited to this method. Specifically, first, a base prepared by using sodium nitrite or the like in an aqueous acid solution such as hydrochloric acid or sulfuric acid for an aromatic amine derivative represented by the following general formula (2) and having an appropriate substituent. By reacting with an aqueous aqueous solution at an appropriate temperature, a compound represented by the following general formula (2a) and / or a salt thereof (diazo component) can be obtained.

[In formula (2), R ^{1 to} R ⁵ have the same meaning as the above definitions. ]

[In formula (2a), R ^{1 to} R ⁵ have the same meaning as the above definitions. ]

On the other hand, a salt (coupler component) of the compound represented by the general formula (3) can be obtained by dissolving the compound represented by the following general formula (3) in an aqueous solution such as sodium hydroxide and reacting. The general formula (3) may be used as it is as a coupler component.

[In the formula, R ^{6 to} R ¹¹ have the same meaning as the above definition. ]

Next, by reacting the diazo component with the coupler component (diazo coupling reaction), a compound represented by the following general formula (1a) and / or a salt thereof can be obtained as an azo compound (azo dye). The method for producing a compound represented by the general formula (1) according to the present embodiment includes a step of obtaining the compound represented by the general formula (1a) obtained as described above.

[In the formula, R ^{1 to} R ¹¹ have the same meaning as the above definition. ]

The compound represented by the general formula (I) can be purified by a known method such as purification by column chromatography; adsorption purification with silica gel, activated carbon, activated clay, etc.; recrystallization with a solvent, crystallization method, or the like. In addition, compound identification and physical property evaluation include ultraviolet visible absorption spectrum analysis (UV-Vis), thermogravimetric analysis-differential thermal analysis (TG-DTA), gas chromatography analysis (GC), and thin layer chromatography analysis (TLC). , Gas chromatography-mass spectrometry (GC / MS), nuclear magnetic resonance analysis (NMR) analysis and the like.

The compound represented by the general formula (I) (Compound (I)) can be used as a component of the dye composition. The compound (I) can also be used alone to color aluminum, aluminum oxide, fibers and the like. That is, compound (I) can be suitably used as a dye compound for coloring aluminum, aluminum oxide, fibers, etc. by using one kind of monochromatic dye alone. Compound (I) may be used in combination of two or more in order to obtain various colors by mixing colors. The dye composition may be mixed with other components for optimum dyeing (coloring with a dye). Specific examples thereof include liquids (solvents) such as water, alcohol and solvents; additives such as surfactants; and the like. Water is preferable as the solvent. Compound (I) may be used as a component of the dye composition in combination with other dyes. Other dyes are compounds other than compound (I), pigments, dyes, etc., and specifically, ruthenium complex, coumarin dye, cyanine dye, merocyanine dye, rodacianin dye, phthalocyanine dye, porphyrin. Examples include system pigments and xanthene pigments. When compound (I) is used in combination with other components, the amount of the other components used with respect to compound (I) is preferably 10 to 200% by mass, more preferably 20 to 100% by mass. .. The aluminum oxide is a composition obtained by oxidizing aluminum and mainly containing aluminum and oxygen, and the composition ratio may be arbitrary, and the aluminum oxide is contained, and the crystal system may be single crystal, polycrystalline or amorphous. It may be present or a mixture thereof.

The above-mentioned dye composition can be applied as a colorant for anodized aluminum. The dye composition described above can also be used as a colorant used in an anodized aluminum alloy. That is, as one embodiment of the present invention, the use (application) of a compound represented by the general formula (I) for coloring aluminum anodic oxide or an aluminum anodic oxide alloy or a dye composition containing the compound is provided. Will be done. Further, as an embodiment of the present invention, the use of a compound represented by the general formula (I) for producing an aluminum anodic oxide or a colorant for an aluminum anodic oxide alloy, or a dye composition containing the compound is used. Provided.

When compound (I) is used as a colorant such as aluminum anodic oxide or an aluminum anodic oxide alloy, the concentration of compound (I) in the dye composition containing compound (I) in the coloring (dyeing) method is a dye. Based on the total mass of the composition, it is preferably 0.02 to 10% by mass, more preferably 0.05 to 3% by mass. The lower the concentration of the compound, the lighter the color can be colored, and the higher the concentration, the more neutral to the dark color can be colored.

