Azo dye, dye composition, coloring agent and coloring method for anodized aluminum, and method for producing said dye

Abstract

The present invention relates to an azo pigment represented by general formula (1), (2), or (3).

Description

[Technical field]

[0001] The present invention relates to an azo dye and dye composition suitable for use as a colorant for anodized aluminum. The present invention also relates to a method for coloring anodized aluminum using the dye and dye composition, and a method for producing the dye. [Background technology]

[0002] Conventionally, a method for coloring the surface of aluminum (including its oxide or alloy) has been used in which an electric current is passed through the aluminum as the anode in an electrolyte containing water and an appropriate acid (anodic oxidation) to form a porous aluminum oxide film (anodized film) on the surface, and then the surface is colored using an organic pigment (or organic dye) as a colorant (Patent Documents 1 to 6).

[0003] Chromium-containing dyes for anodized aluminum coatings (Patent Documents 1 to 6, etc.) have excellent light resistance and heat resistance and have been widely used. However, in recent years, from the environmental perspective, there has been a demand for pigments with a variety of hues that do not contain heavy metals such as chromium and halogens such as chlorine or bromine.

[0004] Although there are dyes for anodizing coatings such as yellow, blue, and red that do not contain heavy metals or halogens, there are few black or brown dyes that do not contain heavy metals. Therefore, it may be necessary to mix multiple pigments to prepare dark colors.

[0005] Sanodye (registered trademark) Black OA from Clariant is known as a black dye for anodized aluminum films that does not contain heavy metals. However, although this dye has good light fastness when dyed in dark colors, it has insufficient light fastness when dyed in light colors (Patent Document 7). [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 9-302256 [Patent Document 2] International Publication No. 2019 / 189209 [Patent Document 3] International Publication No. 2019 / 189211 [Patent Document 4] Japanese Patent Publication No. 60-235867 [Patent Document 5] Japanese Patent Application Publication No. 6-93195 [Patent Document 6] Special Publication No. 2002-522617 [Patent Document 7] U.S. Patent No. 2,580,867 Summary of the Invention [Problem to be solved by the invention]

[0007] One object of the present invention is to provide an azo dye capable of forming an anodized coating film on the surface of aluminum or an aluminum alloy, which has excellent light resistance, is free of heavy metals such as chromium and halogens, and is monochromatic (single dye) and exhibits a black or brown color. Another object of the present invention is to provide a dye composition containing the azo dye, a colorant for anodized aluminum containing the dye composition, a method for coloring anodized aluminum or anodized aluminum alloy using the dye, and a method for producing the azo dye. [Means for solving the problem]

[0008] The inventors have discovered an azo colorant (dye), a dye composition, and a colorant for anodized aluminum that can color anodized aluminum in a single color, black or brown, and form a film that has excellent light resistance. That is, the present invention is configured as follows.

[0009] [1] An azo dye represented by the following general formula (1), (2) or (3):

[0010] [ka]

[0011] [In formulas (1), (2) and (3), R 1 ~R 3 each independently represents —H, an alkyl group having 1 to 3 carbon atoms, —NO2, —SO2CH3, —SO2CH2CH3, or —COOX; R 4 ~R 17 each independently represents —H, —OH, —SO3X, —COOX, or an amide group having 7 to 12 carbon atoms which may have a substituent, R 18 ~R 20 are each independently —H, an alkyl group having 1 to 3 carbon atoms, —NO2, —SO2CH3, or —SO2CH2CH 3、 -SO3X or -COOX, R 21 each independently represents an alkyl group having 1 to 3 carbon atoms or a non-color-forming cation, Each X independently represents a non-chromogenic cation; Each Z independently represents an oxygen atom or a sulfur atom.

[0012] [2] Represented by the general formula (1) or (2), R 1 ~R 3 The azo dye according to [1], wherein one or two of the above are -NO2.

[0013] [3] Represented by the general formula (1) or (2), R 3 The azo dye according to [1] or [2], wherein is —CH3 or —SO2CH3.

[0014] [4] Represented by the general formula (1), R 4 ~R 10 or R 4 ~R 10 The azo dye according to any one of [1] to [3], wherein one or two of the above is —SO3Na.

[0015] [5] Represented by the general formula (2), R11 ~R 17 or R 11 ~R 17 The azo dye according to any one of [1] to [3], wherein one or two of the above is —SO3Na.

[0016] [6] Represented by the general formula (3), R 18 ~R 20 are each independently -H, -CH3, -NO2, -SO2CH3, -SO3H, -SO3Na, -COOH or -COONa.

[0017] [7] X is independently H + , Na + or NH4 + The azo dye according to any one of [1] to [6],

[0018] [8] An azo dye according to any one of [1] to [4] and [7], which is represented by the following general formula (1A): [ka] [In formula (1A), X has the same meaning as defined in general formula (1)]

[0019] [9] An azo dye according to any one of [1] to [3], [5] and [7], which is represented by the following general formula (2A): [ka] [In formula (2A), X has the same meaning as defined in formula (2).]

[0020]

[10] An azo dye according to any one of [1], [6] and [7], which is represented by the following general formula (3A): [ka] [In formula (3A), X has the same meaning as defined in general formula (3)]

[0021]

[11] A dye composition containing the azo dye according to any one of [1] to

[10] .

[0022]

[12] A colorant for anodized aluminum, comprising the dye composition according to

[11] .

[0023]

[13] A method for coloring anodized aluminum or anodized aluminum alloy, comprising using a dye composition containing 0.02 to 10 mass % of the azo dye according to any one of [1] to

[10] .

[0024]

[14] A method for producing the azo dye according to any one of [1] to

[10] , comprising the steps of: The azo dye represented by the general formula (1) or (2) is obtained by a diazo coupling reaction between a diazotized product obtained by diazotizing a compound represented by the following general formula (4) and a compound represented by the following general formula (5) or (6) and / or a salt thereof:

[0025] [ka]

[0026] [In formulas (4) to (6), R 1 ~R 17 and X are as defined above in formulae (1) and (2).

[0027]

[15] A method for producing the azo dye according to any one of [1] to

[10] , comprising the steps of: The azo dye represented by the general formula (3) is obtained by a diazo coupling reaction between a diazotized product obtained by diazotizing a compound represented by the following general formula (7) and a compound represented by the following general formula (8) and / or a salt thereof:

[0028] [ka]

[0029] [In formula (7) and formula (8), R 18 ~R 21 , X and Z are as defined above in formula (3). Effect of the Invention

[0030] The present invention can provide an azo dye capable of forming an anodized coating film on the surface of aluminum or an aluminum alloy, which has excellent light resistance, is free of heavy metals such as chromium and halogens, and is monochromatic (single dye) and exhibits a black to brown color. The present invention can also provide a dye composition containing the azo dye, a colorant for anodized aluminum containing the dye composition, a method for coloring anodized aluminum or anodized aluminum alloy using the dye, and a method for producing the azo dye. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0031] Hereinafter, the embodiments of the present invention will be described in detail. Note that the present invention is not limited to the following embodiments, and can be practiced with various modifications within the scope of the gist of the present invention. Hereinafter, the azo dye represented by the general formula (1), (2) or (3) will be specifically described, but the present invention is not limited thereto.

