KR20180129801A - Sealing solution for anodic oxidation coating of aluminum alloy, concentrate and sealing treatment method - Google Patents

Abstract

The present invention provides a sealing treatment liquid containing no nickel salt, which can provide the same level of sealing performance as in the case of using a sealing treatment liquid containing a nickel salt, and the sealed anodized film can exhibit excellent stain resistance Thereby providing a sealing liquid. The present invention provides a sealing liquid for an anodic oxidation coating of an aluminum alloy containing a metal salt, a pH buffering agent and a surfactant, wherein the metal salt is at least one selected from an alkali metal salt and an alkaline earth metal salt .

Description

Sealing solution for anodic oxidation coating of aluminum alloy, concentrate and sealing treatment method

The present invention relates to a sealing solution for an anodic oxidation coating of aluminum alloy, a concentrate and a sealing treatment method.

The anodic oxidation coating of the aluminum alloy is generally subjected to a sealing treatment in order to prevent contamination and improve corrosion resistance. As the sealing treatment method, there are known boiling water sealing, steam sealing, room temperature sealing, and nickel acetate sealing in which a sealing treatment is performed using a nickel acetate aqueous solution (see Non-Patent Document 1).

Among them, the corrosion resistance of the film is easily obtained compared with the boiling water sealing, the working efficiency is excellent as compared with the steam sealing, and the nickel acetate sealing is particularly used for reasons such as easy maintenance of the liquid compared to the sealing at room temperature.

In recent years, however, there has been a problem in that nickel an allergen or a nickel salt of a fine-powdered nickel salt has a problem of toxicity. Therefore, an anodic oxidation coating having sealing performance such as corrosion resistance and sealing degree the same as nickel acetate sealing by a sealing treatment method not using a nickel salt Is desired to be produced.

Non-Patent Document 1: Aluminum Surface Technical Manual of Light Metal Publishing Co.

SUMMARY OF THE INVENTION The present invention has been made in view of the problems of the prior art described above, and it is an object of the present invention to provide a sealing solution which does not contain a nickel salt and can provide a sealing performance to the same extent as that of a sealing solution containing a nickel salt, It is an object of the present invention to provide a sealing liquid which can exhibit excellent stain resistance with the anodized coating film treated by sealing.

The inventor of the present invention has conducted intensive studies in order to achieve the above object. As a result, according to the sealing liquid for the anodic oxidation coating of the aluminum alloy containing the metal salt, the pH buffering agent and the surfactant, the metal salt is at least one selected from an alkali metal salt and an alkaline earth metal salt, The present invention has been completed.

That is, the present invention relates to a sealing solution for an anodic oxidation coating of an aluminum alloy, a concentrate and a sealing treatment method described below.

1. A sealing treatment liquid for an anodic oxidation coating of an aluminum alloy containing a metal salt, a pH buffering agent and a surfactant, wherein the metal salt is at least one member selected from the group consisting of an alkali metal salt and an alkaline earth metal salt.

2. The sealing liquid according to item 1, wherein the metal salt is a metal salt of at least one metal selected from the group consisting of Na, Mg, K and Ca.

3. The sealing liquid according to item 1, wherein the metal salt is a metal salt of at least one metal selected from the group consisting of Mg and Ca.

4. The sealing liquid according to any one of items 1 to 3, wherein the metal salt is at least one selected from the group consisting of nitrates, sulfamates, sulfates and nitrates.

5. The sealing liquid according to any one of items 1 to 3, wherein the metal salt is a nitrate salt.

6. The sealing liquid according to any one of items 1 to 5, wherein the pH buffer is at least one selected from the group consisting of an organic acid salt, an ammonium salt, an amino acid, a borate salt, an amine compound and a nitrogen-containing heterocyclic compound.

7. The sealing liquid according to any one of items 1 to 5, wherein the pH buffering agent is a nitrogen-containing heterocyclic compound.

8. The sealing liquid according to any one of items 1 to 7, wherein the surfactant is at least one selected from the group consisting of an anionic surfactant and an amphoteric surfactant.

9. The sealing liquid according to any one of items 1 to 7, wherein the surfactant is at least one selected from the group consisting of a sulfate-based surfactant, a sulfonate-based surfactant and a phosphate ester-based surfactant.

10. The sealing liquid according to any one of items 1 to 9, wherein the pH is 7.0 to 10.0.

11. The sealing liquid according to any one of items 1 to 10, which does not contain a nickel metal salt.

12. The sealing liquid according to any one of items 1 to 11, wherein the total content of the metal salt, the pH buffering agent and the surfactant in the sealing liquid is 0.2 to 100 g / L.

13. A concentrated liquid of a sealing liquid for an anodic oxidation coating of an aluminum alloy containing a metal salt, a pH buffering agent and a surfactant,

Wherein the metal salt is at least one selected from the group consisting of an alkali metal salt and an alkaline earth metal salt.

14. A method for sealing an anodic oxide coating of an aluminum alloy, comprising the step of immersing an article having an anodized coating of an aluminum alloy in a sealing solution for an anodic oxidation coating of an aluminum alloy, wherein the sealing treatment solution is a metal salt, And a surfactant, and the metal salt is at least one selected from the group consisting of an alkali metal salt and an alkaline earth metal salt.

15. The sealing treatment method according to item 14, wherein the liquid temperature of the sealing liquid is 85 to 100 占 폚.

16. The sealing treatment method according to item 14 or 15, wherein the pH of the sealing liquid is 7.0 to 10.0.

17. An article sealed by the sealing treatment method according to any one of items 14 to 16.

According to the sealing treatment liquid of the present invention, sealing performance can be imparted to the anodic oxidation coating of aluminum alloy to the same degree as that in the case of using a sealing treatment liquid containing a nickel salt, and excellent stain resistance can be imparted .

