WO2019058648A1 - Surface treatment agent for dyed anode oxidized film of aluminum or aluminum alloy, and surface treatment method, sealing treatment method, and article using said agent - Google Patents

Surface treatment agent for dyed anode oxidized film of aluminum or aluminum alloy, and surface treatment method, sealing treatment method, and article using said agent Download PDF

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Publication number
WO2019058648A1
WO2019058648A1 PCT/JP2018/021315 JP2018021315W WO2019058648A1 WO 2019058648 A1 WO2019058648 A1 WO 2019058648A1 JP 2018021315 W JP2018021315 W JP 2018021315W WO 2019058648 A1 WO2019058648 A1 WO 2019058648A1
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surface treatment
aluminum
treatment agent
aluminum alloy
agent
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PCT/JP2018/021315
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French (fr)
Japanese (ja)
Inventor
原　健二
朋 森口
駿 杉岡
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奥野製薬工業株式会社
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Priority to CN201880044468.7A priority Critical patent/CN110832122B/en
Priority to JP2018548161A priority patent/JP6490878B1/en
Publication of WO2019058648A1 publication Critical patent/WO2019058648A1/en

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/18—After-treatment, e.g. pore-sealing

Definitions

  • the present invention relates to a surface treatment agent for a dyed anodized film of aluminum or aluminum alloy, a surface treatment method using the same, a sealing treatment method, and an article.
  • Anodized films are formed on light metals such as aluminum or aluminum alloys, and are used in various applications. Depending on the application, performance such as corrosion resistance is required for the anodized film formed on such aluminum etc., and surface treatment is performed to impart these properties.
  • a surface treatment method for imparting corrosion resistance and design to the anodized film formed on the light metal as described above the step of forming the anodized film on the light metal or their alloy, and thereafter, the water-soluble zirconium compound And the like.
  • Patent Document 1 in order to provide design property, applying a design by printing and transcribing a design pattern, such as a wood grain pattern, on the surface after performing the above-mentioned surface treatment is examined.
  • Patent Document 1 does not discuss a method of dyeing an anodic oxide film with a dye, such as a method of immersing an anodic oxide film in a dye aqueous solution containing a dye.
  • staining process by the above-mentioned dye it is not examined also about improving dyeing
  • the present invention has been made in view of the problems of the prior art described above, and is to improve the light resistance of the anodized film of aluminum or aluminum alloy dyed with a dye, and to improve the dye fixation. It is an object of the present invention to provide a surface treatment agent that can be used as well as a surface treatment method.
  • the present inventor has intensively studied to achieve the above-mentioned purpose.
  • the above object can be achieved by using a surface treatment agent containing a zirconium fluoride salt and having a pH of 3.4 or less as the surface treatment agent of the dyed anodic oxide film of aluminum or aluminum alloy.
  • the present invention has been completed.
  • the present invention relates to the following surface treatment agent for anodized film of dyed aluminum or aluminum alloy, surface treatment method using the same, sealing method and article.
  • Item 3. The surface treatment agent according to item 1 or 2, further comprising a metal oxide salt not containing fluorine.
  • the surface treatment agent according to any one of Items 1 to 4 further comprising an anionic surfactant. 6.
  • a method for surface treatment of a dyed anodized film of aluminum or aluminum alloy comprising: (1) Step 1 of dyeing an anodic oxide film of aluminum or aluminum alloy, and (2) Step 2 of immersing the dyed anodic oxide film in a surface treatment agent to perform surface treatment;
  • a surface treatment method comprising a zirconium fluoride salt and having a pH of 3.4 or less. 7.
  • the surface treatment method according to Item 6 wherein the pH of the surface treatment agent is 2.3 to 2.8.
  • Item 9 A method for surface treatment of a dyed anodized film of aluminum or aluminum alloy, comprising: (1) Step 1 of dyeing an anodic oxide film of aluminum or aluminum alloy, and (2) Step 2 of immersing the dyed anodic oxide film in a surface treatment agent to perform surface treatment;
  • a surface treatment method comprising a zirconium fluoride salt and having a pH of
  • the sealing treatment method of the anodic oxidation film of aluminum or aluminum alloy which has the process 3 of sealing the anodic oxidation film of aluminum or aluminum alloy surface-treated by the surface treatment method in any one of claim 6-9 .
  • the surface of the anodized film of dyed aluminum or aluminum alloy is subjected to surface treatment using the surface treatment agent to obtain excellent dye fixing property to the anodized film. It is possible to impart an excellent light fastness by suppressing fading when the anodized film is irradiated with light.
  • the anodic oxide film of aluminum or aluminum alloy is surface-treated by the above-mentioned surface treatment method, and excellent dyeing fixability is imparted to the anodic oxide film before sealing treatment. It is possible to suppress fading when light is irradiated to the anodized film after sealing treatment, and to exhibit excellent light resistance.
  • the anodic oxide film of aluminum or aluminum alloy surface-treated by the above surface treatment method is sealed by the above sealing method, so that the anodic oxide film of the article is dyed and fixable It is possible to show excellent light resistance by suppressing fading when the anodic oxide film of the article is irradiated with light.
  • the surface treatment agent of the anodized film of dyed aluminum or aluminum alloy of the present invention (hereinafter, also simply referred to as "surface treatment agent”) contains a zirconium fluoride salt and has a pH of 3.4. It is below.
  • the surface treatment of the anodized film of aluminum or aluminum alloy dyed with the surface treatment agent of the present invention is not clear about the reason why the anodized film can be provided with excellent light resistance and dye fixing properties. , It is guessed as follows. That is, by coating the surface of the anodized film of the dyed aluminum or aluminum alloy with the surface treatment agent of the present invention, a film of ZrO 2 is formed on the surface of the anodized film, and sealing in a later step.
  • the exudation of the dye is suppressed at the time of processing and the like, and excellent dye fixation can be exhibited.
  • the ZrO 2 film formed on the surface of the anodized film can suppress the decomposition of the dye due to light such as ultraviolet light irradiated on the surface of the anodized film, and can exhibit excellent light resistance. Be done.
  • the surface treatment agent of the present invention has a pH of 3.4 or less.
  • pH of the surface treatment agent exceeds 3.4, sufficient dyeing fixation can not be obtained. 3.0 or less are preferable and 2.8 or less are more preferable. Moreover, 2.0 or more are preferable and, as for pH, 2.3 or more are more preferable.
  • the lower limit of the pH is in the above range, the light resistance and the dye fixation are further improved.
  • zirconium fluoride salt The zirconium fluoride salt is not particularly limited, and ammonium zircon fluoride, potassium zircon fluoride, sodium zircon fluoride, zircon hydrofluoric acid and the like can be used. Among these, zircon ammonium fluoride and zircon potassium fluoride are preferable, and zircon ammonium fluoride is more preferable, from the viewpoint that the light resistance and the dye fixation are further excellent.