[0032] In the general formulas (1), (2) and (3), R 1 ~R 3 , R 18~21 Specific examples of the "alkyl group having 1 to 3 carbon atoms" represented by the formula (1) include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.

[0033] The "non-coloring cation" represented by "X" in "X", "-SO3X" or "-COOX" in the general formulas (1), (2) and (3) is a cation that does not have a chromophore (e.g., a nitro group, an azo group, a carbonyl group). Specific examples of non-coloring cations include hydrogen ions (H + ), lithium ion (Li + ), sodium ion (Na + ), potassium ion (K+ ) and other alkali metal ions;NH4 + , N + R 22 R 23 R 24 R 25 An example of the ammonium ion is represented by R 22 ~R 25 Each of X independently represents an alkyl group having 1 to 3 carbon atoms (methyl group, ethyl group, n-propyl group, isopropyl group). In addition, in the general formulas (1), (2), and (3), a plurality of X may be the same or different. Each of X independently represents H. + , Na + or NH4 + It is preferable that:

[0034] In the general formulas (1) and (2), the "amide group having 7 to 12 carbon atoms which may have a substituent" means "-(C=O)-NR 31 R 32 " where "R 31 " and "R 32 " represents a "substituent" in the "amide group having 7 to 12 carbon atoms which may have a substituent". R 31 or R 32 Specific examples of R include -H, -OH, -SO3X, -COOX, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, -NO2, -SO2CH3, -SO2CH2CH3, and a phenyl group. 31 and R 32 The "phenyl group" represented by the following formula may further have the above-mentioned "substituent". 31 and R 32 When the phenyl group represented by the formula (1) has a substituent, the substituent is preferably a methyl group, an ethyl group, or —NO2. In addition, in the general formulas (1) and (2), the "carbon atom number of 7 to 12" in the "amide group having 7 to 12 carbon atoms which may have a substituent" includes the number of carbon atoms contained in the "substituent".

[0035] In the general formulas (1) and (2), R 1 ~R3 Each of R independently represents —H, an alkyl group having 1 to 3 carbon atoms, —NO2, —SO2CH3, —SO2CH2CH3, or —COOX. 1 ~R 3 In another embodiment of the azo dye, R 3 is preferably an alkyl group having 1 to 3 carbon atoms (particularly preferably —CH3) or —SO2CH3.

[0036] R 1 ~R 3 The azo dye represented by general formula (1) or (2) in which one or two of R are -NO2 preferably has a structure represented by the following general formula (Ia) or formula (Ib). In general formula (Ia) and formula (Ib), * indicates the bonding site with the azo group (-N=N-). 1 is R in the general formulas (1) and (2). 1 R in general formula (Ia) has the same meaning as 1 is preferably -H or -NO2, and more preferably -NO2. [ka]

[0037] R 3 The azo dye represented by the general formula (1) or (2) in which R is an alkyl group having 1 to 3 carbon atoms or —SO2CH3 preferably has a structure represented by the following general formula (Ic): 3a R represents an alkyl group having 1 to 3 carbon atoms or -SO2CH3, and * indicates the bonding site with the azo group (-N=N-). 3a is preferably —CH3 or —SO2CH3, and more preferably —SO2CH3. [ka]

[0038] In the general formulas (1) and (2), R 4 ~R 17 Each of R independently represents —H, —OH, —SO3X, —COOX, or an amide group having 7 to 12 carbon atoms which may have a substituent, and each of X independently represents a non-color-forming cation. 4 ~R 10 Preferably, one or two of R 4 ~R 10 In the same manner, in one embodiment of the azo dye of the present invention, in the general formula (2), R 11 ~R 17 Preferably, one or two of R 11 ~R 17 It is preferred that any one or two of these is -SO3Na.

[0039] The azo dye represented by the general formula (1) is 4 or R 6 For example, the azo dye represented by the general formula (1) preferably has a structure represented by the following general formula (IIa) or (IIb). In the formulas (IIa) and (IIb), * indicates the bonding site with the azo group (-N=N-), and R 5 ~R 10 is R in the general formula (1). 5 ~R 10 and R 4a represents —H, —SO3X, —COOX, or an amide group having 7 to 12 carbon atoms which may have a substituent. [ka]

[0040] The azo dye represented by general formula (1) preferably has a structure represented by general formula (IIa), and more preferably has a structure represented by the following general formulas (IIa-1) to (IIa-3). [ka]

[0041] The azo dye represented by the general formula (2) is R 11 In general formula (III), * represents a bonding site with an azo group (-N=N-), and R 12 ~R 17 is R in general formula (1) 12 ~R 17 and R 11a represents —H, —SO3X, —COOX, or an amide group having 7 to 12 carbon atoms which may have a substituent. [ka]

[0042] The azo dye represented by general formula (2) preferably has a structure represented by general formula (IIIa), and more preferably has a structure represented by the following general formula (IIIa-1) or (IIIa-2). [ka]

[0043] In the general formula (3), R 21 Each independently represents an alkyl group having 1 to 3 carbon atoms or a non-color-forming cation. 21 may be the same or different. 21 All of the above may be non-color-forming cations, and an anodic oxide film having excellent light resistance can be easily obtained. 21 may all be -H.

[0044] In general formula (3), Z represents an oxygen atom or a sulfur atom. A plurality of Z's may be the same or different. In general formula (3), 1 to 3 of Z's may be oxygen atoms, 2 to 3 of Z's may be oxygen atoms, and 3 of Z's may be oxygen atoms because an anodized film having better light resistance is easily obtained. The azo dye represented by general formula (3) preferably has a structure represented by the following general formula (IV), and more preferably has a structure represented by the following general formula (IVa), because an anodized film having better light resistance is easily obtained. In formulas (IV) and (IVa), * indicates a bonding site with an azo group (-N=N-). [ka]

[0045] In the general formula (3), R 18 ~R 20 are preferably each independently —H, —CH3, —NO2, —SO2CH3, —SO3H, —SO3Na, —COOH or —COONa. 18 ~R 20 It is preferable that one or two of the groups are —NO2. The azo dye represented by general formula (3) preferably has a structure represented by general formula (Ia), (Ib), or (Ic), and more preferably has a structure represented by general formula (Ia).

