Azo dye, dye composition, colorant for anodized alumina, coloring method, and method for producing dye

Abstract

The present invention relates to an azo dye represented by general formula (1), (2) or (3). # imgabs0 #

Description

Technical Field

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

[0002] In the past, as a method for coloring the surface of aluminum (including its oxides or alloys), the following method was used: aluminum was used as an anode and electricity was passed through an electrolyte containing water and an appropriate acid (anodic oxidation), a porous aluminum oxide film (aluminum film) was formed on the surface, and then an organic pigment (or organic dye) was used as a colorant to color the surface (Patent Documents 1 to 6).

[0003] Chromium-containing dyes for anodic aluminum films (Patent Documents 1 to 6, etc.) have excellent light resistance and heat resistance and have been widely used. In recent years, from environmental considerations, there is a demand for pigments with various hues that do not contain heavy metals such as chromium and halogens such as chlorine or bromine.

[0004] There are yellow, cyan, red and other dyes for aluminum coatings that do not contain heavy metals and halogens, but there are few black and brown dyes that do not contain heavy metals. Therefore, sometimes a mixture of multiple pigments is used to produce a dark color.

[0005] As a black dye for anodized aluminum coatings that does not contain heavy metals, Sanodye (registered trademark) Black OA from Clariant is known. However, this dye has insufficient light fastness when used for dark dyeing and good light fastness when used for light dyeing (Patent Document 7).

[0006] Prior art literature

[0007] Patent Literature

[0008] Patent Document 1: Japanese Patent Application Laid-Open No. 9-302256

[0009] Patent Document 2: International Publication No. 2019 / 189209

[0010] Patent Document 3: International Publication No. 2019 / 189211

[0011] Patent Document 4: Japanese Patent Application Laid-Open No. 60-235867

[0012] Patent Document 5: Japanese Patent Application Laid-Open No. 6-93195

[0013] Patent Document 6: Japanese Patent Application No. 2002-522617

[0014] Patent Document 7: U.S. Patent No. 2580867 Summary of the invention

[0015] Problems to be solved by the invention

[0016] One of the purposes of the present invention is to provide an azo dye that can form an anodic oxidation film on the surface of aluminum or aluminum alloy that has excellent light resistance, does not contain heavy metals such as chromium and halogen, and presents a black or brown color in a single color (single pigment). In addition, one of the purposes of the present invention is to provide a dye composition containing the above azo dye, a colorant for anodic aluminum containing the dye composition, a coloring method for anodic aluminum or anodic aluminum alloy using the dye, and a method for producing the above azo dye.

[0017] Means for solving problems

[0018] The inventors have discovered an azo colorant (dyestuff), a dye composition, and a colorant for anodized aluminum that can color anodized aluminum in black or brown in a single color and form a film having excellent light resistance. That is, the present invention consists of the following contents.

[0019] [1] An azo dye represented by the following general formula (1), (2) or (3),

[0020] [Chemistry 1]

[0021]

[0022] In formulas (1), (2) and (3),

[0023] R 1 ~R 3 Each independently represents -H, an alkyl group having 1 to 3 carbon atoms, -NO2, -SO2CH3, -SO2CH2CH3 or -COOX,

[0024] R 4 ~R 17 Each independently represents -H, -OH, -SO3X, -COOX, or an acylamino group having 7 to 12 carbon atoms which may have a substituent,

[0025] R 18 ~R 20 Each independently represents -H, an alkyl group having 1 to 3 carbon atoms, -NO2, -SO2CH3, -SO2CH2CH 3、 -SO3X or -COOX,

[0026] R 21 each independently represents an alkyl group having 1 to 3 carbon atoms, or a non-color-forming cation,

[0027] X each independently represents a non-color-developing cation,

[0028] Z each independently represents an oxygen atom or a sulfur atom.

[0029] [2] The azo dye according to [1], which is represented by the general formula (1) or (2), wherein R 1 ~R 3 One or two of them are -NO2.

[0030] [3] The azo dye according to [1] or [2], which is represented by the general formula (1) or (2), wherein R 3 It is -CH3 or -SO2CH3.

[0031] [4] The azo dye according to any one of [1] to [3], which is represented by the general formula (1), wherein R 4 ~R 10 Either one or both of them are -OH, or R 4 ~R 10 Either one or both of them are -SO3Na.

[0032] [5] The azo dye according to any one of [1] to [3], which is represented by the general formula (2), wherein R 11 ~R 17 Either one or both of them are -OH, or R 11 ~R 17 Either one or both of them are -SO3Na.

[0033] [6] The azo dye according to [1], which is represented by the general formula (3), wherein R 18 ~R 20 Each is independently -H, -CH3, -NO2, -SO2CH3, -SO3H, -SO3Na, -COOH or -COONa.

[0034] [7] The azo dye according to any one of [1] to [6], wherein each X is independently H + 、Na + or NH4 + .

[0035] [8] The azo dye according to any one of [1] to [4] and [7], which is represented by the following general formula (1A):

[0036] [Chemistry 2]

[0037]

[0038] In the formula (1A), X has the same meaning as defined in the above general formula (1).

[0039] [9] The azo dye according to any one of [1] to [3], [5] and [7], which is represented by the following general formula (2A):

[0040] [Chemistry 3]

[0041]

[0042] In the formula (2A), X has the same meaning as defined in the above general formula (2).

[0043]

[10] The azo dye according to any one of [1], [6] and [7], which is represented by the following general formula (3A):

[0044] [Chemistry 4]

[0045]

[0046] In the formula (3A), X has the same meaning as defined in the above general formula (3).

[0047]

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

[10] .

[0048]

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

[11] .

[0049]

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

[10] .

[0050]

[14] A production method, which is the production method of the azo dye according to any one of [1] to

[10] , wherein

[0051] The azo dye represented by the above general formula (1) or (2) is obtained by diazo coupling reaction of a diazo compound obtained by diazotizing a compound represented by the following general formula (4) with a compound represented by the following general formula (5) or (6) and / or a salt thereof.