  • the said zirconium fluoride salt can be used individually by 1 type or in mixture of 2 or more types.
  • the content of the zirconium fluoride salt in the surface treatment agent is not particularly limited, but 0.1 to 100 g / L is preferable, and 0.2 to 20 g / L is more preferable.
  • the lower limit of the content of the zirconium fluoride salt is in the above range, the light resistance is further improved.
  • the upper limit of content of a zirconium fluoride salt is the said range, it is excellent at the point of color loss suppression in the case of surface treatment.
  • the surface treatment agent of the present invention preferably further contains a metal oxide salt not containing fluorine. Even when the surface treatment of a deep dyed article dyed in a dark color such as black is performed by containing a metal oxide salt not containing fluorine, the appearance defect of the surface of the anodized film is made even more sufficiently. It can be suppressed.
  • the metal which forms the metal oxide salt which does not contain a fluorine is not specifically limited, Metal oxide salts, such as nickel, cobalt, titanium, a zirconium, cesium, tantalum, vanadium, niobium, are mentioned.
  • an inorganic acid salt is preferable as a metal oxide salt which does not contain a fluorine.
  • the surface treatment agent can exhibit more excellent dye fixation.
  • the inorganic acid that forms the inorganic acid salt is not particularly limited, and examples thereof include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, boric acid and the like.
  • the metal oxide salts not containing fluorine may be used singly or in combination of two or more.
  • the content of the fluorine-free metal oxide salt in the surface treatment agent is not particularly limited, and is preferably 0.1 to 10 g / L, and more preferably 0.2 to 1 g / L.
  • the content of the metal oxide salt not containing fluorine is in the above-mentioned range, it is possible to more sufficiently suppress the appearance defect of the surface of the anodized film.
  • the surface treatment agent of the present invention preferably further contains a pH buffer.
  • a pH buffer By containing the pH buffer, the dye fixation can be further improved, and powder blowing on the surface of the anodized film and fogging appearance defects can be suppressed.
  • the pH buffer is not particularly limited, and conventionally known pH buffers can be used.
  • pH buffers include amino acids, organic acid salts, ammonium salts, borates, amine compounds, nitrogen-containing heterocyclic compounds and the like.
  • amino acids are preferable in that they can further improve the dye-fixing property and can suppress powder blowing and fogging appearance defects on the surface of the anodized film.
  • amino acids examples include glutamic acid, glycine, alanine, arginine, cysteine, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, valine, aspartic acid and the like and salts thereof.
  • glutamic acid and a salt thereof, glycine and a salt thereof, histidine and a salt thereof, and aspartic acid and a salt thereof are preferable in view of pH buffering action, and glycine, glutamic acid and aspartic acid and a salt thereof are more preferable.
  • organic acid salts include salts of carboxylic acids and oxycarboxylic acids.
  • the carbon number of the above-mentioned carboxylic acid and oxycarboxylic acid is preferably 4 or less.
  • sodium salt and potassium salt are mentioned as said salt.
  • Ammonium salts include ammonium salts of organic acids and ammonium salts of inorganic acids.
  • Examples of ammonium salts of organic acids include ammonium salts of carboxylic acids and oxycarboxylic acids.
  • the carbon number of the above-mentioned carboxylic acid and oxycarboxylic acid is preferably 4 or less.
  • ammonium salt of inorganic acid ammonium sulfate, ammonium nitrate, ammonium sulfamate and the like can be mentioned.
  • borate sodium borate, potassium borate, ammonium borate and the like can be mentioned.
  • Examples of the amine compound include monoethanolamine, diethanolamine, and ethanolamine which is triethanolamine, and further, alkylamines, aromatic amines, water-soluble carbonylamines such as urea, and the like.
  • the nitrogen-containing heterocyclic compound includes 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.
  • nitrogen-containing heterocyclic compound examples include ethyleneimine ring, azirine ring, azetidine ring, azeto ring, pyrrolidine ring, pyrrole ring, piperidine ring, pyridine ring, hexamethyleneimine ring, azatropylidene ring, imidazole ring, pyrazole ring, oxazole
  • pyrrolidine ring, pyrrole ring, piperidine ring, pyridine ring, hexamethyleneimine ring, azatropylidene ring, imidazole ring, pyrazole ring, oxazole ring, imidazoline ring, pyrazine ring, morpholine ring, pteridine ring, purine ring and the like are included.
  • Nitrogen-containing heterocyclic compounds are preferred.
  • nitrogen-containing heterocyclic compounds examples include ethyleneimine, azirine, azetidine, azeto, pyrrolidine, pyrrole, piperidine, pyridine, hexamethyleneimine, azatropiridene, imidazole, pyrazole, oxazole, imidazoline, pyrazine, morpholine, pteridine, purine and the like. And compounds in which an amino group or a methyl group is added to these skeletons can be used.
  • a cyclic 5- or 7-membered heterocyclic compound having one or two nitrogen atoms as hetero atoms in the ring constituting atoms and consisting of carbon or one hetero oxygen and carbon is preferable, and specifically Compounds such as pyrrolidine, pyrrole, piperidine, pyridine, hexamethyleneimine, azatropiridene, imidazole, pyrazole, oxazole, imidazoline, pyrazine, morpholine and the like and compounds having a cyclic structure as a basic structure can be mentioned.
  • compounds having a heavy polycyclic structure and four or more heteroatom nitrogens for example, compounds such as purine and pteridine and a compound group having a multicyclic skeleton as a basic structure are also preferable.
  • compounds such as purine and pteridine and a compound group having a multicyclic skeleton as a basic structure are also preferable.
  • 5- to 6-membered rings are more preferable, and compounds such as pyrrolidine, pyrrole, piperidine, pyridine, imidazole, pyrazole, oxazole, imidazoline, pyrazine, morpholine and compounds having a cyclic structure as a basic structure can be mentioned.
  • compounds such as pyrrole, pyridine, imidazole, pyrazole, oxazole, imidazoline, pyrazine and the like having a double bond in the ring and compounds having a cyclic structure as a basic structure are particularly preferable.
  • a substituent which comprises these compound groups an amino group, a methyl group, etc. are mentioned, You may use the compound group which these substituents added.
  • aminopyridines such as 2-aminopyridine, 4-aminopyridine and the like, methylimidazole such as 2-methylimidazole and the like are mentioned as particularly preferable ones.
  • pyridine, imidazole, aminopyridine, methylimidazole and the like are most preferable.
  • the above pH buffers can be used singly or in combination of two or more.