Here, the anodic oxide means aluminum that has been subjected to a treatment of forming an oxide layer having pores on the surface of the electrolyzed aluminum in an electrolytic solution such as an acid aqueous solution. The colorant for anodized aluminum means one that can be colored (dyed) by adsorbing the compound (I) in the pores on the aluminum surface having the pores. Usually, in order to improve the durability and light resistance of the colored aluminum surface, a pore-sealing treatment for closing the pores is performed after coloring.

Here, the anodized aluminum alloy means an alloy in which the surface of the aluminum alloy is anodized. The aluminum alloy in the anodized aluminum alloy means an alloy containing aluminum as a main component, and means an alloy with a metal such as copper, manganese, silicon, magnesium, zinc, and nickel. The composition ratio of aluminum and other metals is not particularly limited.

Examples of aluminum in anodized aluminum include aluminum-containing metals or metal compounds such as aluminum, aluminum oxide, and aluminum alloys with other metals.

As the method for coloring aluminum using the above-mentioned colorant, a method known as an alumite dyeing method can be used. For example, the method described in Japanese Industrial Standards (JIS H 8601: 1999 “Aluminum and Aluminum Alloy Anodized Film”), Patent Document 1 and the like can be used. The method for coloring aluminum is not particularly limited, but an example is shown below.

First, the aluminum plate is degreased and washed with an aqueous acid solution such as sulfuric acid, oxalic acid, chromic acid, and sulfonic acid. Next, the degreased aluminum plate is used as an anode and electrolyzed using an acid aqueous solution as an electrolytic solution to form an anodized film (anodized film) having many pores on the surface of the aluminum anode (anodized). , Wash with water. Subsequently, after appropriately performing surface adjustment, washing with water, etc., the dye is immersed in an aqueous solution of a colorant for aluminum anoxide containing a dye composition containing the compound of the present invention, and the dye is adsorbed (dyed, dyed) in the pores. It can be colored by electrolyzing) and sealing the pores on the surface with aluminum oxide hydrate or the like to form a sealing substance.
When two or more kinds of 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 dyes, even if a mixed solution of all the dyes to be used is prepared and aluminum anodized aluminum is immersed. Well, each dye solution may be prepared separately and aluminum anodized may be immersed in each solution in sequence.

The electrolysis conditions at the time of coloring of the present invention may be DC electrolysis or AC electrolysis, and DC electrolysis is preferable. The current density is preferably from ^{0.1~10A / dm 2, 0.5~3A / dm} 2 is more preferable. The energizing time is preferably 10 seconds to 60 minutes. The thickness of the anodized film is preferably 2 to 20 μm. As for these anodizing conditions, the longer the energization time is and the thicker the anodizing film is, the darker the color is. Therefore, by adjusting these conditions, light to neutral to dark colors can be adjusted.

The treatment temperature of each of the above steps is preferably a suitable temperature, and the temperature at the time of anodizing is preferably 0 to 80 ° C. The temperature at the time of dyeing is preferably 10 ° C to 70 ° C. Other treatment temperatures are preferably 10 to 80 ° C.

The dye composition in the present embodiment can also be used for anodized oxides using a metal other than aluminum. For example, magnesium, zinc, titanium, zirconium, etc., which can adsorb dyes in anodized pores, can be applied to non-metals such as conductive plastics.

The colorant for aluminum anodic oxide of the present embodiment can be evaluated by measuring the characteristics of a sample colored in aluminum by measuring hue, light resistance, heat resistance, and the like. Hue can also be evaluated by visually observing hue and / or uniformity, and color difference (K / Sd), tint (L ^* , a ^* , b ^* ) and color difference (ΔE ^{*) with a color difference meter.} ) May be measured.

The color that can be represented by using the colorant for aluminum anoxide of the present embodiment can represent a yellowish to reddish color, and more preferably a yellowish to orangeish color. Yellow, orange, red, peach, brown, these light colors (light yellow, light orange, peach, etc.) or dark colors (dark yellow, dark orange, etc.) can be represented. The colorant for aluminum anodic oxide of the present embodiment can also represent a mixed color (intermediate colors such as yellow-red, yellowish orange, brown, and bronze) by using the above-mentioned compound in combination with another dye.