[0052] [Chemistry 5]

[0053]

[0054] In formulas (4) to (6), R 1 ~R 17 and X have the same meanings as defined in the above-mentioned general formulae (1) and (2).

[0055]

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

[10] , wherein the azo dye represented by the general formula (3) is obtained by diazo coupling a diazo compound obtained by diazotizing a compound represented by the following general formula (7) with a compound represented by the following general formula (8) and / or a salt thereof,

[0056] [Chemistry 6]

[0057]

[0058] In formula (7) and formula (8), R 18 ~R 21 , X and Z have the same meanings as defined in the above general formula (3).

[0059] Effects of the Invention

[0060] According to the present invention, an azo dye can be provided which can form an anodic oxidation film on the surface of aluminum or aluminum alloy which has excellent light resistance, does not contain heavy metals such as chromium and halogen, and presents a black to brown color system in a single color (single pigment). In addition, according to the present invention, a dye composition containing the above azo dye, a colorant for anodic aluminum containing the dye composition, a coloring method for anodic aluminum or anodic aluminum alloy using the dye, and a method for producing the above azo dye can be provided. DETAILED DESCRIPTION

[0061] Hereinafter, the embodiments of the present invention will be described in detail. It should be noted that the present invention is not limited to the following embodiments, and various modifications can be made within the scope of its purpose. Hereinafter, the azo dye represented by the above-mentioned general formula (1), (2) or (3) will be specifically described, but the present invention is not limited to these.

[0062] In the general formulas (1), (2) and (3), as R 1 ~R 3 , R 18～21 Specific examples of the "alkyl group having 1 to 3 carbon atoms" include methyl group, ethyl group, n-propyl group and isopropyl group.

[0063] The "non-color-forming cation" represented by "X" in "-SO3X" or "-COOX" in the general formula (1), (2) and (3) is a cation that does not have a chromophore (e.g., a nitro group, an azo group, or a carbonyl group). Specifically, the non-color-forming cation includes hydrogen ions (H + ), lithium ion (Li + ), sodium ion (Na + ), potassium ion (K + ) and other alkali metal ions; NH4 + , by N+ R 22 R 23 R 24 R 25 As R 22 ~R 25 , each independently of the other, may be an alkyl group having 1 to 3 carbon atoms (methyl, ethyl, n-propyl, isopropyl). In the general formulae (1), (2) and (3), a plurality of Xs may be the same or different. Xs are preferably each independently H + 、Na + or NH4 + .

[0064] In the general formulae (1) and (2), the "acylamino group having 7 to 12 carbon atoms which may have a substituent" can be represented by "-(C=O)-NR 31 R 32 ". Among them, "R 31 ” and “R 32 " represents the "substituent" in "the acylamino group having 7 to 12 carbon atoms which may have a substituent". R 31 or R 32 Specific examples include -H, -OH, -SO3X, -COOX, methyl, ethyl, n-propyl, isopropyl, -NO2, -SO2CH3, -SO2CH2CH3 or phenyl. 31 and R 32 The "phenyl group" represented by R may further have the above-mentioned "substituent". 31 and R 32 When the phenyl group represented by has a substituent, the substituent is preferably a methyl group, an ethyl group or -NO2. In general formulae (1) and (2), the "carbon number 7 to 12" in the "acylamino group having 7 to 12 carbon atoms which may have a substituent" includes the carbon number contained in the "substituent".

[0065] In the general formulas (1) and (2), R 1 ~R 3 Each independently represents -H, an alkyl group having 1 to 3 carbon atoms, -NO2, -SO2CH3, -SO2CH2CH3 or -COOX. As one embodiment of the azo dye of the present invention, in the general formulas (1) and (2), preferably R 1 ~R 3 As another form of the azo dye, in the general formulas (1) and (2), preferably R 3 It is an alkyl group having 1 to 3 carbon atoms (particularly preferably -CH3) or -SO2CH3.

[0066] R 1 ~R 3The azo dye represented by the general formula (1) or (2) in which one or two of the R groups are -NO2 preferably has a structure represented by the following general formula (Ia) or (Ib). In the general formula (Ia) and (Ib), * represents a bonding site with an azo group (-N=N-). R in the general formula (Ia) 1 represents the same as R in the above general formula (1) and (2) 1 The same meanings as R in the general formula (Ia) 1 Preferred is -H or -NO2, more preferred is -NO2.

[0067] [Chemistry 7]

[0068]

[0069] R 3 The azo dye represented by the general formula (1) or (2) which 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 * represents a bonding site with an azo group (-N=N-). 3a Preferred is -CH3 or -SO2CH3, more preferred is -SO2CH3.

[0070] [Chemistry 8]

[0071]

[0072] In the general formulas (1) and (2), R 4 ~R 17 Each independently represents -H, -OH, -SO3X, -COOX, or an acylamino group having 7 to 12 carbon atoms which may have a substituent, and each X independently represents a non-color-forming cation. As one embodiment of the azo dye of the present invention, in the general formula (1), preferably R 4 ~R 10 Any one or both of is -OH, or preferably R 4 ~R 10 Similarly, as one form of the azo dye of the present invention, in the general formula (2), preferably R 11 ~R 17 Any one or both of is -OH, or preferably R 11 ~R 17 Either one or both of them are -SO3Na.

[0073] The azo dye represented by the general formula (1) is preferably R 4 or R 6For 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), * represents the bonding site to the azo group (-N=N-), and R 5 ~R 10 represents the same as R in the above general formula (1) 5 ~R 10 The same meaning, R 4a It represents -H, -SO3X, -COOX, or an acylamino group having 7 to 12 carbon atoms which may have a substituent.

[0074] [Chemistry 9]

[0075]

[0076] The azo dye represented by the general formula (1) preferably has a structure represented by the general formula (IIa), and more preferably has a structure represented by the following general formulas (IIa-1) to (IIa-3).

[0077] [Chemistry 10]

[0078]

[0079] The azo dye represented by the general formula (2) preferably has R 11 The structure represented by the following general formula (III) is -OH. In the general formula (III), * represents the bonding site to the azo group (-N=N-), R 12 ~R 17 It represents the same as R in the general formula (1) 12 ~R 17 The same meaning, R 11a It represents -H, -SO3X, -COOX, or an acylamino group having 7 to 12 carbon atoms which may have a substituent.