Further, according to the concentrate of the present invention, it is possible to easily prepare the sealing liquid for the anodic oxide coating of the aluminum alloy of the present invention by diluting the concentrate.

Further, according to the method of sealing the anodized film of the aluminum alloy of the present invention, sealing performance equivalent to that of the case of using the sealing treatment solution containing the nickel salt can be imparted to the anodized film of the aluminum alloy, In addition, excellent stain resistance can be imparted.

Hereinafter, the present invention will be described in detail.

1. Sealing solution

The sealing liquid of the present invention is a sealing liquid for an anodic oxidation coating of an aluminum alloy containing a metal salt, a pH buffering agent and a surfactant, wherein the metal salt is at least one selected from an alkali metal salt and an alkaline earth metal salt.

(Metal salt)

The metal salt contained in the sealing treatment liquid of the present invention is at least one selected from the group consisting of an alkali metal salt and an alkaline earth metal salt. The alkali metal salt and alkaline earth metal salt are not particularly limited, but water-soluble ones are preferable, and carboxylic acid salts, sulfamic acid salts, sulfate salts, nitrate salts, organic sulfonic acid salts and the like can be given. Of these, carboxylate, sulfamate, sulfate and nitrate are preferable from the viewpoint of excellent anodic oxidation resistance of the anodic oxidation coating of the aluminum alloy subjected to sealing treatment, and nitrates, sulfamates, sulfates and nitrates are more preferable, More preferred are nitrates. The metal salts may be used singly or in combination of two or more.

The metal contained in the metal salt is not particularly limited as long as it is an alkali metal and an alkaline earth metal. Specifically, Li, Be, Na, Mg, K, Ca, Rb, Sr, Cs, Ba, have. Of these, metal salts of Na, Mg, K and Ca are preferable, and metal salts of Mg and Ca are more preferable, and metal salts of Mg are more preferable because the anodic oxidation coating of the aluminum alloy subjected to sealing treatment is excellent in stain resistance. The metal contained in the metal salt may be used alone or in combination of two or more.

The concentration of the metal salt in the sealing liquid is not particularly limited and is preferably 0.001 to 1 mol / L, more preferably 0.01 to 0.5 mol / L. When the concentration of the metal salt is in the above range, the sealing liquid can exhibit sufficient sealing performance, and the anodized coating of the aluminum alloy sealed by the sealing liquid can sufficiently exhibit stain resistance.

(pH buffer)

The pH buffer is not particularly limited and conventionally known pH buffers can be used. Examples of such pH buffering agents include organic acid salts, ammonium salts, amino acids, borate salts, amine compounds, and nitrogen-containing heterocyclic compounds. Of these, a nitrogen-containing heterocyclic compound is preferable in that an excellent antifouling property can be imparted to an anodic oxidation coating of an aluminum alloy which has been subjected to a sealing treatment with a sealing treatment liquid.

Examples of the organic acid salt include salts of carboxylic acid and oxycarboxylic acid. The number of carbon atoms of the carboxylic acid and oxycarboxylic acid is preferably 4 or less. Examples of the salt include a sodium salt and a potassium salt.

Examples of the ammonium salt include an ammonium salt of an organic acid and an ammonium salt of an inorganic acid. Examples of the ammonium salt of the organic acid include an ammonium salt of a carboxylic acid or an oxycarboxylic acid. The number of carbon atoms of the carboxylic acid and oxycarboxylic acid is preferably 4 or less. Examples of the ammonium salt of an inorganic acid include ammonium sulfate, ammonium nitrate and ammonium sulfamate.

Examples of amino acids include glycine, alanine, asparagine and salts thereof. Examples of the borate include sodium borate, potassium borate and ammonium borate. Examples of the amine compound include monoethanolamine, diethanolamine and ethanolamine which is triethanolamine, and water-soluble carbonylamines such as alkylamine, aromatic amine and urea.

Examples of the nitrogen-containing heterocyclic compound include a heterocyclic compound containing at least one nitrogen atom as a hetero atom, and a heterocyclic compound containing at least one nitrogen atom and at least one oxygen atom as a hetero atom.

Examples of the nitrogen-containing heterocyclic compound include at least one selected from the group consisting of ethyleneimine, aziridine, azetidine, azet ring, pyrrolidine, pyrrole, piperidine, pyridine, A pyrazole ring, an oxazole ring, an imidazoline ring, a pyrazine ring, a morpholine ring, a pteridine ring, a purine ring, and the like. Of these, preferred are pyrrolidine ring, pyrrole ring, piperidine ring, pyridine ring, hexamethylene imine ring, azatrophenyl ring, imidazole ring, pyrazole ring, oxazole ring, imidazoline ring, pyrazine ring, morpholine ring, A nitrogen-containing heterocyclic compound including a pyridine ring, a pyridine ring, a pyridine ring, a pyridine ring, and a pyridine ring.

