TWI741166B - Dye fixing treatment agent for anodic oxide film of aluminum alloy and sealing treatment method - Google Patents

Abstract

The present invention provides a dyeing fixation method and a sealing treatment method. Even if the anodic oxide film of aluminum alloy is dyed and then sealed, the discoloration can be suppressed and the dye fixation can be improved. The present invention provides a dye fixing treatment agent for anodic oxide film of aluminum alloy, which is characterized in that it contains manganese salt and has a pH value of 5.0 or less.

Description

Dye fixing treatment agent for anodic oxide film of aluminum alloy and sealing treatment method

The present invention relates to a dye fixing treatment agent for anodic oxide film of aluminum alloy and a sealing treatment method.

Background Art In order to prevent fouling, improve corrosion resistance, etc., generally, the anodic oxide film of aluminum alloy is sealed. As the sealing treatment method, boiling water sealing, steam sealing, normal temperature sealing, and nickel acetate sealing using a nickel acetate aqueous solution for sealing treatment are known.

Among them, the nickel acetate sealing is easier to obtain the corrosion resistance of the film than the boiling water sealing, the work efficiency is better than the steam sealing, and the liquid management is easier than the normal temperature sealing, so nickel acetate sealing is particularly used.

However, in recent years, nickel allergy and the toxicity of finely powdered nickel salts have become problems. Therefore, it is expected that the anodic oxide film can be produced by a sealing treatment method that does not use nickel salt, and the anodic oxide film has the same degree of sealing as nickel acetate. Corrosion resistance, sealing performance and other sealing properties.

Regarding the above-mentioned sealing treatment method, someone has proposed a sealing treatment method using a sealing treatment solution for anodized film of aluminum alloy. An aqueous solution of at least one anionic surfactant from the group consisting of a sulfonate type anionic surfactant and a sulfate ester salt type anionic surfactant (see Patent Document 1).

Although the above-mentioned sealing treatment method using the sealing treatment liquid is also an excellent sealing treatment method, no research has been conducted on the fixation of the dyeing of the aluminum alloy anodic oxide film. For the purpose of design and other purposes, the anodic oxide film will be dyed through a dyeing step. The dyeing step is performed before the sealing treatment, and the anodic oxide film is dyed, and then the sealing treatment is performed. However, there is the problem of discoloration and decreased fixability of dyeing due to the sealing treatment.

Therefore, it is pursued to develop a dyeing fixation method and a sealing treatment method, which can suppress discoloration and improve dye fixation even if the anodic oxide film of aluminum alloy is dyed and then sealed.

Prior Art Document [Patent Document] [Patent Document 1] JP 2015-4083 A

SUMMARY OF THE INVENTION Problems to be Solved by the Invention The present invention was made in view of the above-mentioned problems of the prior art, and its purpose is to provide a dyeing fixing method and a sealing treatment method, which are equivalent to dyeing an anodic oxide film of aluminum alloy. Sealing treatment can also suppress discoloration and improve dye fixability.

Means to Solve the Problem The inventors have repeatedly researched in order to achieve the above-mentioned object. As a result, it was found that the above-mentioned object can be achieved by using a dye fixing treatment agent for an anodic oxide film containing manganese salt and a pH value of 5.0 or less after the dyeing treatment and before the sealing treatment.

That is, the present invention relates to the following dye fixing treatment agent and sealing treatment method. 1. A dye fixing treatment agent for anodic oxide film of aluminum alloy, characterized in that it contains manganese salt and has a pH value of 5.0 or less. 2. The dye fixing treatment agent as described in Item 1, which further contains an anionic surfactant. 3. The dye fixing treatment agent as described in item 1 or 2, which further contains a pH buffer. 4. A sealing treatment method, characterized in that: it is a sealing treatment method for the anodic oxide film of aluminum alloy, and has the following steps: (1) Step 1 of dyeing the anodic oxide film of aluminum alloy; (2) Dyeing The anodic oxide film is immersed in the dye fixing treatment agent for dye fixing treatment step 2; and (3) the dye fixing treatment anodic oxide film is subjected to sealing treatment step 3; and the dye fixing treatment agent contains manganese Salt and pH value below 5.0. 5. The sealing treatment method described in item 4, wherein the temperature of the dye fixing treatment agent is 55~95℃. 6. The sealing treatment method described in item 4 or 5, wherein the immersion time for the dye fixing treatment agent is 1 to 30 minutes. 7. The sealing treatment method described in any one of items 4 to 6, wherein step 3 is a step of immersing the anodic oxide film that has been dyed and fixed in a sealing treatment solution. 8. The sealing treatment method described in any one of items 4 to 7, wherein the pH of the sealing treatment liquid is 5.1 to 8.0. 9. The sealing treatment method described in item 7 or 8, wherein the sealing treatment liquid does not contain nickel-based metal salts. 10. An article having an anodic oxide film of aluminum alloy, and the anodic oxide film of the aluminum alloy is sealed by the method described in item 4.

Effects of the Invention According to the dye fixing treatment agent for the anodic oxide film of aluminum alloy of the present invention, by using the dye fixing treatment agent for dye fixing treatment after dyeing treatment, excellent dye fixing can be given to the anodic oxide film of aluminum alloy It can prevent the discoloration of the anodic oxide film during the sealing treatment in the subsequent steps.

Furthermore, according to the sealing treatment method of the anodic oxide film of the aluminum alloy of the present invention, the anodic oxide film of the aluminum alloy is dyed, a specific dye fixing treatment agent is used for the dye fixing treatment, and then the sealing treatment is performed. The anodic oxide film of aluminum alloy imparts excellent dye fixability and can inhibit the discoloration of the sealing process.

Modes for Carrying Out the Invention Hereinafter, the present invention will be described in detail.