In the light resistance test of aluminum colored with the colorant for aluminum anoxide of the present embodiment, the sample is irradiated with light for a certain period of time using a testing machine that imitates sunlight including ultraviolet light, and before and after the test. This may be done by measuring the change in the hue of the colored aluminum. Specifically, even if it is evaluated by ^{the color difference ΔE *} _ab (or ΔE ^* ) before and after the light irradiation test obtained by measuring the tint with ^{the CIE L *} a ^* b ^* color system using a color difference meter or the like. Good. In the determination of light resistance, the hue of colored aluminum may be visually determined for dyeing fastness using a gray scale according to a method defined by Japanese Industrial Standards (JIS L 0804 "Gray scale for discoloration and fading"). ..

The heat resistance test of aluminum colored with the colorant for aluminum anoxide of the present embodiment is suitable, for example, in a temperature range of 50 to 300 ° C. or in a hot air dryer for 30 minutes to 50 hours. Similar to the light resistance test, there is a method of evaluating the change in hue before and after the test, such as a method of heating for a certain period of time.

The colored aluminum using the colorant for anodized aluminum of the present embodiment is used for a wide variety of aluminum plate materials and products using an aluminum exterior.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to the following Examples. The compounds obtained in the synthetic examples were identified by ¹ H-NMR and ¹³ C-NMR analysis (nuclear magnetic resonance apparatus manufactured by JEOL Ltd., model number: JNM-ECZ400S / L1), and the measurement results are shown below. It is shown in the synthesis example.

[Synthesis Example 1] Synthesis of compound (1-1) (preparation of diazo component) 8.0 g of 4-nitroanthranic acid, 32 mL of water and 6.0 g of 35% hydrochloric acid were placed in a reaction vessel, and the reaction solution was heated to 10 ° C. While stirring below, 8.0 g of a 40 mass% sodium nitrite aqueous solution was added dropwise and reacted for 2 hours to obtain a diazo component solution.

(Preparation of coupler component) In a reaction vessel, 11.4 g of 3-methyl-1- (4-sulfophenyl) -2-pyralizone-5-one (p-SMP), 40 mL of water, and a 24% aqueous sodium hydroxide solution 10. 3 g and 2.4 g of sodium carbonate were added, and the mixture was stirred at 10 ° C. or lower for 30 minutes to obtain a coupler component solution.

(Diazo Coupling Reaction) The diazo component solution was added to the coupler component solution during stirring, and the mixture was stirred overnight at room temperature to carry out the diazo coupling reaction. Completion of the reaction was confirmed by thin layer chromatography (TLC). Product purity was confirmed by high performance liquid chromatography (HPLC) by the observed retention peak positions and areas of typical azo dyes.
After the reaction, sulfuric acid was added to make it acidic, and the precipitated solid was collected by filtration. The solid was dried under reduced pressure to obtain a compound represented by the above formula (1-1) as a solid powder (20.3 g, yield 94.0%).

^{1 1} H-NMR (400 MHz, DMSO-d ₆ ): δ (ppm) = 1.87 (s, 1H), 2.23 (s, 3H), 7.64 (dd, 2H), 7.87 (dd) , 2H), 7.91 (d, 1H), 8.17 (d, 1H), 8.50 (d, 1H).
¹³ C-NMR (100 MHz, DMSO-d ₆ ): δ (ppm) = 12.27, 21.41, 109.34, 117.29, 117.79, 126.84, 130.57, 133.66, 138.64, 145.40, 146.06, 149.47, 150.56, 156.06, 167.24.

[Synthesis Example 2] Synthesis of compound (1-6) (preparation of diazo component) 8.0 g of 2-aminoterephthalic acid, 32 mL of water and 6.0 g of 35% hydrochloric acid were placed in a reaction vessel, and the reaction solution was heated to 10 ° C. While stirring below, 8.0 g of a 40 mass% sodium nitrite aqueous solution was added dropwise and reacted for 2 hours to obtain a diazo component solution.

(Preparation of coupler component) In a reaction vessel, 13.8 g of 3-carboxy-1- (4-sulfophenyl) -2-pyralizone-5-one, 40 mL of water, 10.3 g of a 24% sodium hydroxide aqueous solution, and sodium carbonate 2 .4 g was added and stirred at 10 ° C. or lower for 30 minutes to obtain a coupler component solution.

(Diazo Coupling Reaction) The diazo component solution was added to the coupler component solution during stirring, and the mixture was stirred overnight at room temperature to carry out the diazo coupling reaction. Completion of the reaction was confirmed by thin layer chromatography (TLC). Product purity was confirmed by high performance liquid chromatography (HPLC) by the observed retention peak positions and areas of typical azo dyes.
After the reaction, sulfuric acid was added to make it acidic, and the precipitated solid was collected by filtration. The solid was dried under reduced pressure to obtain a compound represented by the above formula (1-6) as a solid powder (17.3 g, yield 82.4%).