Examples of the nitrogen-containing heterocyclic compound include organic amine compounds such as ethyleneimine, azirine, azetidine, azet, pyrrolidine, pyrrole, piperidine, pyridine, hexamethyleneimine, azatropylidene, imidazole, pyrazole, oxazole, Imidroline, pyrazine, morpholine, pteridine, purine, etc., and compounds in which an amino group or a methyl group is added to the skeleton thereof can be used. Among them, a heterocyclic compound of a cyclic 5-membered to 7-membered ring having one or two nitrogen atoms as a hetero atom in the cyclic constituent atom and consisting of carbon or one heteroatom oxygen and carbon is preferable, and specifically, A compound having a cyclic skeleton as a basic structure and a compound having a cyclic skeleton such as pyridine, pyrrole, piperidine, pyridine, hexamethyleneimine, azatrophenylidene, imidazole, pyrazole, oxazole, imidazoline, pyrazine and morpholine You can count. Also preferred are compounds having a multicyclic structure and having four or more heteroatoms nitrogen, for example, compounds such as purines and pteridines and compounds having a multicyclic skeleton as a basic structure. Among them, a 5- to 6-membered ring is more preferable, and a compound such as pyrrolidine, pyrrole, piperidine, pyridine, imidazole, pyrazole, oxazole, imidazoline, pyrazine and morpholine, A compound group having a basic structure can be mentioned. Among them, a compound having a double bond in the ring such as pyrrole, pyridine, imidazole, pyrazole, oxazole, imidazoline, pyrazine and the like and a compound group having a cyclic skeleton as a basic structure are particularly preferable. Examples of the substituent constituting the group of these compounds include an amino group and a methyl group, and a compound group to which the substituent is added may be used. Aminopyridines such as 2-aminopyridine and 4-aminopyridine, and methylimidazole such as 2-methylimidazole are particularly preferable. Among them, pyridine, imidazole, aminopyridine, methylimidazole and the like are most preferable.

Examples of the nitrogen-containing heterocyclic compound include pyridine; Aminopyridines such as 2-aminopyridine and 4-aminopyridine; Imidazole; Methylimidazole such as 2-methylimidazole; Pyrazole; Pteridine; Oxazole and the like are particularly preferable.

The pH buffer may be used alone or in combination of two or more.

The concentration of the pH buffer in the sealing liquid is not particularly limited, but is preferably 0.1 to 100 g / L, more preferably 0.2 to 20 g / L. When the concentration of the pH buffer is in the above range, the sealing liquid can exhibit buffering properties at a good pH, and the appearance of defective appearance (drying unevenness) of the surface of the treated product caused by excessively high concentration of the pH buffering agent, Decolorization is suppressed.

(Surfactants)

The surfactant is not particularly limited and conventionally known surfactants can be used. Examples of such surfactants include anionic surfactants, nonionic surfactants, and amphoteric surfactants.

As the anionic surfactant, a sulfate-based surfactant, a sulfonate-based surfactant, a phosphorus-based surfactant, and the like can be used.

Examples of the sulfate-based surfactant include an aromatic sulfate-based surfactant and an aliphatic sulfate-based surfactant.

Examples of the aromatic sulfate-based surfactant include polyoxyethylene alkyl phenyl ether sulfate. Examples of the aliphatic sulfate-based surfactant include polyoxyethylene alkyl ether sulfate.

As the sulfonate type surfactant, an aromatic sulfonate type surfactant and the like can be mentioned.

Examples of the aromatic sulfonate surfactants include aromatic sulfonate compounds such as benzenesulfonate and naphthalenesulfonate salts, and aromatic sulfonate compounds such as benzenesulfonate and naphthalenesulfonate salts, such as alkyl groups, polyoxyethylene groups, polyoxyethylene alkyl ether groups , A compound having an alkylene group or a multiple bond such as a carboxyl group, a carbonyl group, a hydroxyl group, an alcohol group, a vinyl group or an allyl group, or a compound in which a sulfonic acid group is further substituted, and the polycondensate of these compounds in formalin and the like And copolymers thereof. Examples of such aromatic sulfonate surfactants include alkylbenzenesulfonates, alkylnaphthalenesulfonates and polycondensates thereof such as formalin, polycondensates such as formalin of naphthalenesulfonates, alkylene benzenesulfonates, alkylene naphthalenesulfonates and the like And the like.

Examples of the aromatic sulfonate surfactant include compounds in which a plurality of phenyl sulfonate salts such as diphenyl ether disulfonate are ether-bonded. In addition, an alkyl group, a polyoxyethylene group, a polyoxyethylene alkyl ether group, etc., These substituted compounds may be mentioned. Examples of such aromatic sulfonate surfactants include alkyl diphenyl ether disulfonate salts and alkyl diphenyl ether disulfonate salts.

As the phosphorus surfactant, a phosphate ester surfactant, a phosphate ester salt surfactant, or the like can be used. Specific examples thereof include polyoxyethylene alkyl ether phosphoric acid esters, polyoxyethylene alkylene phenyl ether phosphoric acid esters, alkyl phosphoric acid esters, and salts thereof.

As the nonionic surfactant, a nonionic surfactant capable of adjusting the concentration in the sealing liquid and combining it with other surfactants to make the cloud point at 85 ° C or higher in the sealing liquid can be suitably used . Examples of such nonionic surfactants include polyoxyethylene alkyl ethers, glycerin ester polyoxyethylene ethers, sorbitan esters, fatty acid alkanolamides, and the like.

Examples of the amphoteric surfactant include alkyl betaines, fatty acid amide betaines, and alkylamine oxides.

As the surfactant, an anionic surfactant is preferable. Among them, a sulfate-based surfactant, a sulfonate-based surfactant, and a phosphorus-based surfactant are more preferable, and a sulfonate-based surfactant is more preferable.

The surfactants may be used alone or in combination of two or more. The nonionic surfactant may be selected so as not to lower the cloud point of the sealing liquid. Further, when a nonionic surfactant and an anionic surfactant are mixed and used, the blur point of the surfactant can be increased. In the case of using an anionic surfactant, it may be selected that does not cause turbidity by reacting with the contained metal or the amphoteric surfactant.