1. Dye fixing treatment agent for anodic oxide film of aluminum alloy The dye fixing treatment agent for anodic oxide film of aluminum alloy of the present invention (hereinafter also referred to as "dye fixing treatment agent") contains manganese salt and has a pH value of Below 5.0.

The manganese salt is not particularly limited, and manganese acetate, manganese nitrate, manganese sulfate, manganese chloride, manganese borate, manganese carbonate, etc. can be used. Among them, from the viewpoint of superior dye fixability, manganese acetate and manganese nitrate are preferred, and manganese acetate is more preferred. The above-mentioned manganese salt can be used singly or in combination of two or more kinds.

The content of the manganese salt in the dye fixing treatment agent is not particularly limited, and is preferably 0.1 to 10.0 g/L, preferably 0.2 to 2.0 g/L. By limiting the lower limit of the manganese salt content to the above range, the dye fixability is further improved. By limiting the upper limit of the manganese salt content to the above-mentioned range, it is excellent from the viewpoint of suppressing discoloration during the dye-fixing treatment.

The pH of the dye fixing treatment agent of the present invention is 5.0 or less. If the pH value of the dye fixing treatment agent exceeds 5.0, sufficient dye fixing property cannot be obtained. The pH value is preferably 4.5 or less, preferably 4.0 or less. Furthermore, the pH value is preferably 2.0 or higher, preferably 3.0 or higher, more preferably 3.5 or higher. When the lower limit of the pH is limited to the above range, the dye fixability is further improved.

(Anionic surfactant) The dye fixing treatment agent of the present invention further contains an anionic surfactant. By containing an anionic surfactant, the dye fixability is further improved and the anodic oxide film surface pulverization and foggy appearance can be suppressed.

The anionic surfactant is not particularly limited, and sulfate-based surfactants, sulfonate-based surfactants, phosphorus-based surfactants, and the like can be used.

Examples of sulfate-based surfactants include aromatic sulfate-based surfactants, aliphatic sulfate-based surfactants, and the like.

Regarding the above-mentioned aromatic sulfate-based surfactants, polyoxyethylene alkyl phenyl ether sulfates can be exemplified. Moreover, as for aliphatic sulfate-based surfactants, polyoxyethylene alkyl ether sulfates can be exemplified.

Regarding sulfonate-based surfactants, aromatic sulfonate-based surfactants and the like can be exemplified.

Regarding the above-mentioned aromatic sulfonate-based surfactants, examples include aromatic sulfonate compounds such as benzenesulfonate and naphthalenesulfonate, or aromatic sulfonate skeletons such as p-benzenesulfonate and naphthalenesulfonate. Alkylene, polyoxyethylene, polyoxyethylene alkyl ether group, carboxyl group, carbonyl group, hydroxyl group, alcohol group, vinyl group, allyl group and other alkylene groups or groups with multiple bonds, and then sulfonic acid group substitution Compounds, etc., as well as formalin and other polycondensates and copolymers of these compounds. Examples of the aromatic sulfonate-based surfactant include: alkylbenzene sulfonate, alkylnaphthalene sulfonate, and polycondensation products such as formalin and the like, and polycondensation products such as formalin of naphthalenesulfonate. And copolymers derived from alkylene benzene sulfonate or alkylene naphthalene sulfonate.

The above-mentioned aromatic sulfonate-based surfactants can also be exemplified: compounds in which a plurality of benzene sulfonates are bonded to ethers such as diphenyl ether disulfonates, and the compounds are subjected to alkyl or polyoxyethylene , Polyoxyethylene alkyl ether group and other substituted compounds. Examples of the aromatic sulfonate-based surfactant include alkyl diphenyl ether disulfonate, alkyl diphenyl ether disulfonyl succinate, and the like.

Regarding the phosphorus-based surfactants, phosphate ester-based surfactants and phosphate ester salt-based surfactants can be used. Specific examples include polyoxyethylene alkyl ether phosphates, polyoxyethylene alkylated phenyl ether phosphates, alkyl phosphates, and salts thereof.

The anionic surfactant is preferably a sulfonate surfactant.

The said anionic surfactant can be used individually by 1 type or in mixture of 2 or more types.

The concentration of the anionic surfactant in the dye fixing treatment agent is not particularly limited, but is preferably 10 mg/L to 10 g/L, and more preferably 20 mg/L to 5 g/L. With the surfactant concentration in the above range, the dye fixability is further improved.

(pH buffer) The dye fixing treatment agent of the present invention preferably further contains a pH buffer. By containing a pH buffer, the dye fixability is further improved and the anodic oxide film surface can be prevented from powdering and foggy appearance.

The pH buffering agent is not particularly limited, and a previously known pH buffering agent can be used. Examples of the aforementioned pH buffering agent include amino acids, organic acid salts, ammonium salts, borate salts, amine compounds, and nitrogen-containing heterocyclic compounds. Among them, from the viewpoint that the dye fixability is further improved and the pulverization of the anodic oxide film surface and the appearance of foggy bad appearance can be suppressed, amino acids are preferred.

Regarding amino acids, examples include glutamine, glycine, alanine, arginine, cysteine, histidine, isoleucine, leucine, lysine, methionine, and amphetamine Acid, proline, serine, threonine, tryptophan, tyrosine, valine, aspartic acid, etc. or their salts. Among them, from the viewpoint of pH buffering effect, glutamic acid and its salts, histidine and its salts, aspartic acid and its salts are preferred, and glutamine, aspartic acid and its salts are preferred. Wait for salt.

Regarding the organic acid salt, for example, a carboxylic acid or a salt of a hydroxycarboxylic acid can be exemplified. The carbon number of the above-mentioned carboxylic acid and hydroxycarboxylic acid is preferably 4 or less. In addition, examples of the above-mentioned salt include sodium salt and potassium salt.