[0080] [Chemistry 11]

[0081]

[0082] The azo dye represented by the general formula (2) preferably has a structure represented by the general formula (IIIa), and more preferably has a structure represented by the following general formula (IIIa-1) or (IIIa-2).

[0083] [Chemistry 12]

[0084]

[0085] 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. 21They may be the same or different from each other. 21 All non-coloring cations can be used, and from the perspective of easily obtaining an anodic oxide film with better light resistance, R 21 All of can be -H.

[0086] In the general formula (3), Z represents an oxygen atom or a sulfur atom. A plurality of Zs may be the same or different from each other. In the general formula (3), 1 to 3 Zs may be oxygen atoms, 2 to 3 Zs may be oxygen atoms, and from the perspective of easily obtaining an anodic oxide film with better light resistance, 3 Zs may be oxygen atoms. The azo dye represented by the general formula (3) preferably has a structure represented by the following general formula (IV), and from the perspective of easily obtaining an anodic oxide film with better light resistance, it more preferably has a structure represented by the following general formula (IVa). In formulas (IV) and (IVa), * represents a bonding site with an azo group (-N=N-).

[0087] [Chemistry 13]

[0088]

[0089] In the general formula (3), as R 18 ~R 20 , preferably each independently is -H, -CH3, -NO2, -SO2CH3, -SO3H, -SO3Na, -COOH or -COONa. Preferably R 18 ~R 20 One or two of them are -NO2. The azo dye represented by the general formula (3) preferably has a structure represented by the general formula (Ia), (Ib), or (Ic), and more preferably has a structure represented by the general formula (Ia).

[0090] The compounds of the azo dye of the present invention represented by the general formula (1), (2) or (3) (hereinafter also simply referred to as dyes (1) to (3)) include all stereoisomers and tautomers that can be generated, and the following specific example compounds are described in 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 to these.

[0091] [Chemistry 14]

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[0189] The pigments (1) to (3) are preferably compounds represented by the following general formula (V-1), and among the compounds represented by the general formula (V-1), compounds represented by the formula (G-2), the formula (G-4) or the formula (A-1) are particularly preferred. When a compound represented by the following general formula (V-1) (particularly a compound represented by the formula (G-2), the formula (G-4) or the formula (A-1)) is used, it is easier to obtain an anodic oxide film that exhibits black color in a single color and has excellent light resistance.

[0190] [Chemistry 63]

[0191]

[0192] 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 With the above X and R 21 Synonymous.

[0193] [Chemistry 64]

[0194]

[0195] The compound represented by the general formula (1) or (2) can be obtained, for example, by a method comprising the step of subjecting a diazo compound obtained by diazotizing a compound represented by the following general formula (4) to a diazo coupling reaction with a compound represented by the following general formula (5) or (6) and / or a salt thereof (coupling step). That is, the compound represented by the general formula (4) can be obtained by subjecting a diazo compound obtained by diazotizing a compound represented by the following general formula (4) to a diazo coupling reaction with a compound represented by the following general formula (5) or (6) and / or a salt thereof.

[0196] [Chemistry 65]

[0197]

[0198] [In formulas (4) to (6), R1 ~R 17 and X have the same meanings as those defined in the above general formulae (1) and (2).]

[0199] In the following, an example of a method for producing a compound (azo dye) of the present invention represented by the above-mentioned general formula (1) or (2) is shown, but it is not limited to this method. Specifically, initially, an aromatic amine derivative represented by the above-mentioned general formula (4) and having a suitable substituent is reacted in an acid aqueous solution such as hydrochloric acid or sulfuric acid with an alkaline aqueous solution prepared using sodium nitrite or the like at a suitable temperature, thereby obtaining a compound represented by the following general formula (4a) and / or its salt (diazo component).

[0200] [Chemistry 66]

[0201]

[0202] [In formula (4a), R 1 ~R 3 and X have the same meanings as defined in the above general formulae (1) and (2).]

[0203] On the other hand, by dissolving and reacting the compound represented by the above general formula (5) or (6) in an aqueous solution of sodium hydroxide or the like, a salt (coupler component) of the compound represented by the general formula (5) or (6) can be obtained. The compound represented by the general formula (5) or (6) can be used directly as a coupler component (also simply referred to as coupler component (5) or (6)).

[0204] Next, the diazo component (4a) represented by the general formula (4a) is reacted with the coupler component (5) or (6) (diazo coupling reaction) 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 (azo dye) represented by the general formula (1) or (2) according to the present embodiment comprises the step of obtaining the compound represented by the general formula (1) or (2) obtained as described above.

[0205] The compound represented by the general formula (3) can be obtained, for example, by a method comprising a step (coupling step) of subjecting a diazo compound obtained by diazotizing a compound represented by the following general formula (7) to a diazo coupling reaction with a compound represented by the following general formula (8) and / or a salt thereof. That is, the compound represented by the general formula (7) can be obtained by subjecting a diazo compound obtained by diazotizing a compound represented by the following general formula (7) to a diazo coupling reaction with a compound represented by the following general formula (8) and / or a salt thereof.

[0206] [Chemistry 67]

[0207]

[0208] [In formulas (7) and (8), R 18 ~R 21 , X and Z have the same meanings as those defined in the above general formula (3).]

[0209] In the following, an example of a method for producing a compound (azo dye) of the present invention represented by the above-mentioned general formula (3) is shown, but it is not limited to this method. Specifically, initially, a compound represented by the following general formula (7a) and / or its salt (diazo component) is obtained by reacting an aromatic amine derivative having a suitable substituent in an acid aqueous solution such as hydrochloric acid or sulfuric acid with an alkaline aqueous solution prepared using sodium nitrite or the like at an appropriate temperature.

[0210] [Chemistry 68]

[0211]

[0212] [In formula (7a), R 18 ~R 20 , and X have the same meanings as those defined in the above general formula (3).]