  • the concentration of the pH buffer in the surface treatment agent is not particularly limited, and is preferably 0.1 to 20 g / L, and more preferably 0.2 to 5 g / L.
  • concentration of the pH buffer is in the above-mentioned range, the surface treatment agent can exhibit excellent pH bufferability, and color stains of the dyed product generated due to the concentration of the pH buffer being too high are suppressed. Be done.
  • the surface treatment agent of the present invention preferably further contains an anionic surfactant.
  • an anionic surfactant By containing the anionic surfactant, the dye fixation can be further improved, and powder blowing on the surface of the anodized film and fogging appearance defects can be suppressed.
  • the anionic surfactant is not particularly limited, and a sulfate surfactant, a sulfonate surfactant, a sulfosuccinic acid surfactant, a phosphorus surfactant and the like can be used.
  • sulfate type surfactant aromatic sulfate type surfactant, aliphatic sulfate type surfactant, etc. are mentioned.
  • aromatic sulfate surfactant examples include polyoxyethylene alkyl phenyl ether sulfate.
  • aromatic sulfate surfactant examples include polyoxyethylene alkyl phenyl ether sulfate.
  • aliphatic sulfate type surfactant a polyoxyethylene alkyl ether sulfate is mentioned, for example.
  • an aromatic sulfonate surfactant As a sulfonate surfactant, an aromatic sulfonate surfactant and the like can be mentioned.
  • aromatic sulfonate surfactant examples include aromatic sulfonate compounds such as benzene sulfonate and naphthalene sulfonate, and aromatic sulfonate backbones such as benzene sulfonate and naphthalene sulfonate.
  • an alkyl group a polyoxyethylene group, a polyoxyethylene alkyl ether group, a carboxyl group, a carbonyl group, a hydroxyl group, an alcohol group, an alkylene group such as a vinyl group or an allyl group or a group having multiple bonds, and a further sulfonic acid group
  • an alkyl group a polyoxyethylene group, a polyoxyethylene alkyl ether group, a carboxyl group, a carbonyl group, a hydroxyl group, an alcohol group, an alkylene group such as a vinyl group or an allyl group or a group having multiple bonds, and a further sulfonic acid group
  • Compounds and the like can be mentioned, and furthermore, polycondensation products of these compounds with formalin and the like, and copolymers and the like can be mentioned.
  • aromatic sulfonate-based surfactants include, for example, alkylbenzene sulfonates, alkyl naphthalene sulfonates, polycondensates of formalins thereof, formalin such as polycondensates of naphthalene sulfonates, alkylene benzene sulfonates Examples thereof include salts and copolymers from alkylene naphthalene sulfonates and the like.
  • aromatic sulfonate-based surfactant examples include compounds in which a plurality of phenyl sulfonates such as diphenyl ether disulfonates are ether-bonded, and the compounds may be selected from alkyl groups, polyoxyethylene groups, poly The compound which the oxyethylene alkyl ether group etc. substituted is mentioned.
  • aromatic sulfonate surfactants include alkyl diphenyl ether disulfonate and the like.
  • sulfosuccinic acid surfactants include those in which an alkyl group or an aromatic ring is bonded to sulfosuccinic acid. Specifically, alkyl sulfosuccinic acid, dialkyl sulfosuccinic acid, alkyl diphenyl ether disulfo succinic acid and the like and salts thereof can be mentioned.
  • a phosphorus surfactant a phosphate ester surfactant, a phosphate ester salt surfactant, etc.
  • a phosphate ester surfactant a phosphate ester salt surfactant, etc.
  • polyoxyethylene alkyl ether phosphate, polyoxyethylene alkylenated phenyl ether phosphate, alkyl phosphate and the like and salts thereof can be mentioned.
  • a sulfonate-based surfactant is preferable.
  • 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 surface treatment agent is not particularly limited, and 10 mg / L to 10 g / L is preferable, and 20 mg / L to 5 g / L is more preferable. When the concentration of the surfactant is in the above range, the dye fixation is further improved.
  • the surface treatment agent of the present invention may further contain a pH adjuster.
  • the pH adjuster is not particularly limited, and conventionally known pH adjusters can be used.
  • pH adjusters for reducing the surface treatment agent to adjust to the acidic side include dilute aqueous solutions of acetic acid, sulfamic acid, sulfuric acid, nitric acid, organic sulfonic acid and the like.
  • acetic acid sulfamic acid
  • sulfuric acid nitric acid
  • organic sulfonic acid nitric acid
  • nitric acid is preferable in that the dye fixation is further improved.
  • Examples of the pH adjuster for raising the pH of the surface treatment agent include aqueous ammonia, aqueous sodium hydroxide solution, aqueous potassium hydroxide solution and the like. Among these, ammonia water is preferable in that the dye fixation is further improved.
  • the said pH adjuster can be used individually by 1 type or in mixture of 2 or more types.
  • the concentration of the pH adjuster in the surface treatment agent is not particularly limited, and is preferably 0 to 20 g / L, more preferably 0 to 10 g / L, and still more preferably 0 to 5 g / L.
  • concentration of the pH adjusting agent is in the above range, the dye fixation is further improved.
  • the surface treatment agent of the present invention may optionally contain an additive component such as an antifungal agent and a complexing agent in order to further improve the dye fixing property and the practicality of using the surface treatment agent.
  • an additive component such as an antifungal agent and a complexing agent
  • the additive include fungicides such as benzoic acid and benzoate; and complexing agents such as citric acid and citrate.
  • fungicides such as benzoic acid and benzoate
  • complexing agents such as citric acid and citrate.
  • a commercially available fungicide for example, "TAC mold colon" (manufactured by Okuno Pharmaceutical Co., Ltd.) may be added.
  • the other components are not particularly limited as long as the surface treatment agent of the present invention contains a zirconium fluoride salt, it is preferably an aqueous solution containing the above-mentioned components.
  • the surface treatment method of the present invention is a surface treatment method of dyed anodized film of aluminum or aluminum alloy, and (1) step 1 of dyeing anodized film of aluminum or aluminum alloy, and (2) Step 2 of immersing a dyed anodic oxide film in a surface treatment agent to perform surface treatment, the surface treatment agent containing a zirconium fluoride salt and having a pH of 3.4 or less It is a surface treatment method.
  • Step 1 is a step of dyeing an anodized film of aluminum or an aluminum alloy.
  • the anodized film of aluminum or aluminum alloy to be subjected to the dyeing process may be an anodized film obtained by applying a known anodizing method using sulfuric acid, oxalic acid or the like to general aluminum or aluminum alloy. Just do it.