The concentration of the surfactant in the sealing liquid is not particularly limited, but is preferably 10 mg / L to 10 g / L, more preferably 20 mg / L to 5 g / L. When the concentration of the surfactant is in the above range, the sealing liquid can exhibit sufficient sealing performance, and the adhesion of dust on the surface of the anodized coating film subjected to the sealing treatment and the defective appearance of whiteness can be suppressed.

(pH adjusting agent)

The sealing liquid of the present invention may further comprise a pH adjusting agent. The pH adjusting agent is not particularly limited and conventionally known pH adjusting agents can be used.

Examples of the pH adjusting agent for adjusting the sealing treatment liquid to the acidic side include dilute aqueous solutions such as acetic acid, sulfamic acid, sulfuric acid, nitric acid, and organic sulfonic acid. Of these, nitric acid is preferable because of its excellent sealing performance.

Examples of the pH adjusting agent for adjusting the sealing treatment liquid to the alkaline side include aqueous ammonia, aqueous sodium hydroxide solution, aqueous potassium hydroxide solution and the like. Of these, an aqueous solution of sodium hydroxide is preferable because of its excellent sealing performance.

The pH adjusters may be used alone or in combination of two or more.

The concentration of the pH adjusting agent in the sealing liquid is not particularly limited and is preferably 0 to 20 g / L, more preferably 0 to 10 g / L, and even more preferably 0 to 5 g / L. When the concentration of the pH adjuster is in the above range, the sealing liquid can exhibit sufficient sealing performance, and the lowering of the degree of sealing of the anodized coating film sealed by the sealing liquid can be suppressed.

(Other components)

The sealing liquid of the present invention may contain an additive component such as a mold inhibitor and a complexing agent, if necessary, in order to improve the sealing performance and practical use of the liquid. Examples of additives include antifungal agents such as benzoic acid and benzoic acid salt; And complexing agents such as citric acid and citric acid salts. As the antifungal agent, commercially available antifungal agents such as "TAC Gavicolone" (manufactured by Okuno Pharmaceutical Co., Ltd.) may be added.

(Sealing solution)

The total content of the metal salt, the pH buffering agent and the surfactant in the sealing treatment liquid of the present invention is preferably 0.2 to 100 g / L, more preferably 0.3 to 50 g / L, and still more preferably 0.5 to 30 g / L. When the total content is in the above range, the sealing liquid can exhibit sufficient sealing performance, and the anodic oxidation coating of the aluminum alloy which has been subjected to the sealing treatment by the sealing liquid can sufficiently exhibit stain resistance, It is possible to suppress the adhesion of dust on the surface of the anodized film and the defective appearance of whiteness.

The pH of the sealing liquid is preferably 7.0 to 10.0, more preferably 7.2 to 9.5, and further preferably 7.5 to 9.0. By setting the pH to the above range, the sealing treatment liquid can exhibit sufficient sealing performance, and the anodic oxidation coating of the aluminum alloy sealed by the sealing treatment liquid can sufficiently exhibit the stain resistance, and the surface of the to- The adhered outer appearance defects (powder adhesion, whitening) are suppressed.

When the sealing liquid of the present invention contains a metal salt, a pH buffering agent and a surfactant, the other components are not particularly limited, but an aqueous solution containing the above components is preferable.

The sealing liquid of the present invention preferably does not contain a metal salt such as a nickel-based metal salt. Examples of the metal salt include metal salts such as Ni, Co, Fe and Cr.

2. Concentrate

The concentrate of the present invention is a concentrate of a sealing treatment liquid for an anodic oxidation coating of an aluminum alloy containing a metal salt, a pH buffering agent and a surfactant, wherein the metal salt is at least one selected from an alkali metal salt and an alkaline earth metal salt. By making the concentrated liquid having a high concentration of components contained in the sealing liquid, the liquid can be easily transported and stored and can be easily prepared by diluting it with a diluent such as water. As the diluent, water is preferable.

The metal salt, the pH buffering agent and the surfactant contained in the concentrate of the present invention can be the same as those contained in the above-mentioned sealing liquid. The concentrated liquid of the present invention contains the same components as the above-mentioned sealing liquid, but the content of the components is different.

The total content of the metal salt, the pH buffering agent and the surfactant in the concentrated liquid is preferably 1 to 800 g / L, more preferably 1.5 to 400 g / L, and still more preferably 2.5 to 250 g / L. When the total content is in the above-mentioned range, it is easy to carry and store, and the sealing liquid can be easily prepared by diluting with water or the like. The total content of the metal salt, the pH buffering agent and the surfactant in the concentrated liquid may be in the range of more than 100 g / L or more and 150 g / L or more in terms of distinction between the sealing liquid and the concentrate.

3. Sealing method

A sealing treatment method of the present invention is a sealing treatment method of an anodic oxidation coating of an aluminum alloy, comprising the step of immersing an article having an anodized coating of an aluminum alloy in a sealing solution for an anodic oxidation coating of an aluminum alloy, Wherein the metal salt is at least one selected from the group consisting of an alkali metal salt and an alkaline earth metal salt, and a metal salt, a pH buffering agent and a surfactant.

As the sealing liquid, the above-described sealing liquid can be used. The sealing treatment method of the present invention has a step of immersing an article having an anodized film of an aluminum alloy in the sealing liquid. The immersion method is not particularly limited, and it may be immersed by a conventionally known method.

The temperature of the sealing liquid in the above step is preferably 85 to 100 占 폚, more preferably 88 to 98 占 폚, and further preferably 90 to 98 占 폚. When the temperature of the sealing liquid is within the above range, sufficient sealing performance can be exhibited.

The pH of the sealing liquid is preferably 7.0 to 10.0, more preferably 7.2 to 9.5, and further preferably 7.5 to 9.0. By setting the pH to the above range, the sealing liquid can exhibit a sufficient sealing performance, and poor appearance (powder adhesion, whitening) in which powder deposits adhere to the surface of the object to be treated is suppressed.