[0213] On the other hand, by dissolving and reacting the compound represented by the general formula (8) in an aqueous solution of sodium hydroxide or the like, a salt (coupler component) of the compound represented by the general formula (8) can be obtained. The compound represented by the general formula (8) can be used directly as a coupler component (also simply referred to as coupler component (8)).

[0214] Next, the diazo component (7a) represented by the general formula (7a) is reacted with the coupler component (8) (diazo coupling reaction) 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 (azo dye) represented by the general formula (3) according to the present embodiment comprises the step of obtaining the compound represented by the general formula (3) obtained as described above.

[0215] The above-mentioned pigment (1), (2) or (3) can be purified by known methods such as purification by column chromatography; purification by adsorption using silica gel, activated carbon, activated clay, etc.; recrystallization using a solvent, various crystallization methods using acids, etc.

[0216] The identification and physical property evaluation of the pigments (1) to (3) of the present invention, their intermediates, or various products obtained by the above-mentioned production method can be carried out using ultraviolet visible absorption spectroscopy analysis (UV-Vis), thermogravimetric measurement-differential thermal analysis (TG-DTA), gas chromatography analysis (GC), thin layer chromatography analysis (TLC), high-speed liquid chromatography (HPLC), liquid chromatography-mass spectrometry (LC / MS), gas chromatography-mass spectrometry (GC / MS), nuclear magnetic resonance analysis (NMR), etc.

[0217] The azo dyes represented by general formulas (1) to (3) in the present invention can be used as components of dye compositions. That is, for dyes (1) to (3), a single-color dye can be used alone and can be suitably used as a dye compound for coloring aluminum or fiber, etc. For dyes (1) to (3), two or more kinds can be used in combination to obtain various colors by mixing colors. For dye compositions, other components can be mixed for optimal dyeing (coloring using dyes). Specifically, liquids (solvents) such as water, alcohol, and solvents; additives such as surfactants, etc. can be listed. As the solvent, water is preferred. For dyes (1) to (3), other dyes can be used in combination as components of the dye composition. The so-called other dyes are other compounds, pigments, or dyes other than dyes (1) or (2), and specifically, ruthenium complexes, coumarin-based dyes, cyanine-based dyes, merocyanine-based dyes, rhodanine-based dyes, phthalocyanine-based dyes, porphyrin-based dyes, other xanthene-based dyes, etc. can be listed. When the pigments (1) to (3) are used in combination with other components, the amount used is preferably 10 to 200% by mass, more preferably 20 to 100% by mass, based on the other components of the pigments (1) to (3).

[0218] The dye composition of the present invention can be used as a colorant for anodized aluminum. When the pigments (1) to (3) are used as colorants for anodized aluminum, in the coloring (dyeing) method, the concentration of the pigments (1) to (3) in the dye composition containing the pigments (1) to (3) is preferably 0.02 to 10% by mass, more preferably 0.05 to 3% by mass. The lower the concentration of the compound, the more light coloring can be performed, and the higher the concentration, the more intermediate to dark colors can be performed.

[0219] Here, the so-called anodized aluminum refers to aluminum that has been treated in an electrolyte such as an acid aqueous solution to form an oxide layer having pores on the surface of the electrolytically treated aluminum. The colorant for anodized aluminum refers to a colorant that can be colored (dyed) by adsorbing a pigment into the pores on the aluminum surface having pores. Usually, in order to improve the durability and light resistance of the colored aluminum surface, a sealing treatment for plugging the pores is performed after coloring.

[0220] Examples of the aluminum in the anodized aluminum include aluminum, aluminum oxide, aluminum alloys with other metals, and metals or metal compounds containing aluminum.

[0221] As for the coloring method of aluminum using the coloring agent for anodized aluminum, a known method as an acid-resistant aluminum dyeing method can be used. For example, the method described in Japanese Industrial Standards (JIS H8601: 1999 "Anodic oxide film of aluminum and aluminum alloys"), Patent Documents 1 to 4, 6, etc. can be used. There is no particular limitation on the coloring method of aluminum, and an example is shown below.

[0222] Initially, the aluminum plate is degreased using an acid aqueous solution such as sulfuric acid, oxalic acid, chromic acid, sulfonic acid, and washed. Secondly, the degreased aluminum plate is used as anode, and an acid aqueous solution is used as an electrolyte to carry out electrolysis, and an anodic oxide film (acid-resistant aluminum film) (anodic oxidation treatment) forming a large number of pores is formed on the aluminum anode surface, and washed. Then, after appropriately implementing surface adjustment, washing, etc. to the anodic oxide film, the anodic oxide film is impregnated in an anodic oxide aluminum colorant aqueous solution containing a dye composition containing the compound of the present invention, so that the pores on the surface of the anodic oxide film are adsorbed with dye (dyeing, electrolytic coloring), and the pores on the surface are sealed with aluminum oxide hydrates, etc., to form a sealing material, so that the anodic oxide film can be colored.

[0223] When two or more dye compositions of the present invention are used in combination, or when the dye composition of the present invention is used in combination with other pigments, a mixed solution of all the pigments used can be prepared to impregnate the anodized aluminum. Alternatively, each pigment solution can be prepared separately and the anodized aluminum can be impregnated in each solution in sequence.

[0224] The electrolysis conditions during the coloring of the present invention may be direct current electrolysis or alternating current electrolysis, but direct current electrolysis is preferred. The current density is preferably 0.1 to 10 A / dm 2 , more preferably 0.5 to 3 A / dm 2 The power-on time is preferably 10 seconds to 60 minutes. The thickness of the anodized film is preferably 2 to 20 μm. As for these anodizing conditions, the longer the power-on time and the thicker the anodized film, the darker the color. Therefore, by adjusting these conditions, the color can be adjusted from light color to intermediate color to dark color.

[0225] The treatment temperatures in the above-mentioned steps are preferably appropriate temperatures for each step. The temperature during anodizing is preferably 0 to 80° C. The temperature during dyeing is preferably 10 to 70° C. The temperature for other treatments is preferably 10 to 80° C.