  • the aluminum alloy is not particularly limited, and various aluminum-based alloys can be targets for anodic oxidation. Specific examples of the aluminum alloy include wrought alloys based on JIS-A series 1 to 7 specified in JIS, cast materials shown on each series of AC and ADC, and die cast materials. Examples include various aluminum-based alloy groups as a representative.
  • an aqueous solution with a sulfuric acid concentration of about 100 g / L to about 400 g / L and a liquid temperature of about 0 to 30 ° C. and 0.5 to 4 A / dm 2 There is a method of performing electrolysis at a certain anodic current density.
  • the coloring by dye is mentioned.
  • coloring by dye the method of immersing an anodic oxide film in conventionally well-known dye aqueous solution is mentioned.
  • dye aqueous solution those marketed as dyes for anodic oxidation film of aluminum or aluminum alloy can be used, and, for example, anionic dyes and the like can be mentioned.
  • the temperature of the aqueous dye solution is preferably 10 to 70 ° C., and more preferably 20 to 60 ° C. Further, the concentration of the dye in the aqueous dye solution and the immersion time may be appropriately set according to the desired color tone of the dye and the color depth.
  • the anodized film of aluminum or aluminum alloy is dyed in the step 1 described above.
  • Step 2 is a step of immersing the dyed anodic oxide film in a surface treatment agent to carry out surface treatment.
  • the surface treatment agent described above may be used as the surface treatment agent.
  • the aluminum or aluminum alloy in which the anodized film is partially formed may be dipped in the surface treatment agent.
  • the aluminum or aluminum alloy is joined to another member to form an article, the article may be immersed in the surface treatment agent.
  • the temperature of the surface treatment agent at the time of immersing the anodized film in the surface treatment agent is preferably 10 to 70 ° C., and more preferably 30 to 50 ° C. When the temperature of the surface treatment agent is in the above range, the light resistance and dye fixation of the anodized film are further improved.
  • the immersion time for immersing the anodized film in the surface treatment agent is preferably 1 to 30 minutes, and more preferably 2 to 10 minutes.
  • the lower limit of the immersion time is in the above range, the light resistance and dye fixation of the anodized film are further improved.
  • the upper limit of immersion time is the said range, it is excellent in production efficiency.
  • step 2 after the dyeing process of step 1, the anodized film of aluminum or aluminum alloy may be thoroughly washed with water, dried and then dipped in the surface treatment agent. This further improves the dyeing and fixing properties of the anodized film.
  • the anodic oxide film is surface-treated by the process 2 described above.
  • the sealing method of the present invention is a method of sealing an anodic oxide film, which has a step 3 of sealing the anodic oxide film surface-treated by the surface treatment method.
  • a sealing treatment method a method of immersing an anodic oxide film of aluminum or an aluminum alloy surface-treated by the above-mentioned surface treatment method in a sealing treatment solution is preferable.
  • the sealing solution containing metal salt is mentioned.
  • the metal contained in the metal salt is preferably an alkali metal, an alkaline earth metal or a transition metal, and specifically, Li, Be, Na, Mg, K, Ca, Rb, Sr, Cs, Ba, Fr, Ra, Zr, Mn, Fe, Ni, Co can be mentioned.
  • metal salts of Na, Mg, K, Ca, Ba, Mn and Ni are more preferable in that the anodic oxide film of sealed aluminum or aluminum alloy is excellent in corrosion resistance, Mg, Ca, Mn, Metal salts of Ni are more preferred.
  • the metals contained in the metal salt can be used singly or in combination of two or more.
  • the concentration of the metal salt in the sealing solution is not particularly limited, and is preferably 0.001 to 1 mol / L, and more preferably 0.003 to 0.3 mol / L.
  • concentration of the metal salt is in the above range, the sealing solution can exhibit sufficient sealing performance, and the corrosion resistance of the anodic oxide film of aluminum or aluminum alloy sealed by the sealing solution is more enhanced. Improve further.
  • the sealing solution may contain additive components such as a pH buffer and a surfactant in order to improve the sealing performance (appearance, corrosion resistance, etc.).
  • additives include pH buffers or pH adjusters such as acetic acid, acetate, nitric acid, nitrate, benzoic acid and benzoate; and sulfonic acid-based dispersants such as naphthalene sulfonic acid formalin condensate sodium salt and the like.
  • the pH of the sealing solution is usually 5.0 to 8.0, preferably 5.3 to 6.0.
  • the pH of the sealing solution may be adjusted to be in the above pH range using, for example, an acid such as acetic acid, nitric acid, benzoic acid or sulfuric acid; or an alkali such as sodium hydroxide, sodium carbonate or aqueous ammonia.
  • the temperature of the sealing solution (processing temperature) is usually about 80 ° C. to boiling point, preferably about 85 ° C. to boiling point.
  • the immersion time is usually about 1 minute to 60 minutes, preferably about 3 minutes to 30 minutes.
  • the sealing solution may contain additive components such as a mildewproofing agent and a complexing agent as needed in order to improve the sealing performance and the practicality of use of the solution.
  • additive include fungicides such as benzoic acid and benzoate; and complexing agents such as citric acid and citrate.
  • fungicides such as benzoic acid and benzoate
  • complexing agents such as citric acid and citrate.
  • a commercially available fungicide for example, "TAC mold colon" (manufactured by Okuno Pharmaceutical Co., Ltd.) may be added.
  • the other components are not particularly limited as long as the sealing solution contains the above-mentioned metal salt, pH buffer, surfactant and the like, it is preferably an aqueous solution containing the above-mentioned components.
  • the anodized film of aluminum or aluminum alloy is surface-treated by the above-mentioned surface treatment method, and excellent dyeing fixability is imparted to the anodic oxide film before sealing treatment.
  • Article The article of the present invention is an article having an anodized film of aluminum or aluminum alloy sealed by the above-mentioned sealing method.
  • the article is not particularly limited as long as it has an anodized film of aluminum or aluminum alloy sealed by the above-mentioned sealing method, and, for example, an exterior of an electronic device, an exterior of a cosmetic product, etc. Can be mentioned.
  • the anodic oxide film of aluminum or aluminum alloy surface-treated by the above-mentioned surface treatment method is sealed by the above-mentioned pore-sealing treatment method, so the anodic oxide film of the article is excellent in dyeing and fixing properties In addition, it is possible to suppress fading when the anodic oxide film of the article is irradiated with light and to exhibit excellent light resistance.
  • Anodized and dyed aluminum alloy test pieces used in the following examples and comparative examples were manufactured according to the following manufacturing conditions.