The sealing treatment time is usually determined by the film thickness of the anodic oxide film to be treated. Specifically, it is preferable that the number obtained by multiplying the number (mu m) representing the film thickness by 0.1 to 10 is the sealing processing time (minute), and the number obtained by multiplying the number (mu m) It is more preferable to set the sealing treatment time (minute), and it is more preferable that the number obtained by multiplying the number (탆) representing the film thickness by 0.5 to 4 is the sealing treatment time (minute). For example, when the film thickness of the anodized film is 10 占 퐉, it is more preferable that the immersion time is set to about 2 to 50 minutes by multiplying 10 by 0.2 to 5. By setting the sealing treatment time within the above-mentioned range, the sealing treatment liquid can exhibit sufficient sealing performance, and the anodized coating of the aluminum alloy sealed by the sealing treatment liquid can sufficiently exhibit stain resistance, and further, Deterioration of the appearance of the object to be treated due to defects can be suppressed.

In this process, an article having an anodized film of an aluminum alloy may be immersed while stirring the sealing solution. As the stirring method, cyclic stirring, air stirring, gas stirring, and swing stirring are suitable. Among them, cyclic stirring and gas stirring are preferable, and cyclic stirring is more preferable. As the gas stirring, gas stirring using an inert gas such as nitrogen gas or argon gas is suitable. In the above process, when a sealing treatment liquid containing a Mg salt, a Ca salt, a Sr salt, a Ba salt and a Ra salt as a metal salt and having a pH of 7 or more is used, the sealing treatment liquid absorbs carbon dioxide in the air, . For this reason, as the stirring method, it is preferable to perform cyclic stirring as described above, but when it is necessary to perform air stirring in the facility, it is preferable to carry out gas stirring using the inert gas to suppress the turbidity of the sealing liquid .

The sealing treatment method of the present invention may be subjected to a turbidity removal treatment for removing the turbidity in the sealing treatment liquid during the step of immersing the article having the anodic oxidation coating of the aluminum alloy in the sealing liquid for the anodic oxidation coating of the aluminum alloy . Further, the turbidity removal treatment may be performed during the period other than the above-mentioned process, for example, during the time of immersing the article in the sealing liquid for anodizing treatment, or during stop of the line. It is possible to suppress deterioration of the external appearance of the anodized film due to appearance defects such as powder adhesion and whitening due to turbidity by carrying out the turbidity removal treatment.

The turbid removal method is not particularly limited, and conventionally known removal methods can be used. Examples of the removal method include filtration removal. Specifically, a part of the sealing treatment liquid is caused to flow from a tank for performing the sealing treatment to a reserve tank such as a cushion tank, which is a solution supply and dissolution tank for chemical supply addition, and the temperature of the sealing treatment liquid is preferably cooled to 50 DEG C or lower, Filtration through filtration through a filter, and filtration to return the filtrate to the tank for carrying out the sealing treatment. If the equipment does not have a cushion tank, filtration may be performed by simple filtration circulation.

In the sealing treatment method of the present invention, the object to be treated is an anodic oxidation film of an aluminum alloy. The anodic oxide coating of the aluminum alloy is not particularly limited and may be an anodic oxide coating of an aluminum alloy obtained by applying a known anodic oxidation method using a general aluminum alloy with sulfuric acid, oxalic acid, or the like. The aluminum alloy is not particularly limited, and various kinds of aluminum-based alloys can be subjected to anodization. Specific examples of the aluminum alloy include representative alloys such as an expanded metal alloy, JIS-A 1,000 to 7,000 times as specified in JIS, castings and die casts represented by AC and ADC numbers And various kinds of alloys such as aluminum-based alloys.

As the anodic oxidation method for the aluminum alloy, for example, an aqueous solution having a sulfuric acid concentration of about 100 g / L to about 400 g / L is used, and the solution temperature is set to about -10 to 30 DEG C, And the electrolysis is carried out.

Further, in the sealing treatment method of the present invention, the anodized film of the aluminum alloy may be electrolytically colored.

As the electrolytic coloring method, a known coloring method can be employed. For example, after the anodic oxidation is carried out, the film is dipped in an electrolytic coloring bath, and secondary electrolysis is carried out, whereby the anodic oxidation coating can be colored. Examples of the electrolytic coloring bath include a nickel salt-boric acid bath, a nickel salt-tin salt-sulfuric acid bath, and the like.

Further, in the sealing treatment method of the present invention, the anodic oxide film of the aluminum alloy may be subjected to dyeing using a dye.

As a dyeing method using a dye, a method of immersing an anodic oxidation film in a conventionally known dye aqueous solution can be mentioned. As such dyes, those commercially available as dyes for aluminum alloy anodic oxidation coatings can be used, and examples thereof include anionic dyes and the like. The temperature of the aqueous dye solution is preferably from 10 to 70 캜, more preferably from 20 to 60 캜. The concentration of the dye in the dye aqueous solution and the immersion time may be suitably set in accordance with the desired color tone and color density of the dye.

When an anodic oxidation film of an aluminum alloy is subjected to dyeing using a dye and the sealing liquid can not impart dye fixability, dye fixing treatment may be performed after dyeing and before sealing. (For example, TAC fixing agent-2 manufactured by Okuno Pharmaceutical Industry Co., Ltd., TAC Sunblock 77-5C, etc.) for the dyeing process of the aluminum alloy anodic oxide film, Can be used. In addition, dye fixability can be imparted to the encapsulating treatment liquid by adjusting the type and blending of the pH buffering agent and the surfactant in the encapsulation treatment liquid.