Regarding ammonium salts, for example: ammonium salts of organic acids and ammonium salts of inorganic acids. Examples of ammonium salts of organic acids include carboxylic acids or ammonium salts of hydroxycarboxylic acids. The carbon number of the above-mentioned carboxylic acid and hydroxycarboxylic acid is preferably 4 or less. In addition, examples of ammonium salts of inorganic acids include ammonium sulfate, ammonium nitrate, ammonium sulfamate, and the like.

Regarding borate, sodium borate, potassium borate, ammonium borate, etc. can be exemplified.

Examples of amine compounds include ethanolamines such as monoethanolamine, diethanolamine, and triethanolamine, and water-soluble carbonyl amines such as alkylamines, aromatic amines, and urea.

Regarding the nitrogen-containing heterocyclic compound, a heterocyclic compound containing at least one nitrogen atom as a heteroatom, and a heterocyclic compound containing at least one nitrogen atom and at least one oxygen atom as a heteroatom can be exemplified.

唑環、咪唑啉環、吡

環、嗎啉環、蝶啶環、嘌呤環等的含氮雜環化合物。其等之中，以包含吡咯啶環、吡咯環、哌啶環、吡啶環、六亞甲基亞胺環、氮呯環、咪唑環、吡唑環、

唑環、咪唑啉環、吡

環、嗎啉環、蝶啶環、嘌呤環等的含氮雜環化合物為佳。Examples of the nitrogen-containing heterocyclic compound include ethyleneimine ring, acridine ring, tetrahydro acridine ring, acridine ring, pyrrolidine ring, pyrrole ring, piperidine ring, pyridine ring, and hexamethylene group. Imine ring, nitrogen ring, imidazole ring, pyrazole ring,

Azole ring, imidazoline ring, pyridine

Nitrogen-containing heterocyclic compounds such as ring, morpholine ring, pteridine ring, purine ring, etc. Among them, pyrrolidine ring, pyrrole ring, piperidine ring, pyridine ring, hexamethyleneimine ring, aza ring, imidazole ring, pyrazole ring,

Azole ring, imidazoline ring, pyridine

Nitrogen-containing heterocyclic compounds such as a ring, a morpholine ring, a pteridine ring, and a purine ring are preferred.

唑、咪唑啉、吡

、嗎啉、蝶啶、嘌呤等；且可使用於其等骨架加成有胺基或甲基的化合物。其等之中，較佳為於環狀結構原子中具有一個或二個氮原子作為雜原子，且由碳或一個氧雜原子與碳構成的環狀五員~七員環雜環化合物，具體可列舉：以吡咯啶、吡咯、哌啶、吡啶、六亞甲基亞胺、氮呯、咪唑、吡唑、

唑、咪唑啉、吡

、嗎啉等化合物及其等環狀骨架作為基本結構的化合物群。且亦宜為具有多環結構且具有四個以上氮雜原子者，例如以嘌呤、蝶啶等化合物及其等多環狀骨架作為基本結構的化合物群。其中更佳為五~六員環者，可列舉：以吡咯啶、吡咯、哌啶、吡啶、咪唑、吡唑、

唑、咪唑啉、吡

、嗎啉等化合物及其等環狀骨架作為基本結構的化合物群。其中最佳為以於環內具有雙鍵的吡咯、吡啶、咪唑、吡唑、

唑、咪唑啉、吡

等化合物及其等環狀骨架作為基本結構的化合物群。作為構成此等化合物群的取代基可舉例胺基或甲基等，亦可使用加成有該等取代基的化合物群。例如尤佳可列舉：2-胺基吡啶、4-胺基吡啶等胺基吡啶等、或2-甲基咪唑等甲基咪唑等。其中，最佳為吡啶、咪唑、胺基吡啶、甲基咪唑等。Examples of the nitrogen-containing heterocyclic compound include: ethyleneimine, acridine, tetrahydro acridine, acridine, pyrrolidine, pyrrole, piperidine, pyridine, hexamethyleneimine, azamethine, imidazole, Pyrazole,

Azole, imidazoline, pyridine

, Morpholine, pteridine, purine, etc.; and can be used in compounds with amine groups or methyl groups added to their skeletons. Among them, a cyclic five- to seven-membered ring heterocyclic compound having one or two nitrogen atoms as heteroatoms in the ring structure atom and consisting of carbon or one oxygen heteroatom and carbon is preferred, specifically Examples include: pyrrolidine, pyrrole, piperidine, pyridine, hexamethyleneimine, azapyridine, imidazole, pyrazole,

Azole, imidazoline, pyridine

, Morpholine and other compounds and their cyclic skeleton as the basic structure of the group of compounds. It is also preferable to have a polycyclic structure and four or more nitrogen heteroatoms, for example, compounds such as purines, pteridines, and other polycyclic skeletons as the basic structure. Among them, those with five to six membered rings are more preferred, and examples include: pyrrolidine, pyrrole, piperidine, pyridine, imidazole, pyrazole,

Azole, imidazoline, pyridine

, Morpholine and other compounds and their cyclic skeleton as the basic structure of the group of compounds. Among them, pyrrole, pyridine, imidazole, pyrazole,

Azole, imidazoline, pyridine

Such compounds and their cyclic skeletons as the basic structure of the group of compounds. Examples of substituents constituting these compound groups include amino groups, methyl groups, and the like, and compound groups to which these substituents are added may also be used. For example, particularly preferable examples include aminopyridines such as 2-aminopyridine and 4-aminopyridine, and methylimidazoles such as 2-methylimidazole. Among them, pyridine, imidazole, aminopyridine, methylimidazole and the like are most preferred.