[0046] The azo dyes of the present invention represented by general formula (1), (2) or (3) (hereinafter also simply referred to as dyes (1) to (3)) include all possible stereoisomers and tautomers, and the specific compounds shown below are shown as planar structural formulas. Preferred specific examples of dyes (1) to (3) are shown in the following formulas (G-0) to (G-105) and (A-1) to (A-39), but the present invention is not limited thereto.

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[0096] The dyes (1) to (3) are preferably compounds represented by the following general formula (V-1), and among the compounds represented by general formula (V-1), it is particularly preferable to use compounds represented by formula (G-2), formula (G-4) or formula (A-1). When a compound represented by the following general formula (V-1) (particularly a compound represented by formula (G-2), formula (G-4) or formula (A-1)) is used, it becomes easier to obtain an anodized coating film that is monochromatically black and also has excellent light resistance. [ka]

[0097] In the general formula (V-1), Y represents a group represented by the following general formula (IIa-3), the following general formula (IIIa-1), or the following general formula (IVa). 21 are the above-mentioned X and R 21 is synonymous with. [ka]

[0098] The compound represented by general formula (1) or (2) can be obtained, for example, by a method including a step of diazo coupling reaction between a diazotized product obtained by diazotizing a compound represented by the following general formula (4) and a compound represented by the following general formula (5) or (6) and / or a salt thereof (coupling step). That is, the compound represented by general formula (4) may be obtained by a diazo coupling reaction between a diazotized product obtained by diazotizing a compound represented by the following general formula (4) and a compound represented by the following general formula (5) or (6) and / or a salt thereof.

[0099] [ka]

[0100] [In formulas (4) to (6), R 1 ~R 17 and X are as defined above in formulae (1) and (2).

[0101] An example of a method for producing the compound (azo dye) of the present invention represented by the general formula (1) or (2) is shown below, but is not limited to this method. Specifically, first, an aromatic amine derivative having an appropriate substituent represented by the general formula (4) is reacted with a basic aqueous solution prepared using sodium nitrite or the like in an aqueous acid solution such as hydrochloric acid or sulfuric acid at an appropriate temperature to obtain a compound represented by the following general formula (4a) and / or a salt thereof (diazo component).

[0102] [ka]

[0103] [In formula (4a), R 1 ~R 3 and X has the same meaning as defined in the general formulas (1) and (2).

[0104] On the other hand, a salt (coupler component) of the compound represented by the general formula (5) or (6) can be obtained by dissolving the compound represented by the general formula (5) or (6) in an aqueous solution of sodium hydroxide or the like and reacting it. The compound represented by the general formula (5) or (6) may be used as it is as a coupler component (also simply referred to as coupler component (5) or (6)).

[0105] Next, the diazo component (4a) represented by the general formula (4a) is reacted (diazo coupling reaction) with the coupler component (5) or (6) to obtain the compound represented by the general formula (1) or (2) and / or its salt as an azo compound (azo dye). The method for producing the compound represented by the general formula (1) or (2) (azo dye) according to this embodiment includes a step of obtaining the compound represented by the general formula (1) or (2) obtained as described above.

[0106] The compound represented by general formula (3) can be obtained, for example, by a method including a step of diazo coupling reaction between a diazotized product obtained by diazotizing a compound represented by the following general formula (7) and a compound represented by the following general formula (8) and / or a salt thereof (coupling step). That is, the compound represented by general formula (7) may be obtained by a diazo coupling reaction between a diazotized product obtained by diazotizing a compound represented by the following general formula (7) and a compound represented by the following general formula (8) and / or a salt thereof.

[0107] [ka]

[0108] [In formulas (7) and (8), R 18 ~R 21 , X and Z are as defined in the general formula (3).

[0109] An example of a method for producing the compound (azo dye) of the present invention represented by the above general formula (3) is shown below, but is not limited to this method. Specifically, first, an aromatic amine derivative having an appropriate substituent represented by the above general formula (7) is reacted with a basic aqueous solution prepared using sodium nitrite or the like in an aqueous acid solution such as hydrochloric acid or sulfuric acid at an appropriate temperature to obtain a compound represented by the following general formula (7a) and / or its salt (diazo component).

[0110] [ka]

[0111] [In formula (7a), R 18 ~R 20 and X are as defined in the general formula (3).

[0112] On the other hand, a salt of the compound represented by the general formula (8) (coupler component) can be obtained by dissolving the compound represented by the general formula (8) in an aqueous solution of sodium hydroxide or the like and reacting it. The compound represented by the general formula (8) can be used as it is as a coupler component (also simply referred to as coupler component (8)).

[0113] Next, the diazo component (7a) represented by the general formula (7a) is reacted (diazo coupling reaction) with the coupler component (8) to obtain the compound represented by the general formula (3) and / or its salt as an azo compound (azo dye). The method for producing the compound represented by the general formula (3) (azo dye) according to this embodiment includes a step of obtaining the compound represented by the general formula (3) obtained as described above.

[0114] The dye (1), (2) or (3) can be purified by a known method such as purification by column chromatography; adsorption purification using silica gel, activated carbon, activated clay or the like; recrystallization using a solvent, or various crystallization methods using an acid or the like.

[0115] The dyes (1) to (3) of the present invention, their intermediates, or various products obtained by the above-mentioned production methods can be identified or their physical properties evaluated by ultraviolet-visible absorption spectroscopy (UV-Vis), thermogravimetry-differential thermal analysis (TG-DTA), gas chromatography (GC), thin-layer chromatography (TLC), high-performance liquid chromatography (HPLC), liquid chromatography-mass spectrometry (LC / MS), gas chromatography-mass spectrometry (GC / MS), nuclear magnetic resonance (NMR) analysis, or the like.

[0116] The azo dyes represented by the general formulas (1) to (3) in the present invention can be used as components of a dye composition. That is, the dyes (1) to (3) can be suitably used as dye compounds for coloring aluminum or fibers by using one type of monochromatic dye alone. The dyes (1) to (3) may be used in combination of two or more types to obtain various colors by mixing colors. The dye composition may be mixed with other components for optimal dyeing (coloring using a dye). Specific examples include liquids (solvents) such as water, alcohol, and solvents; additives such as surfactants; and the like. Water is preferred as the solvent. The dyes (1) to (3) may be used as components of a dye composition in combination with other dyes. The other dyes are compounds, pigments, or dyes other than the dyes (1) or (2), and specific examples include ruthenium complexes, coumarin dyes, cyanine dyes, merocyanine dyes, rhodacyanine dyes, phthalocyanine dyes, porphyrin dyes, and other xanthene dyes. When the dyes (1) to (3) are used in combination with other components, the amount of the other components used relative to the dyes (1) to (3) is preferably 10 to 200% by mass, and more preferably 20 to 100% by mass.