[0226] The dye composition in this embodiment can be used in the same manner for anodic oxides of metals other than aluminum, for example, magnesium, zinc, titanium, zirconium, etc., and can be applied to non-metals such as conductive plastics as long as the dye can be adsorbed into the pores of the anodic oxidation.

[0227] In the case of the coloring agent for anodized aluminum of the present embodiment, the characteristics of the sample colored with aluminum can be evaluated by measuring the hue, light resistance, etc. As for the hue, the color tone and uniformity can also be evaluated visually. As for the hue, the concentration (K / Sd), the hue (L ＊ 、a ＊ 、b ＊ ) and color difference (ΔE ＊ ) to determine.

[0228] The colors that can be expressed using the colorant for anodized aluminum of the present embodiment are, for example, black or brown. These light colors (light black, light brown, etc.) or dark colors (dark black, dark brown, etc.) can be expressed in different shades. The colorant for anodized aluminum of the present embodiment can also express mixed colors (intermediate colors) by using the above-mentioned compounds in combination with other pigments.

[0229] The light resistance test of aluminum colored by using the coloring agent for anodized aluminum of the present embodiment can be conducted by using a tester simulating sunlight including ultraviolet light, irradiating the sample with light for a certain period of time, and measuring the change in the hue of the colored aluminum before and after the test. Specifically, a colorimeter can be used, such as CIE L ＊ a ＊ b ＊ The color tone is measured by the color system, and the color difference ΔE before and after the light irradiation test is obtained. ＊ ab (or ΔE ＊ For the determination of light fastness, the color fastness of the colored aluminum can be determined by visual inspection using gray scale according to the method specified in the Japanese Shovel Press Standard (JIS L 0804 "Gray scale for discoloration and fading").

[0230] Colored aluminum using the coloring agent for anodized aluminum of the present embodiment is used for various products such as aluminum plate materials and aluminum exterior packaging.

[0231] As one embodiment of the present invention, a compound represented by the general formula (1), (2) or (3) for coloring anodized aluminum is provided. In addition, as one embodiment of the present invention, use of a compound represented by the general formula (1), (2) or (3) for coloring anodized aluminum is provided. In addition, as one embodiment of the present invention, use (application) of a compound represented by the general formula (1), (2) or (3) for producing a colorant for anodized aluminum is provided.

[0232] Example

[0233] The present invention is specifically described below by way of 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. are used. It should be noted that in the synthesis examples, with respect to the identification of the structure of the compound (pigment), 1 H-NMR (Nuclear magnetic resonance apparatus manufactured by JEOL Ltd., Model JNM-ECZ400S / L1) was used for the measurement, and the NMR measurement data are described based on the experimental results of each synthesis example described below.

[0234] [Synthesis Example (G-0)] Synthesis of Pigment (G-0)

[0235] (Preparation of diazo component 1)

[0236] 28.2 g of sodium picramate and 242 mL of water were placed in a reaction container, dispersed, 6.9 g of 35% hydrochloric acid (manufactured by Kanto Chemical Co., Ltd.) was added, and stirred for 2 hours at 5°C or below in an ice bath. After stirring, 6.4 g of 40% sodium nitrite aqueous solution (manufactured by Kanto Chemical Co., Ltd.) was dropped into the reaction solution, and stirred for 3 hours. After stirring, aminosulfonic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added to the reaction solution to decompose the excess sodium nitrite, thereby obtaining a diazotized solution 1.

[0237] (Preparation of coupling agent component 1 ~ Diazo coupling reaction 1)

[0238] Next, 38.0 g of H acid hydrate (sodium 4-amino-5-hydroxy-2,7-naphthalene disulfonate hydrate) (manufactured by Tokyo Chemical Industry Co., Ltd.) was placed in a reaction container, and 250 mL of water was added to disperse the mixture. Then, 6.8 g of a 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 to dissolve the mixture. The solution was stirred at 5°C or below in an ice bath to obtain a coupler component liquid. The previously synthesized diazotization solution 1 was added to the stirred coupler component liquid, and the pH was adjusted to 9.0 to 9.5. The mixture was stirred overnight to perform a diazo coupling reaction. After stirring, the reaction was considered to be complete by confirming that no diazotide remained by a resorcinol test. The temperature was raised to 40°C, 95% sulfuric acid (manufactured by Kanto Chemical Co., Ltd.) was added, and the pH was adjusted to 6.0 to 6.5. 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 (amount 52.0 g, yield 100%).

[0239] 1 H-NMR (400MHz, D2O): δ (ppm) = 7.12 (1H), 7.21 (1H), 7.57 (1H), 8.45 (1H), 8.73 (1H)

[0240] [Chemistry 69]

[0241]

[0242] (Preparation of diazo component 2)

[0243] Place 10.9 g of the above compound (3-G-0) in a reaction container, add 140 mL of water, disperse, and add 4.1 g of 35% hydrochloric acid. Stir for 3 hours at 5°C or below in an ice bath. After stirring, drop 3.4 g of a 40% sodium nitrite aqueous solution into the reaction solution and stir for 3 hours. After stirring, add aminosulfonic acid to decompose the excess sodium nitrite to obtain diazotized solution 2.

[0244] (Preparation of coupling agent component 2 ~ Diazo coupling reaction 2)

[0245] 2.74 g of 2-naphthol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 150 mL of water were placed in a reaction container. After dispersion, 3.8 g of 24% aqueous sodium hydroxide solution and 1.9 g of sodium carbonate were added to dissolve. The solution was stirred at a temperature below 5°C in an ice bath to obtain a coupler component liquid. The previously synthesized diazotization solution 2 was added to the stirring coupler component liquid, and the pH was adjusted to 9.0 to 9.5. After stirring overnight, it was confirmed by resorcinol inspection that no diazotide remained, and the reaction was considered to be complete. The temperature was raised to 40°C, 95% sulfuric acid was added, and the pH was adjusted to 6.0 to 6.5, and then filtered. The obtained solid was dried to obtain a pigment (G-0) as a black powder (yield 12.7 g, yield 92%).