  • a test piece of aluminum alloy (JIS A1050P plate) is degreased by immersing in a weak alkaline degreasing solution (Okino Pharmaceutical Industry Co., Ltd. Top Alclean 404 (trade name) 30 g / L aqueous solution, bath temperature 60 ° C.) for 5 minutes After washing with water, anodic oxidation is performed in an anodic oxidation bath (containing free sulfuric acid 180 g / L and dissolved aluminum 8.0 g / L) containing sulfuric acid as the main component (bath temperature 20 ° C. ⁇ 1 ° C., anodic current density: 1 a / dm) 2 , electrolysis time: 30 minutes, film thickness: about 10 ⁇ m).
  • a weak alkaline degreasing solution (Okino Pharmaceutical Industry Co., Ltd. Top Alclean 404 (trade name) 30 g / L aqueous solution, bath temperature 60 ° C.) for 5 minutes
  • anodic oxidation is performed in
  • the anodized film obtained is washed with water, then washed with water, dipped in an aqueous solution of the following dye (bath temperature 55 ° C.) for 1 minute to dye, and washed with water, anodized and dyed aluminum alloy test pieces ( , “Anodized-dyed test piece”) was obtained.
  • the dye used for dyeing, and the concentration and immersion time when using the dye are as follows: TAC BLACK-GLH (5 g / L, 3 minutes); TAC RED-BLH (5 g / L, 3 minutes); TAC YELLOW-RHM (5 g / L, 3 minutes); TAC ORANGE-LH (5 g / L, 3 minutes); TAC YELLOR-SGL (1 g / L, 1 minute).
  • the said dye used the Okino pharmaceutical industry Co., Ltd. product TAC dye in all.
  • Examples 1 to 5 Each anodized-stained test piece prepared using the dyes shown in Tables 1 and 2 was made of 1.2 g / L of ammonium ammonium fluoride, 1 g / L of glycine, and 0.4 g / L of metal oxide salt containing no fluorine.
  • the substrate was immersed for 3 minutes in a surface treatment agent (bath temperature 45 ° C.) containing an aqueous solution adjusted to pH 2.5 with nitric acid, washed with water and surface treated.
  • a surface treatment agent bath temperature 45 ° C.
  • a sealing treatment agent bath temperature 92 ° C.
  • a sealing treatment agent consisting of an aqueous solution of pH 5.7 containing 40 ml / L of Top Seal H-298 manufactured by Okuno Pharmaceutical Co., Ltd. for 15 minutes, followed by washing with water and drying.
  • Example 6 In the same manner as in Examples 1 to 5 except that the metal oxide salt not containing fluorine is not added, the anodized-stained specimen is surface-treated, immersed in a sealing agent, washed with water and dried. The
  • Example 7 The anodized-stained specimen was surface-treated in the same manner as in Examples 1 to 5 except that the pH of the surface treatment solution was adjusted to 3.0, immersed in a sealing agent, washed with water and dried. .
  • Examples 1 to 4 and 6 and Comparative Examples 1 to specimen after sealing treatment obtained in 4 L *, a *, b * an integrating sphere spectrophotometer (X-rite Co. SP64 , A light source D65, a field of view of 10 degrees, and specular light), and these were used as reference values.
  • the test pieces obtained in the above Examples 1 to 4 and 6 and Comparative Examples 1 to 4 were irradiated with an irradiation temperature of 65 using a light resistance tester (Suntest XLS + manufactured by Atlas Corporation) using a xenon lamp as a light source. The light was irradiated for up to 400 hours under the conditions of ° C.
  • Dyeing Fixability L *, a *, b * of the test pieces obtained in the above Examples 5 and 7 and Comparative Example 5 are integrated sphere spectrophotometer (SP64 manufactured by X-rite Co., light source D65, containing regular reflection light) ) And the dye fixation was evaluated. The higher the b *, the darker the yellow color, indicating that the fixing ability of the TAC YELLOW-SGL is high.
  • the photograph of the test piece after each irradiation time in the light resistance test of Example 3 and Comparative Example 3 is shown in FIG. Moreover, the photograph of the test piece after each irradiation time in the light resistance test of Example 4 and Comparative Example 4 is shown in FIG. From FIGS. 1 and 2, in Examples 3 and 4 in which the surface treatment was performed, fading was suppressed even after 400 hours, and it was found that the light resistance was excellent. On the other hand, in Comparative Examples 3 and 4 in which the surface treatment was not performed, it was found that the fading becomes remarkable as the irradiation time becomes long, and the light resistance is inferior.
  • the dyeing is performed in the same manner as in Example 1, and then the surface treatment is performed using a surface treatment agent, and the FE-SEM image of the anodized film of the aluminum alloy not subjected to the pore sealing treatment is manufactured by Nippon Denshi Co., Ltd. Photographed under the condition of 50000 times magnification using JSM-6335F.
  • the surface image is shown in FIG. 3 and the cross-sectional image is shown in FIG. It was found from FIG. 4 that a film was formed on the surface of the anodized film by surface treatment.
  • the film formed by the surface treatment was an aggregate of fine particles of about 30 to 100 nm, and the thickness of the film was about 100 nm.
  • Dyeing is carried out in the same manner as in Example 1, and then surface treatment is carried out using a surface treatment agent, and the anodic oxidation film of an aluminum alloy which has not been subjected to sealing treatment by X-ray photoelectron spectroscopy (XPS) the depth profiling was performed on the conditions of sputtering rate in terms of SiO 2 3 nm / min using a ULVAC-pHI Inc. ESCA-SYSTEM ESCA5800ci / SAM. The results are shown in FIG. As shown in FIG. 5, when the sputtering time is short, the concentration of Zr atoms is high, and the concentration of O atoms is also high. Therefore, the film formed on the surface of the anodic oxide film by the surface treatment is a ZrO 2 film. It is believed that there is.
  • XPS X-ray photoelectron spectroscopy
  • Dyeing is carried out in the same manner as in Example 1, then surface treatment is carried out using a surface treatment agent, and anodized film of aluminum alloy not subjected to pore sealing treatment is narrow by X-ray photoelectron spectroscopy (XPS).
  • Scan analysis was performed using ULVAC-PHI ESCA-SYSTEM ESCA 5800 ci / SAM. The results are shown in FIG. From FIG. 6, the peak by narrow scan analysis is in agreement with 182.3 ⁇ 0.3 ev which is a peak of the binding energy of ZrO 2 . From this, it was found that the film formed on the surface of the anodized film by the surface treatment was a ZrO 2 film.

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Abstract

The present invention provides a surface treatment agent and a surface treatment method capable of improving the light resistance and dye fastness of an anode oxidized film of aluminum or an aluminum alloy, the film being dyed with a dye. This surface treatment agent for a dyed anode oxidized film of aluminum or an aluminum alloy is characterized by containing a zirconium fluoride salt and by having a pH of 3.4 or less.