[0117] The dye composition of the present invention can be used as a colorant for anodized aluminum. When the dyes (1) to (3) are used as colorants for anodized aluminum or the like, in the coloring (dyeing) method, the concentration of the dyes (1) to (3) in the dye composition containing the dyes (1) to (3) is preferably 0.02 to 10 mass%, more preferably 0.05 to 3 mass%. The lower the concentration of the compound, the lighter the coloring can be, and the higher the concentration, the medium to darker the coloring can be.

[0118] Here, anodized aluminum refers to aluminum that has been electrolytically treated in an electrolyte such as an acidic aqueous solution to form an oxide layer having pores on the surface. A colorant for anodized aluminum refers to a material that can color (dye) the aluminum surface having pores by adsorbing a dye into the pores. Usually, a sealing treatment is performed to close the pores after coloring in order to improve the durability and light resistance of the colored aluminum surface.

[0119] The aluminum in the anodized aluminum includes aluminum, aluminum oxide, or a metal or metal compound containing aluminum, such as an aluminum alloy with another metal.

[0120] The method of coloring aluminum using a coloring agent for anodized aluminum can be a method known as anodized dyeing. For example, the methods described in Japanese Industrial Standards (JIS H 8601:1999 "Anodic oxide film of aluminum and aluminum alloys") and Patent Documents 1 to 4, 6, etc. can be used. The method of coloring aluminum is not particularly limited, but an example is shown below.

[0121] First, an aluminum plate is degreased using an aqueous acid solution such as sulfuric acid, oxalic acid, chromic acid, or sulfonic acid, and washed with water. Next, the degreased aluminum plate is used as the anode and electrolyzed using an aqueous acid solution as the electrolyte to form an anodic oxide film (alumite film) that forms many pores on the aluminum anode surface (anodizing treatment), and washed with water. Next, the anodized film is appropriately subjected to surface conditioning, washing with water, etc., and then immersed in an aqueous colorant solution for anodized aluminum that contains a dye composition containing the compound of the present invention, etc., to adsorb the dye into the pores on the surface of the anodized film (dyeing, electrolytic coloring), and the pores on the surface are sealed with aluminum oxide hydrate or the like to form a sealing material, thereby coloring the anodized film. When two or more dye compositions of the present invention are used in combination, or when the dye composition of the present invention is used in combination with other dyes, a mixed solution of all the dyes to be used may be prepared and the anodized aluminum may be immersed in the mixed solution, or each dye solution may be prepared separately and the anodized aluminum may be immersed in each solution in turn.

[0122] The electrolysis conditions during coloring in the present invention may be DC electrolysis or AC electrolysis, and DC electrolysis is preferred. The current density is 0.1 to 10 A / dm 2 is preferable, and 0.5 to 3 A / dm 2 The current application time is preferably 10 seconds to 60 minutes. The thickness of the anodized film is preferably 2 to 20 μm. These anodizing conditions result in a darker color as the current application time is longer and the anodized film is thicker, so by adjusting these conditions, it is possible to adjust the color from light to medium to dark.

[0123] The treatment temperature for each of the above steps is preferably an appropriate temperature, and the temperature for anodization is preferably 0 to 80° C. The temperature for dyeing is preferably 10 to 70° C. The temperatures for other treatments are preferably 10 to 80° C.

[0124] The dye composition of the present embodiment can be used in the same manner for anodized oxides using metals other than aluminum. For example, it can be applied to nonmetals such as conductive plastics as long as the anodized oxides are made of magnesium, zinc, titanium, zirconium, etc., and can adsorb dyes into the anodized pores.

[0125] The colorant for anodized aluminum of this embodiment can be evaluated by measuring the characteristics of a sample colored on aluminum, such as hue and light resistance. The hue can also be evaluated visually for color tone and uniformity. The hue can be measured using a color difference meter to determine the concentration (K / Sd), color tone (L * , a * , b * ) and color difference (ΔE * ) may also be measured.

[0126] The color that can be expressed by using the colorant for anodized aluminum of this embodiment is, for example, black or brown. Different shades of these colors, such as light colors (light black, light brown, etc.) or dark colors (dark black, dark brown, etc.), can be expressed. The colorant for anodized aluminum of this embodiment can also express mixed colors (intermediate colors) by using the above-mentioned compound in combination with other dyes.

[0127] The light resistance test of aluminum colored with the colorant for anodized aluminum of this embodiment may be performed by irradiating a sample with light for a certain period of time using a tester that simulates sunlight, including ultraviolet light, and measuring the change in the hue of the colored aluminum before and after the test. * a * b * Color difference ΔE before and after light irradiation test obtained by measuring the color using a color space system * ab (or ΔE * The light fastness may be evaluated by visually observing the hue of the colored aluminum using a gray scale in accordance with the method defined in the Japanese Industrial Standards (JIS L 0804 "Gray scale for discoloration") to determine color fastness.

[0128] Colored aluminum produced using the colorant for anodized aluminum of this embodiment can be used for a wide variety of aluminum plate materials or aluminum exterior products.

[0129] As one embodiment of the present invention, there is provided a compound represented by the general formula (1), (2) or (3) for coloring anodized aluminum. As another embodiment of the present invention, there is provided a use of a compound represented by the general formula (1), (2) or (3) for coloring anodized aluminum. As another embodiment of the present invention, there is provided a use (application) of a compound represented by the general formula (1), (2) or (3) for producing a colorant for anodized aluminum. EXAMPLES

[0130] The present invention will be described in detail below with reference to examples, but is not limited to the following examples. In the synthesis examples, unless otherwise specified, reagents manufactured by Kanto Chemical Co., Ltd., Fujifilm Wako Pure Chemical Industries, Ltd., Tokyo Chemical Industry Co., Ltd., etc. were used. In the synthesis examples, the structure of the compound (dye) was identified by 1 The measurements were performed using H-NMR (JNM-ECZ400S / L1 nuclear magnetic resonance spectrometer manufactured by JEOL Ltd.), and the NMR measurement data are shown together with the experimental results of each synthesis example below.