The aforementioned pH buffers can be used alone or in combination of two or more.

The concentration of the pH buffer in the dye fixing treatment agent is not particularly limited, and is preferably 0.1-20 g/L, preferably 0.2-5 g/L. With the pH buffer concentration in the above range, the dye fixation treatment agent can show excellent pH buffering properties, and can inhibit the appearance of the processed product surface defects (dry stains) or dyeing caused by the excessive pH buffer concentration. Pint color.

(pH adjuster) The dye fixing treatment agent of the present invention may further contain a pH adjuster. The pH adjuster is not particularly limited, and a previously known pH adjuster can be used.

Regarding the pH adjuster for adjusting the dye fixing treatment agent to the acidic side, for example, dilute aqueous solutions such as acetic acid, aminosulfonic acid, sulfuric acid, nitric acid, and organic sulfonic acid can be cited. Among them, nitric acid is preferred from the viewpoint of further improvement in dye fixability.

Regarding the pH adjusting agent for adjusting the dye fixing treatment agent to the alkaline side, for example, ammonia water, an aqueous sodium hydroxide solution, and an aqueous potassium hydroxide solution can be cited. Among them, the sodium hydroxide aqueous solution is preferred from the viewpoint of further improvement in dye fixability.

The above-mentioned pH adjusters can be used alone or in combination of two or more.

The concentration of the pH adjusting agent in the dye fixing treatment agent is not particularly limited, and is preferably 0-20 g/L, preferably 0-10 g/L, and more preferably 0-5 g/L. With the concentration of the pH adjusting agent in the above range, the dye fixability is further improved.

(Other components) In order to further improve the dye fixability and improve the practicality of the dye fixation treatment agent, the dye fixation treatment agent of the present invention may contain an antifungal agent, a complexing agent and other additive components as necessary. Examples of additives include antifungal agents such as benzoic acid and benzoate; complexing agents such as citric acid and citrate. In addition, a commercially available antifungal agent, for example, "TAC Kabikoron" (manufactured by Okuno Pharmaceutical Co., Ltd.) can be added as an antifungal agent.

The dye fixing treatment agent of the present invention only needs to contain a manganese salt, and other components are not particularly limited, but are preferably an aqueous solution containing the above-mentioned components.

The dye fixing treatment agent of the present invention preferably does not contain metal salts other than manganese salt. As for the metal salt other than the manganese salt, metal salts such as Ni, Co, Fe, Cr, etc. can be exemplified, and among them, it is more preferable that the nickel-based metal salt is not contained.

2. Sealing treatment method The sealing treatment method of the present invention is a sealing treatment method for the anodic oxide film of aluminum alloy. It has the following steps: (1) Step 1 of dyeing the anodic oxide film of aluminum alloy; (2) Dyeing The anodic oxide film is immersed in the dye fixing treatment agent for dye fixing treatment step 2; and (3) the dye fixing treatment anodic oxide film is sealed in step 3; and the dye fixing treatment agent contains manganese Salt and pH value below 5.0.

(Step 1) Step 1 is a step of dyeing the anodic oxide film of aluminum alloy. The dyeing treatment is not particularly limited, and dyes can be used for coloring, for example.

Regarding coloring with dyes, the following method can be exemplified: the anodic oxide film is immersed in a previously known dye aqueous solution. As the dye, commercially available dyes for aluminum alloy anodic oxide films can be used, and anionic dyes and the like can be exemplified. The temperature of the dye aqueous solution is preferably 10 to 70°C, preferably 20 to 60°C. In addition, the dye concentration and immersion time in the above-mentioned dye aqueous solution can be appropriately set according to the desired dyeing hue and color density.

Through the step 1 described above, the anodic oxide film of the aluminum alloy is dyed.

(Step 2) Step 2 is a step of immersing the dyed anodic oxide film in a dye fixing treatment agent for dye fixing treatment. Regarding the dye fixing treatment agent, the dye fixing treatment agent described above can be used.

When the dyed anodic oxide film is immersed in the dye fixing treatment agent, it is only necessary to immerse the aluminum alloy on which the anodic oxide film is partially formed in the dye fixing treatment agent. In addition, when the aluminum alloy is joined to another member to form an article, it is only necessary to immerse each of the articles in the dye fixing agent.

The temperature of the dye fixing treatment agent when the anodic oxide film is immersed in the dye fixing treatment agent is preferably 55 to 95°C, preferably 60 to 90°C, more preferably 70 to 80°C. When the dye fixing treatment agent temperature is in the above range, the dye fixing property of the anodic oxide film is further improved.

The immersion time when the anodic oxide film is immersed in the dye fixing treatment agent is preferably 1 to 30 minutes, preferably 2 to 10 minutes. By limiting the immersion time to the above range, the dye fixability of the anodic oxide film is further improved. In addition, by limiting the immersion time to the above range, the production efficiency is excellent.

In step 2, after the dyeing treatment in step 1, the anodic oxide film of the aluminum alloy is sufficiently washed with water and dried, and then immersed in the dye fixing treatment agent. As a result, the dye fixability of the anodic oxide film is further improved.

Through step 2 described above, the anodic oxide film is dyed and fixed.

(Step 3) Step 3 is a step of sealing the anodic oxide film that has been dyed and fixed.

The sealing treatment is not particularly limited, and a previously known sealing treatment method can be used. As the above-mentioned sealing treatment method, a method of immersing the anodic oxide film that has been dyed and fixed in a sealing treatment liquid is suitable.

The above-mentioned sealing treatment liquid is preferably a sealing treatment liquid for an anodic oxide film of an aluminum alloy containing a metal salt, a pH buffer and a surfactant. Hereinafter, the sealing treatment liquid will be described.