Description

染色された、アルミニウム又はアルミニウム合金の陽極酸化皮膜の表面処理剤及びそれを用いた表面処理方法、封孔処理方法並びに物品Surface treatment agent for dyed anodized film of aluminum or aluminum alloy and surface treatment method using the same, sealing treatment method and article
　本発明は、染色された、アルミニウム又はアルミニウム合金の陽極酸化皮膜の表面処理剤及びそれを用いた表面処理方法、封孔処理方法並びに物品に関する。 The present invention relates to a surface treatment agent for a dyed anodized film of aluminum or aluminum alloy, a surface treatment method using the same, a sealing treatment method, and an article.
　アルミニウム又はアルミニウム合金等の軽金属には、陽極酸化皮膜が形成され、様々な用途に用いられている。このようなアルミニウム等に形成された陽極酸化皮膜には、用途によって耐食性等の性能が要求されており、これらの性能を付与するために、表面処理が行われている。 Anodized films are formed on light metals such as aluminum or aluminum alloys, and are used in various applications. Depending on the application, performance such as corrosion resistance is required for the anodized film formed on such aluminum etc., and surface treatment is performed to impart these properties.
　上述のような軽金属に形成された陽極酸化皮膜に耐食性及び意匠性を付与する表面処理方法として、軽金属又はそれらの合金に対して陽極酸化皮膜を形成する工程と、その後に、水溶性のジルコニウム化合物等の水溶性化合物を含有する水溶液に浸漬する工程を含む表面処理方法が提案されている（例えば、特許文献１参照）。 As a surface treatment method for imparting corrosion resistance and design to the anodized film formed on the light metal as described above, the step of forming the anodized film on the light metal or their alloy, and thereafter, the water-soluble zirconium compound And the like. A surface treatment method including a step of immersing in an aqueous solution containing a water-soluble compound such as is proposed (see, for example, Patent Document 1).
　しかしながら、特許文献１では、意匠性を付与するために、上記表面処理を行った後の表面に木目模様等の意匠模様を印刷、転写することにより模様を付与することが検討されている。特許文献１では、染料を含有する染料水溶液に陽極酸化皮膜を浸漬する方法のように、染料により陽極酸化皮膜を染色処理する方法については検討されていない。また、特許文献１では、上述の染料による染色処理において、染色定着性を向上させることについても検討されていない。 However, in patent document 1, in order to provide design property, applying a design by printing and transcribing a design pattern, such as a wood grain pattern, on the surface after performing the above-mentioned surface treatment is examined. Patent Document 1 does not discuss a method of dyeing an anodic oxide film with a dye, such as a method of immersing an anodic oxide film in a dye aqueous solution containing a dye. Moreover, in patent document 1, in the dyeing | staining process by the above-mentioned dye, it is not examined also about improving dyeing | staining fixing property.
　また、特許文献１では、染料を用いて染色処理された陽極酸化皮膜に耐光性を付与することは検討されていない。上述のように染料を用いて陽極酸化皮膜に染色処理を施した場合、紫外線等の光に曝されることにより染料の色味が退色し、色が薄くなるという問題がある。 Moreover, in patent document 1, giving light resistance to the anodic oxide film dyed and processed using dye is not examined. As described above, when the anodized film is subjected to a dyeing process using a dye, there is a problem that the color tone of the dye is faded by being exposed to light such as ultraviolet light, and the color is lightened.
　従って、染料により染色処理されたアルミニウム又はアルミニウム合金の陽極酸化皮膜の耐光性を向上させ、且つ、染色定着性を向上させることができる表面処理剤、及び表面処理方法の開発が求められている。 Therefore, development of a surface treatment agent and a surface treatment method capable of improving the light resistance of the anodized film of aluminum or aluminum alloy dyed with a dye and improving the dye fixation is required.
特開２００６－１８３０６５号公報JP, 2006-183065, A
　本発明は、上記した従来技術の問題点に鑑みてなされたものであり、染料により染色処理されたアルミニウム又はアルミニウム合金の陽極酸化皮膜の耐光性を向上させ、且つ、染色定着性を向上させることができる表面処理剤、及び表面処理方法を提供することを目的とする。 The present invention has been made in view of the problems of the prior art described above, and is to improve the light resistance of the anodized film of aluminum or aluminum alloy dyed with a dye, and to improve the dye fixation. It is an object of the present invention to provide a surface treatment agent that can be used as well as a surface treatment method.
　本発明者は、上記した目的を達成すべく鋭意研究を重ねてきた。その結果、染色された、アルミニウム又はアルミニウム合金の陽極酸化皮膜の表面処理剤として、フッ化ジルコニウム塩を含有し、ｐＨが３．４以下である表面処理剤を用いることにより、上記目的を達成できることを見出し、本発明を完成するに至った。 The present inventor has intensively studied to achieve the above-mentioned purpose. As a result, the above object can be achieved by using a surface treatment agent containing a zirconium fluoride salt and having a pH of 3.4 or less as the surface treatment agent of the dyed anodic oxide film of aluminum or aluminum alloy. The present invention has been completed.
　即ち、本発明は、下記の染色されたアルミニウム又はアルミニウム合金の陽極酸化皮膜の表面処理剤及びそれを用いた表面処理方法、封孔処理方法並びに物品に関する。
１．染色された、アルミニウム又はアルミニウム合金の陽極酸化皮膜の表面処理剤であって、フッ化ジルコニウム塩を含有し、ｐＨが３．４以下であることを特徴とする、表面処理剤。
２．ｐＨが２．３～２．８である、項１に記載の表面処理剤。
３．更に、フッ素を含有しない金属酸化物塩を含む、項１又は２に記載の表面処理剤。
４．更に、ｐＨ緩衝剤を含有する、項１～３のいずれかに記載の表面処理剤。
５．更に、アニオン系界面活性剤を含有する、項１～４のいずれかに記載の表面処理剤。
６．染色された、アルミニウム又はアルミニウム合金の陽極酸化皮膜の表面処理方法であって、
（１）アルミニウム又はアルミニウム合金の陽極酸化皮膜を染色処理する工程１、及び、
（２）染色された陽極酸化皮膜を表面処理剤に浸漬して表面処理を行う工程２を有し、
　表面処理剤はフッ化ジルコニウム塩を含有し、且つ、ｐＨが３．４以下であることを特徴とする表面処理方法。
７．表面処理剤のｐＨは２．３～２．８である、項６に記載の表面処理方法。
８．表面処理剤の温度は１０～７０℃である、項６又は７に記載の表面処理方法。
９．表面処理剤への浸漬時間は１～３０分である、項６～８のいずれかに記載の表面処理方法。
１０．項６～９のいずれかに記載の表面処理方法により表面処理された、アルミニウム又はアルミニウム合金の陽極酸化皮膜を封孔処理する工程３を有する、アルミニウム又はアルミニウム合金の陽極酸化皮膜の封孔処理方法。
１１．項１０に記載の封孔処理方法により封孔処理された、アルミニウム又はアルミニウム合金の陽極酸化皮膜を有する物品。 That is, the present invention relates to the following surface treatment agent for anodized film of dyed aluminum or aluminum alloy, surface treatment method using the same, sealing method and article.