[0131] [Synthesis Example (G-0)] Synthesis of Dye (G-0) (Preparation of diazo component 1) 28.2 g of sodium picramate was placed in a reaction vessel, 242 mL of water was added and dispersed, 6.9 g of 35% hydrochloric acid (Kanto Chemical Co., Ltd.) was added, and the mixture was stirred for 2 hours at 5°C or less in an ice bath. After stirring, 6.4 g of 40% aqueous sodium nitrite solution (Kanto Chemical Co., Ltd.) was dropped into the reaction solution, and the mixture was stirred for 3 hours. After stirring, sulfamic acid (FUJIFILM Wako Pure Chemical Co., Ltd.) was added to the reaction solution to decompose the excess sodium nitrite, and diazotized solution 1 was obtained. (Preparation of Coupler Components 1 - Diazo Coupling Reaction 1) Next, 38.0 g of H acid hydrate (4-amino-5-hydroxy-2,7-naphthalenedisulfonic acid sodium hydrate) (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to a reaction vessel, and 250 mL of water was added to disperse it, and then 6.8 g of 24% aqueous sodium hydroxide solution (manufactured by Kanto Chemical Co., Ltd.) and 9.0 g of sodium carbonate (manufactured by Kanto Chemical Co., Ltd.) were added and dissolved. This solution was stirred at 5°C or less in an ice bath to obtain a coupler component solution. The previously synthesized diazotized solution 1 was added to the stirred coupler component solution, the pH was adjusted to 9.0-9.5, and the solution was stirred overnight to perform a diazo coupling reaction. After stirring, a resorcinol check was performed to confirm that no diazotized product remained, and the reaction was terminated. The temperature was raised to 40°C, and 95% sulfuric acid (manufactured by Kanto Chemical Co., Ltd.) was added to adjust the pH to 6.0-6.5, and the precipitated solid was filtered. The obtained solid was dried to obtain a compound represented by the following formula (3-G-0) as a black purple powder (yield: 52.0 g, 100%).

[0132] 1 H-NMR (400MHz, D2O): δ(ppm)=7.12(1H), 7.21(1H), 7.57(1H), 8.45(1H), 8.73(1H)

[0133] [ka]

[0134] (Preparation of diazo component 2) 10.9 g of the compound (3-G-0) was placed in a reaction vessel, 140 mL of water was added, and 4.1 g of 35% hydrochloric acid was added. The mixture was stirred for 3 hours at 5°C or less in an ice bath. After stirring, 3.4 g of 40% aqueous sodium nitrite solution was added dropwise to the reaction liquid, and the mixture was stirred for 3 hours. After stirring, sulfamic acid was added to decompose the excess sodium nitrite, and diazotized liquid 2 was obtained. (Preparation of Coupler Components 2 - Diazo Coupling Reaction 2) 2.74g of 2-naphthol (Tokyo Chemical Industry Co., Ltd.) and 150mL of water were added to a reaction vessel, and after dispersing, 3.8g of 24% aqueous sodium hydroxide solution and 1.9g of sodium carbonate were added and dissolved. This solution was stirred below 5°C in an ice bath to obtain a coupler component solution. The previously synthesized diazotized solution 2 was added to the stirred coupler component solution, and the pH was adjusted to 9.0-9.5. After stirring overnight, it was confirmed by a resorcinol check that no diazotized product remained, and the reaction was terminated. The temperature was raised to 40°C, and 95% sulfuric acid was added to adjust the pH to 6.0-6.5, and then filtered. The obtained solid was dried to obtain a dye (G-0) as a black powder (yield 12.7g, 92%).

[0135] 1 H-NMR (400MHz, D2O): δ(ppm)=6.36(1H), 7.04(2H), 7.15(1H), 7.25(1H), 7.56(1H), 7.62(1H), 8.11(1H), 8.15(1H), 8.31(1H), 8.37(1H)

[0136] [Synthesis Example 1] Synthesis of dye (G-1) The dye (G-1) was obtained as a black powder (yield: 16.1 g, 91%) in the same manner as in Synthesis Example (G-0), except that R acid (3-hydroxynaphthalene-2,7-disulfonic acid) was used instead of 2-naphthol.

[0137] 1 H-NMR (400MHz, D2O): δ(ppm)=7.77(1H), 7.86(1H), 7.97(2H), 8.00(1H), 8.36(1H), 8.64(2H), 8.80(1H)

[0138] [Synthesis Example 2] Synthesis of dye (G-2) A dye (G-2) was obtained as a black powder (yield: 9.6 g, 61%) in the same manner as in Synthesis Example (G-0), except that sodium 2-naphthol-7-sulfonate was used instead of 2-naphthol.

[0139] 1H-NMR (400MHz, D2O): δ(ppm)=6.74(1H), 7.69(1H), 7.75(2H), 7.86(1H), 7.95(1H), 8.41(1H), 8.78-8.90(3H)

[0140] [Synthesis Example 3] Synthesis of dye (G-3) A dye (G-3) was obtained as a black powder (yield: 14.1 g, 78%) in the same manner as in Synthesis Example (G-0), except that disodium 3,6-dihydroxynaphthalene-2,7-disulfonate was used instead of 2-naphthol.

[0141] 1 H-NMR (400MHz, D2O): δ(ppm)=7.66(2H), 7.76(1H), 7.88(1H), 7.99(1H), 8.18(1H), 8.48(1H), 8.78(1H)

[0142] [Synthesis Example 4] Synthesis of dye (G-4) A dye (G-4) was obtained as a black powder (yield: 14.1 g, 80%) in the same manner as in Synthesis Example (G-0), except that disodium 1-naphthol-3,6-disulfonate was used instead of 2-naphthol.

[0143] 1 H-NMR (400MHz, D2O): δ(ppm)=7.66(1H), 7.74(1H), 7.85(1H), 7.89(1H), 8.05(1H), 8.50(1H), 8.55(1H), 8.62(1H), 8.74(1H)

[0144] [Synthesis Example 5] Synthesis of dye (G-5) A dye (G-5) was obtained as a black powder (yield: 11.6 g, 71%) in the same manner as in Synthesis Example (G-0), except that sodium 1-naphthol-4-sulfonate was used instead of 2-naphthol.

[0145] 1H-NMR (400MHz, D2O): δ(ppm)=7.47(1H), 7.52(1H), 7.62(1H), 7.69(1H), 7.74(1H), 8.12(1H), 8.27(1H), 8.40(1H), 8.44(1H), 8.54(1H)

[0146] [Synthesis Example 6] Synthesis of dye (G-6) The dye (G-6) was obtained as a black powder (yield 11.9 g, 81%) in the same manner as in Synthesis Example (G-0), except that disodium R acid was used instead of 2-naphthol and 3-amino-4-hydroxyphenylmethylsulfone was used instead of sodium picramate.