[0246] 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)

[0247] [Synthesis Example 1] Synthesis of Pigment (G-1)

[0248] In Synthesis Example (G-0), except that R acid (3-hydroxynaphthalene-2,7-disulfonic acid) was used instead of 2-naphthol, a pigment (G-1) was obtained as a black powder in the same manner (amount 16.1 g, yield 91%).

[0249] 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)

[0250] [Synthesis Example 2] Synthesis of Pigment (G-2)

[0251] In Synthesis Example (G-0), a pigment (G-2) was obtained as a black powder in the same manner except that sodium 2-naphthol-7-sulfonate was used instead of 2-naphthol (amount 9.6 g, yield 61%).

[0252] 1 H-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)

[0253] [Synthesis Example 3] Synthesis of Pigment (G-3)

[0254] In Synthesis Example (G-0), except that disodium 3,6-dihydroxynaphthalene-2,7-disulfonate was used instead of 2-naphthol, a pigment (G-3) was obtained as a black powder in the same manner (amount 14.1 g, yield 78%).

[0255] 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)

[0256] [Synthesis Example 4] Synthesis of Pigment (G-4)

[0257] In Synthesis Example (G-0), except that 1-naphthol-3,6-disulfonic acid disodium was used instead of 2-naphthol, a pigment (G-4) was obtained as a black powder in the same manner (amount 14.1 g, yield 80%).

[0258] 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)

[0259] [Synthesis Example 5] Synthesis of Pigment (G-5)

[0260] A pigment (G-5) was obtained as a black powder in the same manner as in Synthesis Example (G-0) except that sodium 1-naphthol-4-sulfonate was used instead of 2-naphthol (amount 11.6 g, yield 71%).

[0261] 1 H-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)

[0262] [Synthesis Example 6] Synthesis of Pigment (G-6)

[0263] 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, a pigment (G-6) was obtained as a black powder (amount 11.9 g, yield 81%) in the same manner.

[0264] 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)

[0265] [Synthesis Example 7] Synthesis of Pigment (G-7)

[0266] 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, a pigment (G-7) was obtained as a black powder in the same manner (amount 10.6 g, yield 76%).

[0267] 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)

[0268] [Synthesis Example 8] Synthesis of Pigment (G-8)

[0269] A pigment (G-8) (amount 15.0 g, yield 95%) was obtained as a black powder in the same manner as in Synthesis Example (G-0), except that sodium 2-naphthol-6-sulfonate hydrate was used instead of 2-naphthol.

[0270] 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)

[0271] [Synthesis Example 9] Synthesis of Pigment (G-9)

[0272] In Synthesis Example (G-0), a pigment (G-9) was obtained as a black powder in the same manner except that sodium 6,7-dihydroxynaphthalene-2-sulfonate was used instead of 2-naphthol (amount 14.5 g, yield 90%).

[0273] 1H-NMR (400MHz, D2O): δ (ppm) = 6.88 (1H), 7.39 (1H), 7.06-7.66 (3H), 7.86 (1H), 8.64-8.70 (3H)

[0274] [Synthesis Example 10] Synthesis of Pigment (G-10)

[0275] A pigment (G-10) was obtained as a black powder in the same manner as in Synthesis Example (G-0) except that sodium 1-naphthol-8-sulfonate was used instead of 2-naphthol (amount 10.8 g, yield 69%).

[0276] 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)

[0277] [Synthesis Example 11] Synthesis of Pigment (G-11)

[0278] In Synthesis Example (G-0), a pigment (G-11) was obtained as a black powder in the same manner except that disodium chromotropyte dihydrate was used instead of 2-naphthol (yield 11.0 g, yield 61%).

[0279] 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)

[0280] [Synthesis Example 12] Synthesis of Pigment (G-12)

[0281] In Synthesis Example (G-0), except that dipotassium 2-naphthol-6,8-disulfonate was used instead of 2-naphthol, a pigment (G-12) was obtained as a black powder in the same manner (amount 3.5 g, yield 20%).

[0282] 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)

[0283] [Synthesis Example 13] Synthesis of Pigment (G-13)

[0284] In Synthesis Example (G-0), a pigment (G-13) was obtained as a black powder (amount 48.7 g, yield 97%) in the same manner except that 2-amino-4-nitrophenol was used instead of sodium picramate.

[0285] 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)

[0286] [Synthesis Example 14] Synthesis of Pigment (G-14)

[0287] 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, a pigment (G-14) was obtained as a black powder in the same manner (amount 7.0 g, yield 55%).

[0288] 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)

[0289] [Synthesis Example 15] Synthesis of Pigment (G-15)

[0290] A pigment (G-15) was obtained as a black powder in the same manner as in Synthesis Example (G-0) except that 3-amino-4-hydroxyphenylmethylsulfone was used instead of sodium picramate (amount 9.2 g, yield 80%).

[0291] 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)

[0292] [Synthesis Example 16] Synthesis of Pigment (G-16)

[0293] In Synthesis Example (G-0), except that sodium 2-naphthol-7-sulfonate was used instead of 2-naphthol, and 3-amino-4-hydroxyphenylmethylsulfone was used instead of sodium picramate, a pigment (G-16) was obtained as a black powder (amount 10.5 g, yield 80%) by the same method.

[0294] 1 H-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)

[0295] [Synthesis Example 17] Synthesis of Pigment (G-17)

[0296] In Synthesis Example (G-0), a pigment (G-17) was obtained as a black powder (amount 5.4 g, yield 44%) in the same manner except that 2-amino-p-cresol was used instead of sodium picramate.

[0297] 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)

[0298] [Synthesis Example 18] Synthesis of Pigment (G-18)

[0299] 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, a pigment (G-18) was obtained as a black powder in the same manner (amount 7.5 g, yield 60%).