[Synthesis Example 3] Synthesis of compound (1-10) (preparation of diazo component) 8.0 g of 2-aminoterephthalic acid, 32 mL of water and 6.0 g of 35% hydrochloric acid were placed in a reaction vessel, and the reaction solution was heated to 10 ° C. While stirring below, 8.0 g of a 40 mass% sodium nitrite aqueous solution was added dropwise and reacted for 2 hours to obtain a diazo component solution.

(Preparation of coupler component) In a reaction vessel, 7.9 g of 3-amino-1-phenyl-2-pyrazolin-5-one, 50 mL of water, 10.3 g of a 24% sodium hydroxide aqueous solution, and 2.4 g of sodium carbonate were placed. The mixture was stirred at 10 ° C. or lower for 30 minutes to obtain a coupler component solution.

(Diazo Coupling Reaction) The diazo component solution was added to the coupler component solution during stirring, and the mixture was stirred overnight at room temperature to carry out the diazo coupling reaction. Completion of the reaction was confirmed by thin layer chromatography (TLC). Product purity was confirmed by high performance liquid chromatography (HPLC) by the observed retention peak positions and areas of typical azo dyes.
After the reaction, sulfuric acid was added to make it acidic, and the precipitated solid was collected by filtration. The solid was dried under reduced pressure to obtain a compound represented by the above formula (1-10) as a solid powder (15.1 g, yield 93.2%).

[Synthesis Example 4] Synthesis of compound (1-36) (preparation of diazo component) 8.0 g of 2-aminoterephthalic acid, 32 mL of water and 6.0 g of 35% hydrochloric acid were placed in a reaction vessel, and the reaction solution was heated to 10 ° C. While stirring below, 8.0 g of a 40 mass% sodium nitrite aqueous solution was added dropwise and reacted for 2 hours to obtain a diazo component solution.

(Preparation of coupler component) In a reaction vessel, 5.1 g of 1,3-dimethyl-5-pyralysolone, 50 mL of water, 10.3 g of 24% sodium hydroxide aqueous solution, and 2.4 g of sodium carbonate were placed, and the temperature was 10 ° C. or lower for 30 minutes. The mixture was stirred to obtain a coupler component solution.

(Diazo Coupling Reaction) The diazo component solution was added to the coupler component solution during stirring, and the mixture was stirred overnight at room temperature to carry out the diazo coupling reaction. Completion of the reaction was confirmed by thin layer chromatography (TLC). Product purity was confirmed by high performance liquid chromatography (HPLC) by the observed retention peak positions and areas of typical azo dyes.
The reaction proceeded quantitatively, acidified with sulfuric acid, and the precipitated solid was collected by filtration. The solid was dried to obtain a compound represented by the following formula (1-36) as a solid powder.

<Evaluation of hue and light resistance>
[Example 1]
Colored aluminum was produced by anodizing the aluminum substrate in the following procedure. In the anodizing and dyeing steps, two types of dyeing conditions were set in which the treatment time and the dye compound concentration were changed.
(Solvent degreasing) A mixture of 150 mL of a degreasing agent (Top ADD-100, manufactured by Okuno Pharmaceutical Industry Co., Ltd.), 70 mL of 98% sulfuric acid, and 1000 mL of water was prepared as a degreasing solution, and aluminum for dyeing was cut to an appropriate size. The substrate was immersed, degreased at 60 ° C. for 3 minutes, and then washed with water.
(Anodizing) 180 g / L electrolytic solution was prepared using 98% sulfuric acid, an aluminum substrate was connected to the electrodes of the electrolytic device, immersed in an electrolytic solution tank, and the temperature was 20 ± 1 ° C. and the current density was 1.0 A /. Anodization ^{was performed under the condition of energization time of dm 2} or less to obtain an anodized film having the following thickness. After oxidation, it was washed with water.
Anodizing condition (1): 25 minutes of energization Anodized film thickness: 7 μm
Anodizing condition (2): 40 minutes of energization Anodized film thickness: 11 μm
Anodizing condition (3): 54 minutes of energization Anodized film thickness: 15 μm
(Surface adjustment) A surface adjustment solution having a concentration of 50 mL / L was prepared using a surface conditioner (TAC Somar 121 manufactured by Okuno Pharmaceutical Industry Co., Ltd.) and water, and the aluminum substrate was immersed at 45 ° C. for 1 minute. After the immersion, the aluminum substrate was washed with water.
(Dyeing) Synthesis Using the compound (1-1) obtained in Example 1 as a dye, an aqueous solution for dyeing containing each of the following concentrations of the dye was prepared as the dye composition of the present invention, and immersed in the following dyeing time. Both were dyed at a temperature (building bath temperature) of 55 ° C. After dyeing, the aluminum substrate was washed with water.
Dyeing condition (1): Dye concentration 2.0% by mass Dyeing time: 30 seconds Dyeing condition (2): Dye concentration 1.0% by mass Dyeing time: 5 minutes (sealing) Sealing agent (manufactured by Okuno Pharmaceutical Industry Co., Ltd.) , Topseal H-298) and water were used to prepare a 40 mL / L sealing solution, which was sealed at about 90 ° C. for 15 minutes. After the sealing treatment, it was dried with warm air.