[0147] 1 H-NMR (400MHz, D2O): δ(ppm)=3.33(3H), 7.06(1H), 7.64(2H), 7.74(1H), 7.89(1H), 7.92(1H), 8.28(2H), 8.50(1H), 8.59(1H)

[0148] [Synthesis Example 7] Synthesis of dye (G-7) The dye (G-7) was obtained as a black powder (yield 10.6 g, 76%) in the same manner as in Synthesis Example (G-0), except that 1-naphthol-4-sodium sulfonate was used instead of 2-naphthol and 3-amino-4-hydroxyphenylmethylsulfone was used instead of sodium picramate.

[0149] 1 H-NMR (400MHz, D2O): δ(ppm)=3.20(3H), 6.87(1H), 7.38(1H), 7.46-7.51(2H), 7.63(1H), 7.71(1H), 7.76(1H), 8.15-8.19(3H), 8.54(1H)

[0150] [Synthesis Example 8] Synthesis of dye (G-8) A dye (G-8) was obtained as a black powder (yield: 15.0 g, 95%) in the same manner as in Synthesis Example (G-0), except that sodium 2-naphthol-6-sulfonate hydrate was used instead of 2-naphthol.

[0151] 1 H-NMR (400MHz, D2O): δ(ppm)=6.70(1H), 7.59-7.72(4H), 7.80(1H), 8.13(1H), 8.43(2H), 8.77(1H)

[0152] [Synthesis Example 9] Synthesis of dye (G-9) A dye (G-9) was obtained as a black powder (yield: 14.5 g, 90%) in the same manner as in Synthesis Example (G-0), except that sodium 6,7-dihydroxynaphthalene-2-sulfonate was used instead of 2-naphthol.

[0153] 1 H-NMR (400MHz, D2O): δ(ppm)=6.88(1H), 7.39(1H), 7.06-7.66(3H), 7.86(1H), 8.64-8.70(3H)

[0154] [Synthesis Example 10] Synthesis of dye (G-10) A dye (G-10) was obtained as a black powder (yield: 10.8 g, 69%) in the same manner as in Synthesis Example (G-0), except that sodium 1-naphthol-8-sulfonate was used instead of 2-naphthol.

[0155] 1 H-NMR (400MHz, D2O): δ(ppm)=6.75(1H), 7.16(1H), 7.43(1H), 7.56(2H), 7.67(1H), 7.76(1H), 7.93(1H), 7.25(1H), 8.61(1H)

[0156] [Synthesis Example 11] Synthesis of dye (G-11) A dye (G-11) was obtained as a black powder (yield: 11.0 g, 61%) in the same manner as in Synthesis Example (G-0), except that disodium chromotropic acid dihydrate was used instead of 2-naphthol.

[0157] 1 H-NMR (400MHz, D2O): δ(ppm)=7.43(1H), 7.64(1H), 7.79(2H), 7.98(1H), 8.63(1H), 8.70(1H), 8.86(1H)

[0158] [Synthesis Example 12] Synthesis of dye (G-12) A dye (G-12) was obtained as a black powder (yield: 3.5 g, 20%) in the same manner as in Synthesis Example (G-0), except that dipotassium 2-naphthol-6,8-disulfonate was used instead of 2-naphthol.

[0159] 6.80(1H), 7.72(1H), 7.80(1H), 7.94(1H)8.02(1H), 8.41(1H), 8.76(1H), 8.85(1H), 8.90(1H)

[0160] [Synthesis Example 13] Synthesis of dye (G-13) A dye (G-13) was obtained as a black powder (yield: 48.7 g, 97%) in the same manner as in Synthesis Example (G-0), except that 2-amino-4-nitrophenol was used instead of sodium picramate.

[0161] 1 H-NMR (400MHz, D2O): δ(ppm)=6.77-6.86(2H), 6.97(2H), 7.10(2H), 7.46(1H), 7.56(1H), 7.98(2H), 8.17(1H), 8.46(1H)

[0162] [Synthesis Example 14] Synthesis of dye (G-14) The dye (G-14) was obtained as a black powder (yield 7.0 g, 55%) in the same manner as in Synthesis Example (G-0), except that 1-naphthol-4-sodium sulfonate was used instead of 2-naphthol and 2-amino-4-nitrophenol was used instead of sodium picramate.

[0163] 1 H-NMR (400MHz, D2O): δ(ppm)=6.87(1H), 7.38(1H), 7.46-7.51(2H), 7.63(1H), 7.72(1H), 7.79(1H), 8.20-8.28(3H), 8.75(1H)

[0164] [Synthesis Example 15] Synthesis of dye (G-15) A dye (G-15) was obtained as a black powder (yield 9.2 g, 80%) in the same manner as in Synthesis Example (G-0), except that 3-amino-4-hydroxyphenylmethylsulfone was used instead of sodium picramate.

[0165] 1 H-NMR (400MHz, D2O): δ(ppm)=3.33(3H), 6.70-6.82(2H), 6.95(2H), 7.05(2H), 7.46(1H), 7.52(1H), 7.90(2H), 8.10(1H), 8.35(1H)

[0166] [Synthesis Example 16] Synthesis of dye (G-16) The dye (G-16) was obtained as a black powder (yield 10.5 g, 80%) in the same manner as in Synthesis Example (G-0), except that sodium 2-naphthol-7-sulfonate was used instead of 2-naphthol and sodium picramate was used instead of 3-amino-4-hydroxyphenylmethylsulfone.

[0167] 1H-NMR (400MHz, D2O): δ(ppm)=3.32(3H), 7.05(1H), 7.39(1H), 7.48-7.53(2H), 7.59(2H), 7.80(1H), 7.88(1H), 8.07(1H), 8.46(1H), 8.70(1H)

[0168] [Synthesis Example 17] Synthesis of dye (G-17) A dye (G-17) was obtained as a black powder (yield: 5.4 g, 44%) in the same manner as in Synthesis Example (G-0), except that 2-amino-p-cresol was used instead of sodium picramate.

[0169] 1 H-NMR (400MHz, D2O): δ(ppm)=2.29(3H), 6.80-6.91(4H), 7.01(2H), 7.40(2H), 7.57(1H), 7.89(1H), 8.27(1H)

[0170] [Synthesis Example 18] Synthesis of dye (G-18) The dye (G-18) was obtained as a black powder (yield 7.5 g, 60%) in the same manner as in Synthesis Example (G-0), except that 1-naphthol-4-sodium sulfonate was used instead of 2-naphthol and 2-amino-4-nitrophenol was used instead of sodium picramate.