[0300] 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)

[0301] [Synthesis Example 19] Synthesis of Pigment (A-1)

[0302] Sodium picramate (28.2 g) was placed in a reaction vessel, dispersed in water (242 mL), and 35% hydrochloric acid (6.9 g, manufactured by Kanto Chemical Co., Ltd.) was added. After stirring at a temperature below 5°C in an ice bath, a 40% aqueous sodium nitrite solution (6.4 g, manufactured by Kanto Chemical Co., Ltd.) was added dropwise. After stirring for 3 hours, aminosulfonic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added to remove excess sodium nitrite to obtain a diazotized solution. H acid hydrate (38.0 g, manufactured by Tokyo Chemical Industry Co., Ltd.) was placed in a reaction vessel, dispersed in water (250 mL), and a 24% aqueous sodium hydroxide solution (6.8 g) and sodium carbonate (9.0 g, manufactured by Kanto Chemical Co., Ltd.) were added to dissolve. The solution was stirred at a temperature below 5°C in an ice bath, and the above-mentioned diazotized solution synthesized previously was added to adjust the pH to 9.0 to 9.5. After stirring overnight (2 hours or more), the resorcinol test confirmed that no diazo compound remained. The temperature was raised to 40°C, and the pH was adjusted to 6.0 to 6.5 using 95% sulfuric acid (manufactured by 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%).

[0303] 1 H-NMR (400MHz, D2O): δ (ppm) = 7.12 (1H), 7.21 (1H), 7.57 (1H), 8.45 (1H), 8.73 (1H)

[0304] [Chemistry 70]

[0305]

[0306] The above compound (2-A-1) (10.9 g) was placed in a reaction vessel, 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, a 40% sodium nitrite aqueous solution (3.4 g, manufactured by Kanto Chemical Co., Ltd.) was added dropwise. After stirring for 3 hours, aminosulfonic 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, dispersed in water (150 mL), and then a 24% sodium hydroxide aqueous solution (3.8 g) and sodium carbonate (1.9 g) were added to dissolve. The solution was stirred at 5°C or less in an ice bath, and the previously synthesized diazotization solution was added to adjust the pH to 9.0 to 9.5. After stirring overnight (2 hours or more), the resorcinol test confirmed that no diazotide remained. The temperature was raised to 40°C, and the pH was adjusted to 6.0 to 6.5 using 95% sulfuric acid (manufactured by Kanto Chemical Co., Ltd.), followed by filtration. The obtained solid was dried to obtain a pigment (A-1) as a black powder (yield: 11.7 g, yield: 86%).

[0307] 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)

[0308] [Synthesis Example 20] Synthesis of Pigment (A-2)

[0309] Pigment (A-2) was obtained as a black powder in the same manner as in Synthesis Example 19 except that sodium 2-thiobarbiturate was used instead of barbituric acid (amount: 10.0 g, yield: 70%).

[0310] 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)

[0311] [Synthesis Example 21] Synthesis of Pigment (A-3)

[0312] A pigment (A-3) was obtained as a black powder in the same manner as in Synthesis Example 19 except that 2-amino-4-nitrophenol was used instead of sodium picramate (amount: 16.1 g, yield: 91%).

[0313] 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)

[0314] [Synthesis Example 22] Synthesis of Pigment (A-4)

[0315] A pigment (A-4) was obtained as a black powder in the same manner as in Synthesis Example 19 except that 2-amino-5-nitrophenol was used instead of sodium picramate (amount: 9.84 g, yield: 78%).

[0316] 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)

[0317] [Synthesis Example 23] Synthesis of Pigment (A-5)

[0318] A pigment (A-6) was obtained as a black powder in the same manner as in Synthesis Example 19 except that 2-aminophenol-4-sulfonic acid was used instead of sodium picramate (amount: 6.1 g, yield: 45%).

[0319] 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)

[0320] [Synthesis Example 24] Synthesis of Pigment (A-6)

[0321] A pigment (A-6) was obtained as a black powder in the same manner as in Synthesis Example 19 except that nitramine was used instead of sodium picramate (amount: 13.5 g, yield: 92%).

[0322] 1 H-NMR (400MHz, D2O): δ (ppm) = 4.75 (1H), 7.75 (1H), 8.01 (1H), 8.51-8.52 (2H), 8.64 (1H)

[0323] [Example 1]

[0324] <Production of Colored Aluminum>

[0325] Colored aluminum was produced by anodizing an aluminum substrate according to the following procedure. In the anodizing and dyeing steps, the treatment time and the dye compound concentration were set.

[0326] (Degreasing) In a degreasing container, prepare a degreasing liquid by mixing 150 mL of a degreasing agent (manufactured by Okuno Pharmaceutical Co., Ltd., product name: Top ADD-100), 70 mL of 98% sulfuric acid, and 1000 mL of water. Immerse a dyeing aluminum substrate cut to an appropriate size in the mixture, and perform a degreasing treatment at 60°C for 3 minutes, followed by washing with water.

[0327] (Anodization) In a container for electrolyte, use 98% sulfuric acid to prepare 180g / L electrolyte, connect the aluminum substrate to the electrode of the electrolysis device, immerse it in the electrolyte tank, and heat it at a temperature of 20±1℃ (19~21℃) and a current density of 1.0A / dm 2 Anodization was performed under the following conditions of the power supply time to obtain an anodic oxide film with the following thickness. After oxidation, the film was washed with water.

[0328] Anodizing conditions: Power on for 15 minutes Anodizing film thickness: 5 μm

[0329] (Surface Conditioning) A surface conditioning agent (TAC Somar 121 manufactured by OKUNO Pharmaceutical Industries, Ltd.) and water were used to prepare a surface conditioning solution having a concentration of 50 mL / L. The aluminum substrate was immersed in the solution at 45° C. for 1 minute and then washed with water.

[0330] (Dyeing) Using the pigment (G-1) obtained in Synthesis Example 1 as the dye composition of the present invention, aqueous dyeing solutions containing the pigments at the following concentrations were prepared, and dyeing was performed at a temperature (bath temperature) of 55° C. while immersing for the following dyeing time. After dyeing, the aluminum substrate was washed with water.

[0331] Dyeing conditions: Pigment concentration 2.0 mass% Dyeing time: 30 seconds

[0332] (Sealing) A sealing agent (manufactured by OKUNO CHEMICAL CO., LTD., product name: Topsil H-298) and water were used to prepare a 40 mL / L sealing solution, and the sealing treatment was performed at about 90° C. for 15 minutes. After the sealing treatment, the film was dried with warm air.