In the sealing treatment method of the present invention, an article having an anodic oxide film of the above-described aluminum alloy may be used as the object to be treated, and the object to be treated may be immersed in the sealing liquid. If required, the product having an anodized film of an aluminum alloy may be subjected to electrolytic coloring, dyeing, and the like, and then subjected to thorough washing with water to dope the object to be treated in the sealing liquid. Thus, the sealing performance of the anodized film of the aluminum alloy of the object to be treated can be greatly improved.

Example

EXAMPLES The present invention will be described in more detail with reference to the following examples and comparative examples. However, the present invention is not limited to the embodiments.

An aluminum alloy test piece subjected to anodization used in the following examples and comparative examples was prepared according to the following production conditions.

Preparation of anodic oxidation-completed test piece A (without dyeing treatment and dyeing fixing treatment)

A test piece of aluminum (JIS A1050P plate) was immersed in a weak alkaline degreasing solution (30 g / L aqueous solution of TOPACLEAN 101 (trade name) manufactured by Okuno Pharmaceutical Co., Ltd., bath temperature: 60 캜) for 3 minutes and degreased. Subsequently, the plate was washed with water and subjected to anodic oxidation (bath temperature: 20 占 1 占 폚, anodic current density: 1 A / min) with an anodic oxidation bath containing 180 g / L of free sulfuric acid and 8.0 g / dm < 2 >, electrolysis time: 30 minutes, film thickness: about 10 mu m). The resulting anodized film was washed with water to obtain an aluminum alloy test piece subjected to anodic oxidation (hereinafter referred to as " anodized test piece A ").

Preparation of Anodized Finished Specimen B (with dyeing treatment and dyeing and fixing treatment)

A test piece of aluminum (JIS A1050P plate) was immersed in a weak alkaline degreasing solution (30 g / L aqueous solution of TOPACLEAN 101 (trade name) manufactured by Okuno Pharmaceutical Co., Ltd., bath temperature: 60 캜) for 3 minutes and degreased. Subsequently, the plate was washed with water and subjected to anodic oxidation (bath temperature: 20 占 1 占 폚, anodic current density: 1A / dm2) with an anodic oxidation bath containing sulfuric acid as a main component (containing 180 g / L of free sulfuric acid and 8.0 g / Electrolytic time: 30 minutes, film thickness: about 10 mu m). The obtained anodized film was washed with water, immersed in an acid bath (bath temperature: room temperature) containing 100 mL / L of 98% sulfuric acid for 1 minute, acid activated, and washed with water. Subsequently, the plate was immersed in a dyeing treatment liquid (TAC dye TAC black 402, 1 g / L, manufactured by Okuno Pharmaceutical Co., Ltd.) for 1 minute at 50 DEG C, washed with water and subjected to dyeing treatment. Subsequently, the substrate was immersed in a dyeing fixing solution (20 mL / L of TAC fixing agent-2 (trade name) manufactured by Okuno Pharmaceutical Co., Ltd.) for 3 minutes at room temperature and washed with water to perform dye fixing processing, (Hereinafter referred to as " anodized test piece B ").

Preparation of Anodic Oxidized Test Specimen C (with dyeing treatment, no dye fixing treatment)

A test piece of aluminum (JIS A1050P plate) was immersed in a weak alkaline degreasing solution (30 g / L aqueous solution of TOPACLEAN 101 (trade name) manufactured by Okuno Pharmaceutical Co., Ltd., bath temperature: 60 캜) for 3 minutes and degreased. Subsequently, the plate was washed with water and subjected to anodic oxidation (bath temperature: 20 占 1 占 폚, anodic current density: 1A / dm2) with an anodic oxidation bath containing sulfuric acid as a main component (containing 180 g / L of free sulfuric acid and 8.0 g / Electrolytic time: 30 minutes, film thickness: about 10 mu m). The obtained anodized film was washed with water, immersed in an acid bath (bath temperature: room temperature) containing 100 mL / L of 98% sulfuric acid for 1 minute, acid activated, and washed with water. Subsequently, the plate was dipped in a dyeing treatment liquid (TAC dye TAC black 402, 1 g / L, manufactured by Okuno Pharmaceutical Co., Ltd.) for 1 minute at 50 ° C, washed with water to give a dyeing treatment, Alloy test piece (hereinafter referred to as " anodized test piece C ").

(Example 1)

The anodized test piece A prepared in accordance with the above production conditions was mixed with 1 g / L of sodium acetate as a metal salt, 1 g / L of ammonium acetate as a pH buffer and 0.5 g / L of a sodium naphthalenesulfonate sulfonic acid polycondensate as a surfactant, (Bath temperature: 92 ° C), which is an aqueous solution adjusted to pH 7.0, 8.0, and 9.0, respectively, with ammonia water for 5 minutes, 10 minutes, and 20 minutes for each pH. did.

(Example 2)

A sealing treatment was carried out in the same manner as in Example 1 except that the anodic oxidation complete test piece B was used.

(Example 3)

A sealing solution containing 5 g / L of magnesium acetate as a metal salt, 0.5 g / L of triethanolamine as a pH buffering agent and 0.2 g / L of sodium dodecylbenzenesulfonate as a surfactant and adjusting the pH with acetic acid and sodium hydroxide A sealing treatment was carried out in the same manner as in Example 1 except for using.

(Example 4)

A sealing solution containing 5 g / L of calcium nitrate as a metal salt, 4 g / L of alanine as a pH buffering agent and 0.2 g / L of an alkylenephenyl sulfonic acid sodium copolymer as a surfactant and adjusting the pH with nitric acid and ammonia water Except for this, sealing treatment was carried out in the same manner as in Example 1.