(Metal salt) The sealing treatment liquid should contain metal salt. The above-mentioned metal salt is preferably at least one selected from the group consisting of alkali metal salts, alkaline earth metal salts and transition metal salts. The above-mentioned alkali metal salt, alkaline earth metal salt, and transition metal salt are not particularly limited, and are preferably water-soluble. Examples thereof include carboxylate, sulfamate, sulfate, nitrate, and organic sulfonate. Among these, from the viewpoint that the anodic oxide film of the sealed aluminum alloy has excellent pollution resistance, carboxylate, sulfamate, sulfate, nitrate are preferred, and acetate and sulfonate are preferred. Acid salt, sulfate, nitrate, more preferably acetate, nitrate, most preferably nitrate. The above-mentioned metal salt can be used singly or in combination of two or more kinds.

The metal contained in the above metal salt is preferably alkali metal, alkaline earth metal, and transition metal. Specific examples include: Li, Be, Na, Mg, K, Ca, Rb, Sr, Cs, Ba, Fr, Ra, Zr, Mn, Fe. Among these, from the viewpoint that the anodic oxide film of the sealed aluminum alloy has excellent contamination resistance, metal salts of Na, Mg, K, Ca, Ba, and Mn are preferred, and metal salts of Mg, Ca, and Mn are more preferred. Metal salt. The metal contained in the said metal salt can be used individually by 1 type or in mixture of 2 or more types.

The concentration of the metal salt in the sealing treatment liquid is not particularly limited, and is preferably 0.001 to 1 mol/L, preferably 0.003 to 0.3 mol/L. With the metal salt concentration in the above range, the sealing treatment solution can exhibit sufficient sealing performance, and the anodic oxide film of the aluminum alloy that has been sealed with the sealing treatment solution can fully exhibit contamination resistance.

(pH buffer) The pH buffer is not particularly limited, and a previously known pH buffer can be used. Regarding the aforementioned pH buffering agent, for example, organic acid salts, ammonium salts, amino acids, borates, amine compounds, and nitrogen-containing heterocyclic compounds can be cited. Among these, from the viewpoint that the dye fixability of the anodic oxide film is further improved and the anodic oxide film of the aluminum alloy that has been sealed by the sealing treatment liquid can be imparted with excellent pollution resistance, it is preferable to use nitrogen-containing impurities. Cyclic compound.

Regarding the organic acid salt, for example, a carboxylic acid or a salt of a hydroxycarboxylic acid can be exemplified. The carbon number of the above-mentioned carboxylic acid and hydroxycarboxylic acid is preferably 4 or less. In addition, examples of the above-mentioned salt include sodium salt and potassium salt.

Regarding ammonium salts, for example: ammonium salts of organic acids and ammonium salts of inorganic acids. Examples of ammonium salts of organic acids include carboxylic acids or ammonium salts of hydroxycarboxylic acids. The carbon number of the above-mentioned carboxylic acid and hydroxycarboxylic acid is preferably 4 or less. In addition, examples of ammonium salts of inorganic acids include ammonium sulfate, ammonium nitrate, ammonium sulfamate, and the like.

Regarding amino acids, glycine, alanine, asparagine, etc. or their salts can be exemplified. Regarding borate, sodium borate, potassium borate, ammonium borate, etc. can be exemplified. Examples of amine compounds include ethanolamines such as monoethanolamine, diethanolamine, and triethanolamine, and water-soluble carbonyl amines such as alkylamines, aromatic amines, and urea.

Regarding the nitrogen-containing heterocyclic compound, a heterocyclic compound containing at least one nitrogen atom as a heteroatom, and a heterocyclic compound containing at least one nitrogen atom and at least one oxygen atom as a heteroatom can be exemplified.

唑環、咪唑啉環、吡

環、嗎啉環、蝶啶環、嘌呤環等的含氮雜環化合物。其等之中，以包含吡咯啶環、吡咯環、哌啶環、吡啶環、六亞甲基亞胺環、氮呯環、咪唑環、吡唑環、

唑環、咪唑啉環、吡

環、嗎啉環、蝶啶環、嘌呤環等的含氮雜環化合物為佳。Examples of the nitrogen-containing heterocyclic compound include ethyleneimine ring, acridine ring, tetrahydro acridine ring, acridine ring, pyrrolidine ring, pyrrole ring, piperidine ring, pyridine ring, and hexamethylene group. Imine ring, nitrogen ring, imidazole ring, pyrazole ring,

Azole ring, imidazoline ring, pyridine

Nitrogen-containing heterocyclic compounds such as ring, morpholine ring, pteridine ring, purine ring, etc. Among them, pyrrolidine ring, pyrrole ring, piperidine ring, pyridine ring, hexamethyleneimine ring, aza ring, imidazole ring, pyrazole ring,

Azole ring, imidazoline ring, pyridine

Nitrogen-containing heterocyclic compounds such as a ring, a morpholine ring, a pteridine ring, and a purine ring are preferred.

唑等。With regard to the aforementioned nitrogen-containing heterocyclic compound, pyridine; aminopyridines such as 2-aminopyridine and 4-aminopyridine; imidazole; methylimidazole such as 2-methylimidazole; pyrazole; pteridine;

Azole and so on.

The aforementioned pH buffers can be used alone or in combination of two or more.

The concentration of the pH buffer in the sealing treatment liquid is not particularly limited, and is preferably 0.1-100 g/L, preferably 0.2-20 g/L. With the pH buffer concentration in the above range, the sealing treatment solution can exhibit excellent pH buffering properties, and the dye fixability of the anodic oxide film is improved, and the surface of the treated product caused by the excessively high pH buffer concentration can be suppressed. Poor appearance (dry stains).