[0171] 1 H-NMR (400MHz, D2O): δ(ppm)=6.87(1H), 7.38(1H), 7.46-7.51(2H), 7.63(1H), 7.72(1H), 7.79(1H), 8.20-8.28(3H), 8.77(1H)

[0172] [Synthesis Example 19] Synthesis of dye (A-1) Sodium picramate (28.2 g) was placed in a reaction vessel and dispersed in water (242 mL), and 35% hydrochloric acid (6.9 g, manufactured by Kanto Chemical Co., Ltd.) was added. After stirring at 5°C or less in an ice bath, 40% aqueous sodium nitrite solution (6.4 g, manufactured by Kanto Chemical Co., Ltd.) was added dropwise. After stirring for 3 hours, sulfamic acid (manufactured by Fujifilm Wako Pure Chemical Co., Ltd.) was added to remove excess sodium nitrite to obtain a diazotized liquid. H acid hydrate (38.0 g, manufactured by Tokyo Chemical Industry Co., Ltd.) was placed in a reaction vessel and dispersed in water (250 mL), and then 24% aqueous sodium hydroxide solution (6.8 g) and sodium carbonate (9.0 g, manufactured by Kanto Chemical Co., Ltd.) were added and dissolved. While stirring this solution at 5°C or less in an ice bath, the previously synthesized diazotized liquid was added, and the pH was adjusted to 9.0 to 9.5. After stirring overnight (2 hours or more), it was confirmed by a resorcin check that no diazotized product remained. The temperature was raised to 40°C, and the pH was adjusted to 6.0 to 6.5 using 95% sulfuric acid (Kanto Chemical Co., Ltd.), and then filtered. The obtained solid was dried to obtain a compound represented by the following formula (2-A-1) as a black-purple powder (yield: 52.0 g, yield: 100%).

[0173] 1 H-NMR (400MHz, D2O): δ(ppm)=7.12(1H), 7.21(1H), 7.57(1H), 8.45(1H), 8.73(1H)

[0174] [ka]

[0175] The compound (2-A-1) (10.9 g) was placed in a reaction vessel and dispersed in water (140 mL), and 35% hydrochloric acid (4.1 g, manufactured by Kanto Chemical Co., Ltd.) was added. After stirring at 5°C or less in an ice bath, 40% aqueous sodium nitrite solution (3.4 g, manufactured by Kanto Chemical Co., Ltd.) was added dropwise. After stirring for 3 hours, sulfamic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added to remove excess sodium nitrite. Barbituric acid (2.6 g, manufactured by Tokyo Chemical Industry Co., Ltd.) was placed in a reaction vessel and dispersed in water (150 mL), and then 24% aqueous sodium hydroxide solution (3.8 g) and sodium carbonate (1.9 g) were added and dissolved. While stirring this solution at 5°C or less in an ice bath, the previously synthesized diazotization solution was added to adjust the pH to 9.0 to 9.5. After stirring overnight (2 hours or more), a resorcin check confirmed that no diazotized product remained. The temperature was raised to 40° C., and the pH was adjusted to 6.0 to 6.5 with 95% sulfuric acid (Kanto Chemical Co., Ltd.), followed by filtration. The resulting solid was dried to obtain dye (A-1) as a black powder (yield: 11.7 g, yield: 86%).

[0176] 1 H-NMR (400MHz, D2O): δ(ppm)=4.94(1H), 7.75(1H), 7.96(1H), 8.41(1H), 8.50(1H), 8.76(1H)

[0177] [Synthesis Example 20] Synthesis of dye (A-2) The same procedure as in Synthesis Example 19 was followed except that sodium 2-thiobarbiturate was used instead of barbituric acid, to obtain dye (A-2) as a black powder (yield: 10.0 g, 70%).

[0178] 1 H-NMR (400MHz, D2O): δ(ppm)=4.75(1H), 7.68(1H), 7.89(1H), 8.32(1H), 8.39(1H), 8.66(1H)

[0179] [Synthesis Example 21] Synthesis of dye (A-3) The procedure was the same as in Synthesis Example 19, except that 2-amino-4-nitrophenol was used instead of sodium picramate, to obtain dye (A-3) as a black powder (yield: 16.1 g, yield: 91%).

[0180] 1 H-NMR (400MHz, D2O): δ(ppm)=4.82(1H), 6.63(1H), 7.72(1H), 7.96(1H), 8.00(1H), 8.44(1H), 8.58(1H)

[0181] [Synthesis Example 22] Synthesis of dye (A-4) The procedure was the same as in Synthesis Example 19, except that 2-amino-5-nitrophenol was used instead of sodium picramate, to obtain dye (A-4) as a black powder (yield: 9.84 g, 78%).

[0182] 1 H-NMR (400MHz, D2O): δ(ppm)=4.84(1H), 7.06(1H), 7.37(1H), 7.52(1H), 7.72(1H), 7.85(1H), 8.28(1H)

[0183] [Synthesis Example 23] Synthesis of dye (A-5) The procedure was the same as in Synthesis Example 19, except that 2-aminophenol-4-sulfonic acid was used instead of sodium picramate, to obtain dye (A-6) as a black powder (yield: 6.1 g, 45%).

[0184] 1 H-NMR (400MHz, D2O): δ(ppm)=4.86(1H), 6.81(1H), 7.42(1H), 7.73(1H), 7.94(1H), 8.16(1H), 8.42(1H)

[0185] [Synthesis Example 24] Synthesis of dye (A-6) The same procedure as in Synthesis Example 19 was followed except that nitramic acid was used instead of sodium picramate, to obtain dye (A-6) as a black powder (yield: 13.5 g, yield: 92%).

[0186] 1 H-NMR (400MHz, D2O): δ(ppm)=4.75(1H), 7.75(1H), 8.01(1H), 8.51-8.52(2H), 8.64(1H)