(Hue evaluation) Compound (1-1) Hue visual and color difference meter of the colored aluminum plate was colored with the dye (device name: Konica Minolta spectrometer color difference meter Model: CM-3700A) CIE in ^L * ^a * b ^* Evaluated by color system. The results of the evaluated hues are shown in Table 1.

(Light resistance test) A light resistance test was conducted on a colored aluminum plate colored with the dye of compound (1-1) by the following method. Using a xenon fade meter / ATLAS Ci3000 + Xenon Weather Ometer (manufactured by Atlas), irradiance: 300-400 nm, 60 W / m ² , test tank temperature: 38 ° C, humidity: 50%, black panel (BP) temperature: 63 When a colored aluminum plate was irradiated for 50 hours, 100 hours, and 200 hours under the condition of ° C., the hue and the color difference ΔE ^* before and after light irradiation were measured with a color difference meter, and the dyeing fastness was determined by the gray scale grade. The light resistance was judged by visual judgment (JIS L 0804 "gray scale for discoloration and fading"). As for the series, the fifth series is the highest, the first grade is the lowest, and the higher the series, the darker the color (the ^{smaller the color difference ΔE *} ) and the more the hue before irradiation is maintained. In the evaluation method of the present invention, the judgment result of the series is divided into three stages, evaluated according to the following judgment criteria, and the results are summarized in Table 1.
Grayscale criteria: Correspondence between series and evaluation in the present invention Grades 5 to 4: A (especially good light resistance)
Grade 3: B (normal level of light resistance)
Level 2 or lower: C (low light resistance)
As a result, it was found that the dye of compound (1-1) had particularly good light resistance under any of the above anodizing conditions, dyeing conditions, and irradiation time.

[Examples 2 to 4]
Instead of the dye of compound (1-1) evaluated in Example 1, the anodic oxidation conditions (1-6), compounds (1-10) and (1-36) were the same as in Example 1. Table 1 summarizes the results of producing colored aluminum under the dyeing conditions of 1) and (1) ^{and evaluating the hue, color difference ΔE *, and visual light resistance.}

[Comparative Examples 1 to 2]
Instead of the dye of compound (1-1) evaluated in Example 1, the following dye not belonging to the present invention:
(D-1) Acid Yellow 23,
(D-2) TAC Yellow RHM (201) (manufactured by Hodoya Chemical Industry Co., Ltd., a known yellow alumite dye, a mixture of a dye containing Cr and a plurality of dyes) is anodized in the same manner as in Example 1. Table 1 summarizes the results of producing colored aluminum under the dyeing conditions of condition (1) and dyeing condition (1) ^{and evaluating the hue, color difference ΔE *, and visual light resistance.}

(Heat resistance test)
[Examples 5 to 8]
Regarding the dyes (1-1), (1-6), (1-10) and (1-36), the heat resistance test was performed on the colored aluminum plate in the same manner as in Examples 1 to 4 by the following method. Was done. The sample was heated under the following exposure conditions using a constant temperature dryer (manufactured by AS ONE Corporation, model: 87L EOP-450V).
Dryer temperature and heating time: 200 ° C-5 hours or 250 ° C-3 hours The heat resistance evaluation method of the present invention measures the color difference of a colored aluminum sample before and after heating with the following color difference meter and visually. , Evaluated according to the following criteria. The results are shown in Table 2.
Equipment: Color difference meter (Spectroscopic color 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)
Viewing angle: 10 °
Heat resistance criteria:
A: Good heat resistance ΔE ^* ≤ 2.0
B: Normal level heat resistance 2.0 <ΔE ^* ≦ 5.0
C: Low heat resistance ΔE ^* > 5.0

[Comparative Examples 4 to 5]
Table 2 summarizes the results of evaluating the heat resistance of the samples colored in the same manner for the compounds (D-1) to (D-2) of Comparative Examples 1 to 2 in the same manner as in Examples 5 to 8. Shown.