(Surfactant) The surfactant is not particularly limited, and conventionally known surfactants can be used. Examples of the aforementioned surfactant include anionic surfactants, nonionic surfactants, and amphoteric surfactants.

Regarding anionic surfactants, sulfate-based surfactants, sulfonate-based surfactants, phosphorus-based surfactants, and the like can be used.

Examples of sulfate-based surfactants include aromatic sulfate-based surfactants, aliphatic sulfate-based surfactants, and the like.

Regarding the above-mentioned aromatic sulfate-based surfactants, polyoxyethylene alkyl phenyl ether sulfates can be exemplified. Moreover, as for aliphatic sulfate-based surfactants, polyoxyethylene alkyl ether sulfates can be exemplified.

Regarding sulfonate-based surfactants, aromatic sulfonate-based surfactants and the like can be exemplified.

Regarding the above-mentioned aromatic sulfonate-based surfactants, examples include aromatic sulfonate compounds such as benzenesulfonate and naphthalenesulfonate, or aromatic sulfonate skeletons such as p-benzenesulfonate and naphthalenesulfonate. Alkylene, polyoxyethylene, polyoxyethylene alkyl ether group, carboxyl group, carbonyl group, hydroxyl group, alcohol group, vinyl group, allyl group and other alkylene groups or groups with multiple bonds, and then sulfonic acid group substitution Compounds, etc., as well as formalin and other polycondensates and copolymers of these compounds. Examples of the aromatic sulfonate-based surfactant include: alkylbenzene sulfonate, alkylnaphthalene sulfonate, and polycondensation products such as formalin and the like, and polycondensation products such as formalin of naphthalenesulfonate. And copolymers derived from alkylene benzene sulfonate or alkylene naphthalene sulfonate.

The above-mentioned aromatic sulfonate-based surfactants can also be exemplified: compounds in which a plurality of benzene sulfonates are bonded to ethers such as diphenyl ether disulfonates, and the compounds are subjected to alkyl or polyoxyethylene , Polyoxyethylene alkyl ether group and other substituted compounds. Examples of the aromatic sulfonate-based surfactant include alkyl diphenyl ether disulfonate, alkyl diphenyl ether disulfonyl succinate, and the like.

Regarding the phosphorus-based surfactants, phosphate ester-based surfactants and phosphate ester salt-based surfactants can be used. Specific examples include polyoxyethylene alkyl ether phosphates, polyoxyethylene alkylated phenyl ether phosphates, alkyl phosphates, and salts thereof.

Regarding the nonionic surfactant, it is preferable to use the following nonionic surfactant: by adjusting the concentration in the sealing treatment liquid or combining with other surfactants, the cloud point of the sealing treatment liquid can be made 85°C or higher. Examples of the nonionic surfactant include polyoxyethylene alkyl ether, glyceride polyoxyethylene ether, sorbitan ester, and fatty acid alkanolamide.

Regarding amphoteric surfactants, examples include alkyl betaines, fatty acid amide betaines, alkyl amine oxides, and the like.

It is suitable to use an anionic surfactant as the above-mentioned surfactant. Among them, sulfate-based surfactants, sulfonate-based surfactants, and phosphorus-based surfactants are preferred, and sulfonate-based surfactants are more preferred.

The above-mentioned surfactants can be used singly or in combination of two or more kinds. In addition, the above-mentioned nonionic surfactant may be selected as long as it does not lower the cloud point of the sealing treatment liquid. In addition, when a nonionic surfactant and an anionic surfactant are used in combination, the cloud point of the surfactant can be increased. When an anionic surfactant is used, it is only necessary to select one that does not produce turbidity after reacting with the contained metal or amphoteric surfactant.

The concentration of the surfactant in the sealing treatment liquid is not particularly limited, and is preferably 10 mg/L to 10 g/L, preferably 20 mg/L to 5 g/L. With the surfactant concentration in the above range, the dye fixability of the anodic oxide film is further improved, the sealing treatment solution can exhibit sufficient sealing performance, and the pulverization of the anodic oxide film surface after the sealing treatment and the poor appearance of fog can be suppressed.

(pH adjuster) The sealing treatment liquid of the present invention may further contain a pH adjuster. The pH adjuster is not particularly limited, and a previously known pH adjuster can be used.

Regarding the pH adjuster for adjusting the sealing treatment liquid to the acidic side, for example, dilute aqueous solutions such as acetic acid, aminosulfonic acid, sulfuric acid, nitric acid, and organic sulfonic acid can be cited. Among them, nitric acid is preferred from the viewpoint of excellent sealing performance.

Regarding the pH adjuster for adjusting the sealing treatment liquid to the alkaline side, for example, ammonia water, an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, and the like can be cited. Among them, from the viewpoint of excellent sealing performance, an aqueous sodium hydroxide solution is preferred.

The above-mentioned pH adjusters can be used alone or in combination of two or more.

The concentration of the pH adjuster in the sealing treatment liquid is not particularly limited, and is preferably 0-20 g/L, preferably 0-10 g/L, and more preferably 0-5 g/L. When the concentration of the pH adjuster is in the above range, the sealing treatment liquid can exhibit sufficient sealing performance, and it is possible to suppress the decrease in the sealing degree of the anodic oxide film that is sealed by the sealing treatment liquid.

(Other components) In order to improve the sealing performance and the practicability of the liquid, the sealing treatment liquid may contain anti-fungal agents, complexing agents and other additives as necessary. Examples of additives include antifungal agents such as benzoic acid and benzoate; complexing agents such as citric acid and citrate. In addition, a commercially available antifungal agent, for example, "TAC Kabikoron" (manufactured by Okuno Pharmaceutical Co., Ltd.) can be added as an antifungal agent.