(Example 5)

A sealing solution containing 10 g / L of magnesium nitrate as a metal salt, 4 g / L of pyridine as a pH buffering agent and 0.5 g / L of a sodium naphthalenesulfonate sodium formalin condensate as a surfactant and adjusting the pH with nitric acid and potassium hydroxide Except for this, sealing treatment was carried out in the same manner as in Example 1.

(Example 6)

Anodic oxidation finished test piece B was used, and an aqueous solution containing 10 g / L of magnesium nitrate as a metal salt, 4 g / L of pyridine as a pH buffer and 0.5 g / L of a sodium naphthalenesulfonate formalin polycondensate and having a pH adjusted with nitric acid and potassium hydroxide A sealing treatment was carried out in the same manner as in Example 1 except that the phosphorus-containing sealing solution was used.

(Example 7)

The anodized test piece A prepared in accordance with the above manufacturing conditions was coated with 10 g / L potassium nitrate as a metal salt, 0.5 g / L 2-aminopyridine and 0.5 g / L 2-methylimidazole as a pH buffer, (Bath temperature: 92 占 폚) containing 0.2 g / L of ethylene styrenated phenyl ether phosphate and adjusted to pH 7.5 and 9.5 with nitric acid and ammonia water for 5 minutes each for 20 minutes And the sealing treatment was carried out.

(Example 8)

L of magnesium nitrate as a metal salt, 0.5 g / L of 2-aminopyridine and 0.5 g / L of 2-methylimidazole as a pH buffer, and 0.2 g / L of polyoxyethylene styrenated phenyl ether phosphate as a surfactant , Sealing treatment was carried out in the same manner as in Example 7, except that the sealing solution was an aqueous solution in which the pH was adjusted with nitric acid and ammonia water.

(Example 9)

1 g / L of barium nitrate as a metal salt, 1 g / L of pyrazole as pH buffering agent, 1 g / L of pteridine, 1 g / L of fatty acid amide alkylbetaine as a surfactant, A sealing treatment was carried out in the same manner as in Example 7, except that a sealing solution containing 0.2 g / L of a sodium copolymer and an aqueous solution of pH adjusted with nitric acid and ammonia water was used.

(Example 10)

Anodic oxidation finished test piece A was used, and 20 g / L of magnesium nitrate as a metal salt, 2 g / L of imidazole as a pH buffer, 0.1 g / L of polyoxyethylene alkyl ether sodium sulfate as a surfactant and 0.2 g / L of sodium polyoxyethylene phenyl ether sulfate And a sealing treatment liquid which was an aqueous solution in which pH was adjusted with nitric acid and ammonia water was used.

(Example 11)

Anodic oxidation test piece A was used, and 20 g / L of magnesium nitrate as a metal salt, 2 g / L of imidazole as a pH buffer, 0.01 g / L of a polyoxyethylene alkyl ether as a surfactant and 0.2 g of a sodium alkylenephenyl sulfonate copolymer / L and a pH value of which was adjusted with nitric acid and ammonia water was used as the sealing solution.

(Example 12)

Anodic oxidation finished test piece B was used, and 5 g / L of calcium nitrate as a metal salt, 1 g / L of oxazole as a pH buffer, 0.2 g / L of fatty acid amide alkyl betaine and 0.5 g / L of sodium dodecylbenzenesulfonate as a surfactant And the pH value of which was adjusted with nitric acid and ammonia water was used as the sealing solution.

(Comparative Example 1)

The anodic oxidation-completed specimen A was immersed in a boiling water seal (ion-exchanged water) at 92 占 폚 for 20 minutes to perform a sealing treatment.

(Comparative Example 2)

The anodic oxidation finished test piece A was subjected to a sealing treatment liquid (bath temperature: 92 DEG C) comprising an aqueous solution of pH 5.6 containing 40 mL / L of a nickel acetate based sealing agent (Top Seal H-298 (trade name) manufactured by Okuno Pharmaceutical Co., For 5 minutes, 10 minutes, and 20 minutes, respectively, for sealing treatment.

(Comparative Example 3)

A sealing treatment was carried out in the same manner as in Comparative Example 2 except that the anodic oxidation finished test piece C was used.

(Comparative Example 4)

L of ammonium persulfate, 0.5 g / L of 2-aminopyridine and 0.5 g / L of 2-methylimidazole as a pH buffer, and 0.2 g / L of polyoxyethylene styrenated phenyl ether phosphate as a surfactant, And a sealing solution which was an aqueous solution in which the pH was adjusted with ammonia water was used as the sealing solution.

In the above-mentioned Examples and Comparative Examples, immediately after the anodizing test piece was subjected to the sealing treatment, washing with flowing water was performed for 1 minute with tap water. Subsequently, the anodic oxidation finished test piece was dried with a drier and allowed to stand overnight in a room temperature environment to prepare an anodic oxidation finished test piece after the sealing treatment.

The anodized test pieces after the sealing treatment prepared in the above Examples and Comparative Examples were evaluated by the following test methods.

Sealing degree

Each of the test pieces after the sealing treatment was immersed in an aqueous phosphoric acid-chromic acid solution in accordance with JIS H 8683-2: 1999 (Test method for sealing the anodic oxide coating of aluminum and aluminum alloy Part 2: Immersion test for aqueous solution of phosphoric acid and chromic acid) The mass loss of the test piece per unit area was measured. The smaller the value, the better the sealability.

Stain resistance (magic test - adhesion decontamination test)

Each of the test pieces after the sealing treatment was allowed to stand at room temperature for 1 day, a mark was written on the surface thereof with an oil-based black magic ink, and was left standing for 30 seconds. Then, it was wiped with a box tissue impregnated with water or isopropyl alcohol, and evaluated according to the following evaluation criteria.