[0187] [Example 1] <Preparation of colored aluminum> Colored aluminum was produced by anodizing an aluminum substrate in the following manner: In the anodizing and dyeing steps, the treatment time and the dye compound concentration were set. (Degreasing) A degreasing solution was prepared by mixing 150 mL of a degreasing agent (manufactured by Okuno Chemical Industries Co., Ltd., product name: TOP ADD-100), 70 mL of 98% sulfuric acid, and 1000 mL of water in a degreasing container. The aluminum substrate for dyeing cut to an appropriate size was immersed in the solution and degreased at 60°C for 3 minutes, and then washed with water after the treatment. (Anodization) Prepare 180 g / L of electrolyte using 98% sulfuric acid in an electrolyte container, connect an aluminum substrate to the electrode of an electrolysis device, and immerse it in an electrolyte tank at a temperature of 20±1°C (19-21°C) and a current density of 1.0 A / dm 2 Anodization was performed under the conditions of the current flow time shown below, and an anodized film having the following thickness was obtained. After oxidation, the sample was washed with water. Anodizing conditions: Electric current for 15 minutes Anodizing film thickness: 5 μm (Surface Conditioning) A surface conditioner (TAC Somar 121, manufactured by Okuno Chemical Industries Co., Ltd.) and water were used to prepare a surface conditioner solution with a concentration of 50 mL / L, and the aluminum substrate was immersed in the solution for 1 minute at 45° C. After immersion, the aluminum substrate was washed with water. (Dyeing) Using the dye (G-1) obtained in Synthesis Example 1, dyeing aqueous solutions containing the dye at the following concentrations were prepared as the dye compositions of the present invention, and the substrates were immersed for the following dyeing times and dyed at a temperature (make-up bath temperature) of 55° C. After dyeing, the aluminum substrate was washed with water. Dyeing conditions: dye concentration 2.0% by mass Dyeing time: 30 seconds (Sealing) A 40 mL / L sealing solution was prepared using a sealant (manufactured by Okuno Chemical Industries Co., Ltd., product name: Topseal H-298) and water, and sealing treatment was carried out for 15 minutes at about 90° C. After sealing treatment, the sample was dried with hot air.

[0188] <Evaluation of Hue> The hue of the colored aluminum plate colored with the dye (G-1) was visually observed and measured with a colorimeter (device name: Konica Minolta spectrophotometer, model: CM-3700A) using the CIE L * a * b * The evaluation was performed using a color system. The results of the evaluated hues are shown in Table 1.

[0189] <Evaluation of light resistance> A light resistance test was carried out on the colored aluminum plate colored with the dye (G-1) by the following method. A xenon fade meter / ATLAS Ci3000+Xenon Weather Ometer (manufactured by ATLAS) was used, and irradiance was 300-400 nm, 60 W / m 2 The colored aluminum plate was irradiated for 50 hours under the conditions of a test chamber temperature of 38°C, humidity of 50%, and black panel (BP) temperature of 63°C. The hue measured by a color difference meter and the color difference ΔE before and after light irradiation were measured. * The color fastness was measured, and the light fastness was judged by visual judgment of the color fastness according to the gray scale grade (JIS L 0804 "Gray scale for discoloration") The grade is the highest grade 5 and the lowest grade 1, and the higher the grade, the darker the color (color difference ΔE * In the evaluation method of the present invention, the results of the series are divided into three stages and evaluated according to the following criteria. The results are shown in Table 1. Grayscale criterion: series and its correspondence to the evaluation in this invention Grades 5 to 4: A (particularly good light resistance) Grade 3: B (normal level of light resistance) Grade 2 or lower: C (low light resistance)

[0190] [Examples 2 to 10] Colored aluminum sheets were prepared in the same manner as in Example 1, except that the dyes (G-2) to (G-7) or (A-1) to (A-3) were used instead of the dye (G-1). The hue and color difference ΔE * The results of the visual evaluation of light resistance are shown in Table 1.

[0191] [Comparative Example 1] Instead of the dye (G-1), the following dye (D-1) not belonging to the present invention and represented by the following formula was used to prepare colored aluminum under the same preparation conditions as in Example 1, and the hue and color difference ΔE * The results of the visual evaluation of light resistance are shown in Table 1.

[0192] [ka]

[0193] [Table 1]

[0194] As is clear from the results in Table 1, by using an anodized aluminum colorant consisting of a dye composition containing the azo dye of the present invention, it is possible to form a coating on aluminum that is black or brown in color and has better light resistance than those using conventional dyes. [Industrial Applicability]

[0195] By using a dye composition containing the azo dye according to the present invention, it is possible to obtain a colorant for anodized aluminum that is free of heavy metals such as chromium and halogens and that forms a monochromatic (single dye) black or brown colored coating having excellent light resistance. In addition, by using the colorant, it is possible to obtain an anodized aluminum coating that is monochromatically colored black or brown and has excellent light resistance.

Claims

1. A colorant for anodized aluminum, comprising a dye composition containing an azo dye represented by the following general formula (1): 【Chemistry 1】 [In formula (1), Each X independently represents a non-color-forming cation; Y 1 represents any one of the following formulae (Y 1 -1) to (Y 1 -3); Y 2 represents any one of the following formulas (Y 2 -1) to (Y 2 -9). 【Chemistry 2】 [In formulae (Y 1 -1) to (Y 1 -3), * indicates a bonding site with an azo group.] 【Chemistry 3】 [In formulas (Y 2 -1) to (Y 2 -9), Each X independently represents a non-color-forming cation; Each Z independently represents an oxygen atom or a sulfur atom. R 21 each independently represents an alkyl group having 1 to 3 carbon atoms or a non-color-forming cation; * indicates the bonding site with the azo group.]

2. X is independently H ＋ , Na ＋ or NH ４ ＋ 2. The colorant for anodized aluminum according to claim 1,

3. An azo dye represented by the following general formula (1A): 【Chemistry 4】 [In formula (1A), each X independently represents a non-color-forming cation.]

4. An azo dye represented by the following general formula (2A): 【Chemistry 5】 [In formula (2A), each X independently represents a non-color-forming cation.]

5. An azo dye represented by the following general formula (3A): 【Chemistry 6】 [In formula (3A), each X independently represents a non-color-forming cation, and each R independently represents an alkyl group having 1 to 3 carbon atoms or a non-color-forming cation.]

6. A dye composition comprising the azo dye according to any one of claims 3 to 5.

7. A colorant for anodized aluminum, comprising the dye composition according to claim 6.

8. A method for coloring anodized aluminum or anodized aluminum alloy, comprising using a dye composition containing 0.02 to 10 mass % of the azo dye according to any one of claims 3 to 5.

9. A method for producing the colorant for anodized aluminum according to claim 1, comprising the steps of: The azo dye represented by the general formula (1) is obtained by a diazo coupling reaction between a diazotized product obtained by diazotizing a compound represented by the following general formula (4A) and a compound represented by any one of the following general formulas (5A) to (5H) and / or a salt thereof: 【Chemistry 7】 【Chemistry 8】 [In formula (4A) and formulas (5A) to (5H), X and Y 1 are the same as defined in general formula (1) and formulas (Y 2 -1) to (Y 2 -8).]

10. A method for producing the colorant for anodized aluminum according to claim 1, comprising the steps of: The azo dye represented by the general formula (1) is obtained by a diazo coupling reaction between a diazotized product obtained by diazotizing a compound represented by the following general formula (4A) and a compound represented by the following general formula (8) and / or a salt thereof: 【Chemistry 9】 【Chemistry 10】 [In formula (4A) and formula (8), R ２１ , X, Y1 and Z are the same as defined in the general formula (1) and the formula (Y 2 -9).]

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