The total content of the metal salt, pH buffer and surfactant in the sealing treatment liquid is preferably 0.2-100 g/L, preferably 0.3-50 g/L, more preferably 0.5-30 g/L. By adding the above content in the above range, the dye fixability of the anodic oxide film is further improved, the sealing treatment liquid can exhibit sufficient sealing performance, and the anodic oxide film of the aluminum alloy sealed by the sealing treatment liquid can fully express Contamination resistance, and can prevent the anodic oxide film surface pulverization and foggy appearance after sealing treatment.

The sealing treatment liquid only needs to contain a metal salt, a pH buffer, and a surfactant, and other components are not particularly limited, but are preferably an aqueous solution containing the above-mentioned components.

The sealing treatment fluid should preferably not contain metal salts such as nickel-based metal salts. Examples of the metal salt include metal salts such as Ni, Co, Fe, and Cr.

In step 3, the pH value of the sealing treatment liquid is preferably 5.1 to 8.0, preferably 5.3 to 7.0, and more preferably 5.5 to 6.0. With the pH value in the above range, the dye fixability is further improved, the sealing treatment liquid can exhibit sufficient sealing performance, the anodic oxide film of the aluminum alloy that has been sealed with the sealing treatment liquid can fully exhibit stain resistance, and It can suppress poor appearance (powdering, fogging) of powdery deposits adhering to the surface of the processed object.

The temperature of the sealing treatment liquid is preferably 85 to 100°C, preferably 88 to 98°C, more preferably 90 to 98°C. By setting the temperature of the sealing treatment liquid within the above range, the dye fixability of the anodic oxide film is further improved, and sufficient sealing performance can be expressed.

Generally, the sealing treatment time can be determined according to the thickness of the anodic oxide film to be treated. Specifically, the value obtained by multiplying the value (μm) of the film thickness by 0.1 to 10 is preferably used as the sealing treatment time (minutes), and it is preferably obtained by multiplying the value (μm) of the film thickness by 0.2 to 5 The value of is regarded as the sealing treatment time (minutes), and more preferably the value obtained by multiplying the numerical value (μm) indicating the film thickness by 0.5 to 4 is regarded as the sealing treatment time (minutes). For example, if the thickness of the anodic oxide film is 10 μm, the immersion time is preferably 10 times 0.2 to 5, which is about 2 to 50 minutes. By setting the sealing treatment time within the above range, the dye fixability is further improved, the sealing treatment liquid can exhibit sufficient sealing performance, and the anodic oxide film of the aluminum alloy sealed by the sealing treatment liquid can fully exhibit resistance to contamination It can prevent the appearance of the processed object from deteriorating due to poor appearance such as chalking and fogging.

In step 3, it is also possible to stir the sealing treatment solution while immersing the anodic oxide film that has been dyed and fixed. Regarding the stirring method, suitable: circulating stirring, air stirring, gas stirring, and shaking stirring. Among them, circulation stirring and gas stirring are preferred, and circulation stirring is preferred. Regarding the above-mentioned gas stirring, gas stirring using an inert gas such as nitrogen and argon is suitable. In the above steps, when using a sealing treatment liquid containing Mg salt, Ca salt, Sr salt, Ba salt, and Ra salt as the metal salt and having a pH of 7 or higher, the sealing treatment liquid absorbs carbon dioxide in the air and produces turbidity. situation. Therefore, the stirring method is preferably cyclic stirring as described above, but when air stirring is required on the equipment, from the viewpoint of suppressing the turbidity of the sealing treatment liquid, the above-mentioned gas stirring using an inert gas is preferred.

In step 3, a turbidity removal process for removing turbidity in the above-mentioned sealing treatment liquid may also be performed. In addition, the above-mentioned turbidity removal treatment may be performed in addition to step 3, for example, while waiting before immersing the dye-fixed anodic oxide film in the sealing treatment liquid or during the suspension of the production line. The turbidity removal treatment can prevent the appearance of the anodic oxide film from deteriorating due to poor appearance such as powdering and fog due to turbidity.

The turbidity removal method is not particularly limited, and a previously known removal method can be used. As the above removal method, filtering removal can be exemplified. Specifically, it can be filtered and removed as follows: a part of the sealing treatment liquid flows from the tank where the sealing treatment is performed into a buffer tank, such as a buffer tank as a chemical supply and dissolution tank, and the temperature of the sealing treatment liquid is cooled to 50°C or less, and passed through a filter After filtering, return to the above-mentioned tank for sealing treatment, and circulate. When the equipment does not have a buffer tank, it can also be filtered and removed simply by filtration cycle.

In the sealing treatment method of the present invention, the treatment target is an aluminum alloy anodic oxide film. The anodic oxide film of the aluminum alloy is not particularly limited, as long as it is an anodic oxide film of an aluminum alloy obtained by applying a well-known anodizing method, which uses sulfuric acid, oxalic acid, etc., for general aluminum alloys. The aluminum alloy is not particularly limited, and various aluminum-based alloys can be the target of anodization. Specific examples of aluminum alloys include: JIS-A defined by JIS No. 1000 to No. 7000 tensile material alloys, casting materials represented by the numbers of AC and ADC, aluminum represented by die-casting materials, etc. Various alloys as the main body.

Regarding the anodizing method performed on aluminum alloys, for example, the following method can be exemplified: using an aqueous solution with a sulfuric acid concentration of about 100g/L to 400g/L, setting the liquid temperature to about -10 to 30°C, and 0.5 to 4A/dm ² Electrolysis is performed around the anode current density.

[Examples] Hereinafter, the present invention will be specifically explained with examples and comparative examples. However, the present invention is not limited to the Examples.