From the results in Tables 1 and 2, by using an aluminum anodic oxide colorant composed of a dye composition containing the compound of the present invention, a yellowish or reddish yellowish film is formed on aluminum, and light resistance is obtained. And a film with high heat resistance could be formed. On the other hand, the dyes of the comparative examples did not have sufficient light resistance and / or heat resistance.

Specifically, the compounds (1-1), (1-6) and (1-10) and the compound (1-36) were excellent in light resistance and heat resistance as compared with the compounds of Comparative Examples. Compounds (1-1), (1-6) and (1-10) were capable of forming a monochromatic, reddish-yellowish colored film. When Acid Yellow3, which is a known dye compound, was used, it was difficult to form such a monochromatic, reddish-yellow colored film.

According to the dye composition containing the compound according to the present invention, it is possible to obtain a colorant for aluminum anodic oxide having excellent light resistance and heat resistance, which does not contain heavy metals such as chromium, and which forms a colored film. Further, by using the colorant, an anodized aluminum film having excellent light resistance and heat resistance can be obtained. According to some aspects of the present invention, it is possible to obtain a colorant for aluminum anodic oxide that forms a monochromatic, yellowish, orangeish, particularly reddish yellowish colored film.

Claims (9)

A compound represented by the following general formula (I).

[In the formula (1), A represents an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, or a group represented by the following formula (Ia).

R ¹ is -COO ^- represents or -COOH,
The R ² to R ¹¹ are each _{^{independently, -H, -OH, -COO -,}} -COOH, -NO 2, -NO, -CN, -SO 3 -, -SO 3 H, -SH,
An amino group having 0 to 20 carbon atoms, which may have a substituent,
A sulfonyl group having 0 to 20 carbon atoms, which may have a substituent,
A linear or branched alkyl group having 1 to 20 carbon atoms, which may have a substituent,
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,
A cycloalkoxy group having 3 to 20 carbon atoms, which may have a substituent,
A linear or branched alkenyl group having 2 to 20 carbon atoms, which may have a substituent,
Acyl groups having 1 to 20 carbon atoms, which may have substituents,
It represents an aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent, or a heterocyclic group having 5 to 30 ring-forming atoms which may have a substituent.
^{R 2 ~R 5, R 7 ~R} 11 is bonded together with the adjacent group together may form a ring,
X represents a non-coloring cation and k represents an integer of 1-6. ] The compound according to claim 1, which is represented by the following general formula (1).

[In formula (1), R ^{1 to} R ¹¹ , X and k have the same meaning as the above definitions. ] In Formula (1) ^{independently} R 7 ^{to R 11} are _each, -H, _-NO ^2, -SO 3 -, a _-SO 3 H or _-SO 2 NH _2,, according to claim 2 Compound. In the formula (I), independently ^{of R 4} and ^{R 5} are each, ^-H, -COO -, -COOH or _{^{-NO 2, -SO 3 -, -SO}} 3 H , or substituted The compound according to any one of claims 1 to 3, which is a linear or branched alkyl group having 1 to 10 carbon atoms. In the general formula (I), R ⁶ has —COO ⁻ , —COOH, an amino group having 0 to 10 carbon atoms which may have a substituent, or a carbon which may have a substituent. The compound according to any one of claims 1 to 4, which is a linear or branched alkyl group having 1 to 10 atoms. A dye composition containing the compound according to any one of claims 1 to 5. A colorant for anodized aluminum containing the dye composition according to claim 6. A method for coloring aluminum anodized aluminum or an aluminum anodized alloy, which comprises using a dye composition containing 0.02 to 10% by mass of the compound according to any one of claims 1 to 5. The method for producing a compound according to any one of claims 1 to 5.
The compound represented by the general formula (I) is a diazodide obtained by diazotizing a compound represented by the following general formula (II), a compound represented by the following general formula (III), and / or a salt thereof. A production method obtained by a diazo coupling reaction with.

[In formulas (II) and (III), A and R ^{1 to} R ¹¹ have the same meaning as the above definitions. ]