1. A surface treatment agent of a dyed anodized film of aluminum or aluminum alloy, wherein the surface treatment agent contains a zirconium fluoride salt and has a pH of 3.4 or less.
2. Item 2. The surface treatment agent according to item 1, wherein the pH is 2.3 to 2.8.
3. Item 3. The surface treatment agent according to item 1 or 2, further comprising a metal oxide salt not containing fluorine.
4. The surface treatment agent according to any one of Items 1 to 3, further comprising a pH buffer.
5. The surface treatment agent according to any one of Items 1 to 4, further comprising an anionic surfactant.
6. What is claimed is: 1. A method for surface treatment of a dyed anodized film of aluminum or aluminum alloy, comprising:
(1) Step 1 of dyeing an anodic oxide film of aluminum or aluminum alloy, and
(2) Step 2 of immersing the dyed anodic oxide film in a surface treatment agent to perform surface treatment;
A surface treatment method comprising a zirconium fluoride salt and having a pH of 3.4 or less.
7. The surface treatment method according to Item 6, wherein the pH of the surface treatment agent is 2.3 to 2.8.
8. Item 8. The surface treatment method according to Item 6 or 7, wherein the temperature of the surface treatment agent is 10 to 70 ° C.
9. Item 9. The surface treatment method according to any one of Items 6 to 8, wherein the immersion time in the surface treatment agent is 1 to 30 minutes.
10. The sealing treatment method of the anodic oxidation film of aluminum or aluminum alloy which has the process 3 of sealing the anodic oxidation film of aluminum or aluminum alloy surface-treated by the surface treatment method in any one of claim 6-9 .
11. 11. An article having an anodized film of aluminum or aluminum alloy sealed by the sealing method according to item 10.
　本発明の表面処理剤及び表面処理方法によれば、染色されたアルミニウム又はアルミニウム合金の陽極酸化皮膜に当該表面処理剤を用いて表面処理を行うことにより、陽極酸化皮膜に優れた染色定着性を付与することができ、且つ、陽極酸化皮膜に光が照射された際の退色が抑制されて、優れた耐光性を示すことができる。 According to the surface treatment agent and the surface treatment method of the present invention, the surface of the anodized film of dyed aluminum or aluminum alloy is subjected to surface treatment using the surface treatment agent to obtain excellent dye fixing property to the anodized film. It is possible to impart an excellent light fastness by suppressing fading when the anodized film is irradiated with light.
　また、本発明の封孔処理方法によれば、アルミニウム又はアルミニウム合金の陽極酸化皮膜が上記表面処理方法により表面処理されており、封孔処理前の陽極酸化皮膜に優れた染色定着性を付与することができ、且つ、封孔処理後の陽極酸化皮膜に光が照射された際の退色が抑制されて、優れた耐光性を示すことができる。 Moreover, according to the sealing treatment method of the present invention, the anodic oxide film of aluminum or aluminum alloy is surface-treated by the above-mentioned surface treatment method, and excellent dyeing fixability is imparted to the anodic oxide film before sealing treatment. It is possible to suppress fading when light is irradiated to the anodized film after sealing treatment, and to exhibit excellent light resistance.
　更に、本発明の物品は、上記表面処理方法により表面処理されたアルミニウム又はアルミニウム合金の陽極酸化皮膜が、上記封孔処理方法により封孔処理されているので、物品の陽極酸化皮膜が染色定着性に優れており、且つ、物品の陽極酸化皮膜に光が照射された際の退色が抑制されて、優れた耐光性を示すことができる。 Furthermore, in the article of the present invention, the anodic oxide film of aluminum or aluminum alloy surface-treated by the above surface treatment method is sealed by the above sealing method, so that the anodic oxide film of the article is dyed and fixable It is possible to show excellent light resistance by suppressing fading when the anodic oxide film of the article is irradiated with light.
実施例３及び比較例３の耐光性試験における各照射時間後の試験片の写真である。It is a photograph of the test piece after each irradiation time in the light resistance test of Example 3 and Comparative Example 3. 実施例４及び比較例４の耐光性試験における各照射時間後の試験片の写真である。It is a photograph of the test piece after each irradiation time in the light resistance test of Example 4 and Comparative Example 4. アルミニウム合金の陽極酸化皮膜に本発明の表面処理剤を用いて表面処理を行った後の、陽極酸化皮膜の表面のＦＥ-ＳＥＭ像である。It is a FE-SEM image of the surface of the anodized film after the anodized film of the aluminum alloy is surface-treated using the surface treatment agent of the present invention. アルミニウム合金の陽極酸化皮膜に本発明の表面処理剤を用いて表面処理を行った後の、陽極酸化皮膜の断面のＦＥ-ＳＥＭ像である。It is a FE-SEM image of a cross section of the anodized film after the anodized film of aluminum alloy is surface-treated using the surface treatment agent of the present invention. アルミニウム合金の陽極酸化皮膜に本発明の表面処理剤を用いて表面処理を行った後の、陽極酸化皮膜のＸ線光電子分光法（ＸＰＳ）による元素深さ方向分析の結果を示す図である。It is a figure which shows the result of an element depth direction analysis by X ray photoelectron spectroscopy (XPS) of an anodic oxide film after performing surface treatment using a surface treating agent of the present invention to an anodic oxide film of aluminum alloy. アルミニウム合金の陽極酸化皮膜に本発明の表面処理剤を用いて表面処理を行った後の、陽極酸化皮膜のＸ線光電子分光法（ＸＰＳ）によるナロースキャン分析の結果を示す図である。It is a figure which shows the result of narrow scan analysis by X ray photoelectron spectroscopy (XPS) of the anodic oxide film after surface-treating using the surface treating agent of this invention to the anodic oxide film of aluminum alloy.
　以下、本発明について詳細に説明する。 Hereinafter, the present invention will be described in detail.