[0333] <Evaluation of hue>

[0334] The hue of the colored aluminum plate colored with the pigment (G-1) was measured visually and with a colorimeter (device name: Konica Minolta spectrocolorimeter model: CM-3700A) using the CIE L ＊ a ＊ b ＊ The results of the hue evaluation are shown in Table 1.

[0335] <Evaluation of light resistance>

[0336] The colored aluminum plate colored with the pigment (G-1) was subjected to a light resistance test by the following method. A Xenon Fade Meter / ATLAS Ci3000+Xenon Weather Ometer (manufactured by ATLAS) was used at an irradiance of 300 to 400 nm and 60 W / m 2 , the temperature in the test tank: 38°C, humidity: 50%, blackboard (BP) temperature: 63°C, the product of the colored aluminum plate irradiated for 50 hours was measured by a colorimeter and the color difference ΔE before and after light irradiation ＊ In addition, light fastness is determined by visually judging the color fastness using gray scale (JIS L 0804 "Gray scale for discoloration and fading"). The highest level is 5 and the lowest is 1. The higher the level, the darker the color (color difference ΔE ＊ In the evaluation method of the present invention, the results of the grade determination are divided into three levels, and the evaluation is performed using the following determination criteria. The results are shown in Table 1.

[0337] Grayscale judgment criteria: Correspondence between levels and evaluation in the present invention

[0338] Level 5 to Level 4: A (particularly good light resistance)

[0339] Grade 3: B (normal level of light resistance)

[0340] Below level 2: C (low light resistance)

[0341] [Example 2 to Example 10]

[0342] A colored aluminum plate was prepared in the same manner as in Example 1 except that the coloring matter (G-2) to (G-7) or (A-1) to (A-3) was used instead of the coloring matter (G-1). The hue and color difference ΔE ＊ The evaluation results of light resistance by visual observation are summarized in Table 1.

[0343] [Comparative Example 1]

[0344] Instead of the pigment (G-1), the following pigment represented by the following formula which does not belong to the present invention was used: (D-1). Colored aluminum was prepared under the same production conditions as in Example 1, and the hue and color difference ΔE ＊ The evaluation results of light resistance by visual observation are summarized in Table 1.

[0345] [Chemistry 71]

[0346]

[0347] [Table 1]

[0348] pigment Hue Lightfastness Example 1 G-1 Tea B Example 2 G-2 black B Example 3 G-3 Tea B Example 4 G-4 black A Example 5 G-5 black A Example 6 G-6 Tea B Example 7 G-7 Tea B Example 8 A-1 black A Example 9 A-2 black B Example 10 A-3 black B Comparative Example 1 D-1 black C

[0349] The results in Table 1 show that the use of an anodic aluminum oxide colorant composed of the dye composition containing the azo dye of the present invention can form a black or brown film on aluminum having superior light resistance than a colorant using a conventional dye.

[0350] Industrial Applicability

[0351] By using the dye composition containing the azo pigment of the present invention, a colorant for anodized aluminum having excellent light resistance, being free of heavy metals such as chromium and halogen, and forming a colored film of black or brown with a single color (single pigment) can be obtained. In addition, by using the colorant, an anodized aluminum film having excellent light resistance and being colored black or brown with a single color can be obtained.

Claims

1. An azo dye represented by the following general formula (1), (2) or (3), 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 acylamino group having 7 to 12 carbon atoms which may have a substituent, R 18 ~R 20 Each independently represents -H, an alkyl group having 1 to 3 carbon atoms, -NO2, -SO2CH3, -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, X each independently represents a non-color-developing cation, Z each independently represents an oxygen atom or a sulfur atom.

2. The azo dye according to claim 1, which is represented by the general formula (1) or (2), R 1 ~R 3 One or two of them are -NO2.

3. The azo dye according to claim 1, which is represented by the general formula (1) or (2), R 3 It is -CH3 or -SO2CH3.

4. The azo dye according to claim 1, which is represented by the general formula (1): R 4 ~R 10 Either one or both of them are -OH, or R 4 ~R 10 Either one or both of them are -SO3Na.

5. The azo dye according to claim 1, which is represented by the general formula (2): R 11 ~R 17 Either one or both of them are -OH, or R 11 ~R 17 Either one or both of them are -SO3Na.

6. The azo dye according to claim 1, which is represented by the general formula (3): R 18 ~R 20 Each is independently -H, -CH3, -NO2, -SO2CH3, -SO3H, -SO3Na, -COOH or -COONa.

7. The azo dye according to claim 1, wherein X is each independently H + 、Na + or NH4 + .

8. The azo dye according to claim 1, which is represented by the following general formula (1A): In the formula (1A), X has the same meaning as defined in the general formula (1).

9. The azo dye according to claim 1, which is represented by the following general formula (2A): In the formula (2A), X has the same meaning as defined in the general formula (2).

10. The azo dye according to claim 1, which is represented by the following general formula (3A): In the formula (3A), X has the same meaning as defined in the general formula (3). 11 . A dye composition comprising the azo dye according to claim 1 . 12 . A colorant for anodized aluminum, comprising the dye composition according to claim 11 .

13. A method for coloring anodized aluminum or anodized aluminum alloy, characterized in that: A dye composition containing 0.02 to 10% by mass of the azo dye according to claim 1 is used.

14. A production method, which is the production method of the azo dye according to claim 1, wherein The azo dye represented by the general formula (1) or (2) is obtained by diazo coupling reaction of a diazo compound obtained by diazotizing a compound represented by the following general formula (4) with a compound represented by the following general formula (5) or (6) and / or a salt thereof. In formulas (4) to (6), R 1 ~R 17 and X have the same meanings as defined in the above-mentioned general formulae (1) and (2).

15. A production method, which is the production method of the azo dye according to claim 1, wherein: The azo dye represented by the general formula (3) is obtained by diazo coupling reaction of a diazo compound obtained by diazotizing a compound represented by the following general formula (7) with a compound represented by the following general formula (8) and / or a salt thereof. In formula (7) and formula (8), R 18 ~R 21 , X and Z have the same meanings as defined in the above general formula (3).

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