Anodized and dyed aluminum alloy test pieces used in the following Examples and Comparative Examples were manufactured under the following manufacturing conditions.

The aluminum alloy test piece (JIS A1050P board) was immersed in a weakly alkaline degreasing solution (Toparuclean404 (trade name) 30g/L aqueous solution, bath temperature 60℃) made by Okuno Pharmaceutical Co., Ltd. The main component anodizing bath (including free sulfuric acid 180g/L and dissolved aluminum 8.0g/L) for anodizing (bath temperature 20℃±1℃, anode current density: 1a/dm ² , electrolysis time: 30 minutes, film thickness : About 10μm). The obtained anodic oxide film was washed with water, and after washing, immersed in an aqueous solution of the following dye (bath temperature 55°C) for 1 minute, dyed and washed, thereby obtaining anodized and dyed aluminum alloy test pieces (hereinafter referred to as "Anodic oxidation-dyeing finished test piece").

In addition, the dye used TAC YELLOW-SLH, TAC VIOLET-SLH, or TAC YELLOW-SGL (all are TAC dyes manufactured by Okuno Pharmaceutical Co., Ltd.). Prepare each dye aqueous solution separately. The dye concentration in the dye aqueous solution of each dye is 1 g/L.

(Example 1) The anodic oxidation-dyeing completed test piece manufactured under the above-mentioned manufacturing conditions was immersed in a dye fixing treatment agent (bath temperature of 75°C) for 5 minutes, washed with water, and the dye fixing treatment was completed. It is composed of an aqueous solution containing 1 g/L of manganese acetate, 1 g/L of sodium L-glutamate, and 0.5 g/L of naphthalenesulfonic acid formaldehyde condensate, and adjusted to pH 4.0 with nitric acid. Next, immerse in the sealing treatment liquid (bath temperature 95℃) for 20 minutes, and then wash and dry to complete the sealing treatment. The sealing treatment liquid contains 20ml/L of Topseal NIF manufactured by Okuno Pharmaceutical Co., Ltd. and has a pH value. It is composed of 5.7 aqueous solution.

(Examples 2 to 7) Except for changing the processing conditions as shown in Tables 1 and 2, the dyeing treatment, dye fixing treatment, and sealing treatment were performed in the same manner as in Example 1.

(Comparative Example 1) The dyeing treatment and the sealing treatment were performed in the same manner as in Example 1, except that the dye fixing treatment was not performed.

(Comparative Example 2) The dyeing treatment and the sealing treatment were performed in the same manner as in Example 2 except that the dye fixing treatment was not performed.

The above-mentioned Examples and Comparative Examples were evaluated by the following test methods.

Dyeing fixation L*, a*, and b* of the anodic oxidation-dyeing finished test piece manufactured using each of the above-mentioned dyes were measured with a spectrophotometer (CM-3700A manufactured by Konica Minolta) as a reference value. Next, L*, a*, and b* of the test pieces obtained in the above-mentioned Examples and Comparative Examples were measured, and evaluated from the total amount of change ΔE*ab from the above-mentioned reference value. In addition, the lower ΔE*ab, the higher the dye fixability.

The results are shown in Tables 1 and 2.

[Table 1]

[Table 2]

It can be seen from Table 1 that, in Examples 1 and 2, in which a dye fixing treatment agent containing a manganese salt and a pH value of 5.0 or less was used for the dye fixing treatment, compared with Comparative Examples 1 and 2 which were not subjected to the dye fixing treatment, ΔE *The ab value is low. It can be understood that high dye fixability can be achieved by using the above-mentioned dye fixation treatment agent for dye fixation after dyeing treatment and before sealing treatment.

It can be seen from Table 2 that in Examples 3-7 using TAC YELLOW-SGL as the dye, the ΔE*ab value is also lower. Processing can show high dye fixation. It can also be seen that in Examples 4, 5, and 6 where the pH values of the dye fixing treatment agent are 3.5, 4.0, and 4.5, respectively, the ΔE*ab value is particularly low, and it can exhibit particularly high dye fixing properties.

(without)

Claims (10)

A dye fixing treatment agent for anodic oxide film of aluminum alloy, which is characterized by containing at least one manganese salt selected from the group consisting of manganese acetate, manganese nitrate, manganese sulfate, manganese chloride, manganese borate and manganese carbonate, And the pH is below 5.0. Such as the dye fixing treatment agent of claim 1, which further contains an anionic surfactant. Such as the dye fixing treatment agent of claim 1 or 2, which further contains a pH buffer. A sealing treatment method, characterized in that it is a sealing treatment method of an anodic oxide film of aluminum alloy, and has the following steps: (1) step 1 of dyeing the anodic oxide film of aluminum alloy; (2) dyeing the anodic oxide film Step 2 of immersing the anodic oxide film in a dye fixing treatment agent for dye fixing treatment; and (3) Step 3 of sealing the anodic oxide film after dye fixing treatment; and, the dye fixing treatment agent contains manganese Salt and pH value below 5.0. Such as the sealing treatment method of claim 4, wherein the temperature of the dye fixing treatment agent is 55~95℃. Such as the sealing treatment method of claim 4 or 5, wherein the immersion time for the dye fixing treatment agent is 1 to 30 minutes. Such as the sealing treatment method of claim 4 or 5, wherein step 3 is to immerse the anodic oxide film that has been dyed and fixed in the sealing treatment Liquid steps. Such as the sealing treatment method of claim 7, wherein the pH of the sealing treatment liquid is 5.1~8.0. Such as the sealing treatment method of claim 7, wherein the sealing treatment liquid does not contain a nickel-based metal salt. An article with an anodic oxide film of aluminum alloy, wherein the anodic oxide film of the aluminum alloy is sealed by the method of claim 4.