◎: It can be completely removed by rubbing lightly

○: The mark can be removed if rubbed strongly

△: A little mark remains even if rubbed strongly

X: The mark black does not fall off

In addition, if it is? Evaluated by the test using water, it can be judged that there is no problem in actual use.

Appearance evaluation

The occurrence of dust adhesion on the surface of the anodized test piece subjected to the sealing treatment, whitening, or the occurrence of the irregularity of the interference film by them was visually observed and evaluated according to the following evaluation criteria.

&Amp; cir &: No adhesion of powder, white or interference film by them, no appearance of rainbow, and good appearance

○: Though slight irregularity occurs with powder adhesion, whitening, or interference film therebetween, there is no problem in appearance

?: Irregular irregularities of powder adhesion, whitening, or interference film therebetween occur, resulting in a poor appearance defect

X: irregularity of the interference film due to powder adhesion, whitening, or interference therebetween is strongly generated, and appearance defect of a serious degree occurs

The results are shown in Tables 1 to 5.

As is apparent from Tables 1 to 5, the use of the sealing treatment liquids of Examples 1 to 12 can provide a sealing performance equivalent to that of the case of using a sealing treatment liquid containing a nickel salt even in a sealing treatment liquid containing no nickel salt It can be grasped. It was also found that the use of the sealing treatment solutions of Examples 1 to 12 enabled the sealing treatment of the anodized coating film to exhibit excellent stain resistance.

(Example 13)

The anodic oxidation finished test piece A contained 10 g / L of magnesium nitrate as a metal salt, 4 g / L of pyridine as a pH buffering agent and 0.5 g / L of a sodium naphthalenesulfonate sulfonate polycondensate as a surfactant, and the pH was adjusted to 9.0 with nitric acid and potassium hydroxide And immersed in 1 L of a sealing solution (bath temperature: 92 ° C) which was an adjusted aqueous solution and subjected to sealing treatment. Concretely, 20 pieces of test pieces were immersed in turn for 20 minutes each while the argon gas was stirred to the sealing solution. The test pieces were 5 cm x 10 cm in size and had a total area of 1 dm 2 on both sides.

(Example 14)

A sealing treatment was carried out in the same manner as in Example 13 except that air stirring was performed instead of argon gas stirring.

In Example 14, the sealing bath was thickly cloudy by air agitation, but in Example 13 in which the argon gas was stirred, the sealing bath was slightly cloudy. In addition, the whitened materials of Examples 13 and 14 were able to be filtered off.

Claims (17)

A sealing liquid for an anodic oxidation coating of an aluminum alloy containing a metal salt, a pH buffering agent and a surfactant,
Wherein the metal salt is at least one selected from the group consisting of an alkali metal salt and an alkaline earth metal salt
Sealing solution.
The method according to claim 1,
Wherein the metal salt is a metal salt of at least one metal selected from the group consisting of Na, Mg, K and Ca
Sealing solution.
The method according to claim 1,
Wherein the metal salt is a metal salt of at least one metal selected from the group consisting of Mg and Ca
Sealing solution.
4. The method according to any one of claims 1 to 3,
The metal salt is at least one selected from the group consisting of nitrates, sulfamates, sulfates and nitrates
Sealing solution.
4. The method according to any one of claims 1 to 3,
The metal salt is a nitrate
Sealing solution.
6. The method according to any one of claims 1 to 5,
The pH buffer may be at least one selected from the group consisting of an organic acid salt, an ammonium salt, an amino acid, a borate, an amine compound and a nitrogen-containing heterocyclic compound
Sealing solution.
6. The method according to any one of claims 1 to 5,
The pH buffer is a nitrogen-containing heterocyclic compound
Sealing solution.
8. The method according to any one of claims 1 to 7,
Wherein the surfactant is at least one selected from the group consisting of an anionic surfactant and an amphoteric surfactant
Sealing solution.
8. The method according to any one of claims 1 to 7,
The surfactant is at least one selected from the group consisting of a sulfate-based surfactant, a sulfonate-based surfactant, and a phosphate ester-based surfactant
Sealing solution.
10. The method according to any one of claims 1 to 9,
pH 7.0 to 10.0
Sealing solution.
11. The method according to any one of claims 1 to 10,
Non-nickel metal salt-free
Sealing solution.
12. The method according to any one of claims 1 to 11,
The total content of the metal salt, the pH buffering agent and the surfactant in the encapsulation treatment liquid is preferably 0.2 to 100 g / L
Sealing solution.
1. A concentrated liquid of a sealing liquid for an anodic oxidation coating of an aluminum alloy containing a metal salt, a pH buffering agent and a surfactant,
Wherein the metal salt is at least one selected from the group consisting of an alkali metal salt and an alkaline earth metal salt
concentrate.
A method of sealing an anodic oxide film of an aluminum alloy,
There is provided a method for manufacturing an anodic oxidation coating of an aluminum alloy, comprising the step of immersing an article having an anodized film of an aluminum alloy in a sealing solution for an anodic oxidation coating of an aluminum alloy,
Wherein the sealing treatment liquid contains a metal salt, a pH buffering agent, and a surfactant,
Wherein the metal salt is at least one selected from the group consisting of an alkali metal salt and an alkaline earth metal salt
Sealing method.
15. The method of claim 14,
When the liquid temperature of the sealing liquid is 85 to 100 占 폚
Sealing method.
16. The method according to claim 14 or 15,
When the pH of the sealing liquid is 7.0 to 10.0
Sealing method.
A process for producing a semiconductor device comprising the steps of: performing a sealing treatment by the sealing treatment method according to any one of claims 14 to 16
article.