１．表面処理剤
　本発明の、染色されたアルミニウム又はアルミニウム合金の陽極酸化皮膜の表面処理剤（以下、単に「表面処理剤」とも示す。）は、フッ化ジルコニウム塩を含有し、ｐＨが３．４以下である。本発明の表面処理剤により染色されたアルミニウム又はアルミニウム合金の陽極酸化皮膜を表面処理すれば、当該陽極酸化皮膜に優れた耐光性及び染色定着性を付与することができる理由については明らかではないが、以下のように推測される。すなわち、本発明の表面処理剤を用いて、染色されたアルミニウム又はアルミニウム合金の陽極酸化皮膜を表面処理することにより、当該陽極酸化皮膜の表面にＺｒＯ２の皮膜が形成され、後工程の封孔処理等の際に染料の染み出しが抑制され、優れた染色定着性を示すことができると推測される。また、当該陽極酸化皮膜の表面に形成されたＺｒＯ２の皮膜が、陽極酸化皮膜の表面に照射される紫外線等の光による染料の分解を抑制し、優れた耐光性を示すことができると推測される。 1. Surface Treatment Agent The surface treatment agent of the anodized film of dyed aluminum or aluminum alloy of the present invention (hereinafter, also simply referred to as "surface treatment agent") contains a zirconium fluoride salt and has a pH of 3.4. It is below. The surface treatment of the anodized film of aluminum or aluminum alloy dyed with the surface treatment agent of the present invention is not clear about the reason why the anodized film can be provided with excellent light resistance and dye fixing properties. , It is guessed as follows. That is, by coating the surface of the anodized film of the dyed aluminum or aluminum alloy with the surface treatment agent of the present invention, a film of ZrO 2 is formed on the surface of the anodized film, and sealing in a later step. It is surmised that the exudation of the dye is suppressed at the time of processing and the like, and excellent dye fixation can be exhibited. In addition, it is speculated that the ZrO 2 film formed on the surface of the anodized film can suppress the decomposition of the dye due to light such as ultraviolet light irradiated on the surface of the anodized film, and can exhibit excellent light resistance. Be done.
　本発明の表面処理剤は、ｐＨが３．４以下である。表面処理剤のｐＨが３．４を超えると、十分な染色定着性が得られない。ｐＨは、３．０以下が好ましく、２．８以下がより好ましい。また、ｐＨは、２．０以上が好ましく、２．３以上がより好ましい。ｐＨの下限が上記範囲であることにより、耐光性及び染色定着性がより一層向上する。 The surface treatment agent of the present invention has a pH of 3.4 or less. When the pH of the surface treatment agent exceeds 3.4, sufficient dyeing fixation can not be obtained. 3.0 or less are preferable and 2.8 or less are more preferable. Moreover, 2.0 or more are preferable and, as for pH, 2.3 or more are more preferable. When the lower limit of the pH is in the above range, the light resistance and the dye fixation are further improved.
（フッ化ジルコニウム塩）
フッ化ジルコニウム塩としては特に限定されず、ジルコンフッ化アンモニウム、ジルコンフッ化カリウム、ジルコンフッ化ナトリウム、ジルコンフッ化水素酸等を用いることができる。これらの中でも、耐光性及び染色定着性がより一層優れる点で、ジルコンフッ化アンモニウム、ジルコンフッ化カリウムが好ましく、ジルコンフッ化アンモニウムがより好ましい。上記フッ化ジルコニウム塩は、一種単独で又は二種以上を混合して用いることができる。 (Zirconium fluoride salt)
The zirconium fluoride salt is not particularly limited, and ammonium zircon fluoride, potassium zircon fluoride, sodium zircon fluoride, zircon hydrofluoric acid and the like can be used. Among these, zircon ammonium fluoride and zircon potassium fluoride are preferable, and zircon ammonium fluoride is more preferable, from the viewpoint that the light resistance and the dye fixation are further excellent. The said zirconium fluoride salt can be used individually by 1 type or in mixture of 2 or more types.
　表面処理剤中のフッ化ジルコニウム塩の含有量は特に限定されず、０．１～１００ｇ／Ｌが好ましく、０．２～２０ｇ／Ｌがより好ましい。フッ化ジルコニウム塩の含有量の下限が上記範囲であることにより、耐光性がより一層向上する。また、フッ化ジルコニウム塩の含有量の上限が上記範囲であることにより、表面処理の際の色抜け抑制の点で優れている。 The content of the zirconium fluoride salt in the surface treatment agent is not particularly limited, but 0.1 to 100 g / L is preferable, and 0.2 to 20 g / L is more preferable. When the lower limit of the content of the zirconium fluoride salt is in the above range, the light resistance is further improved. Moreover, when the upper limit of content of a zirconium fluoride salt is the said range, it is excellent at the point of color loss suppression in the case of surface treatment.
（フッ素を含有しない金属酸化物塩）
　本発明の表面処理剤は、更に、フッ素を含有しない金属酸化物塩を含むことが好ましい。フッ素を含有しない金属酸化物塩を含むことにより、黒等の濃い色に染色された濃染色品の表面処理を行った場合であっても、陽極酸化皮膜の表面の外観不良をより一層十分に抑制することができる。 (Fluoride-free metal oxide salt)
The surface treatment agent of the present invention preferably further contains a metal oxide salt not containing fluorine. Even when the surface treatment of a deep dyed article dyed in a dark color such as black is performed by containing a metal oxide salt not containing fluorine, the appearance defect of the surface of the anodized film is made even more sufficiently. It can be suppressed.
　フッ素を含有しない金属酸化物塩を形成する金属は特に限定されず、ニッケル、コバルト、チタン、ジルコニウム、セシウム、タンタル、バナジウム、ニオブ等の金属酸化物塩が挙げられる。 The metal which forms the metal oxide salt which does not contain a fluorine is not specifically limited, Metal oxide salts, such as nickel, cobalt, titanium, a zirconium, cesium, tantalum, vanadium, niobium, are mentioned.
　また、フッ素を含有しない金属酸化物塩としては、無機酸塩が好ましい。無機酸塩を用いることにより、表面処理剤がより一層優れた染色定着性を示すことができる。無機酸塩を形成する無機酸としては特に限定されず、塩酸、硫酸、硝酸、リン酸、ホウ酸等が挙げられる。 Moreover, as a metal oxide salt which does not contain a fluorine, an inorganic acid salt is preferable. By using the inorganic acid salt, the surface treatment agent can exhibit more excellent dye fixation. The inorganic acid that forms the inorganic acid salt is not particularly limited, and examples thereof include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, boric acid and the like.
　上記フッ素を含有しない金属酸化物塩は、一種単独で又は二種以上を混合して用いることができる。 The metal oxide salts not containing fluorine may be used singly or in combination of two or more.
　表面処理剤中のフッ素を含有しない金属酸化物塩の含有量は特に限定されず、０．１～１０ｇ／Ｌが好ましく、０．２～１ｇ／Ｌがより好ましい。フッ素を含有しない金属酸化物塩の含有量が上記範囲であることにより、陽極酸化皮膜の表面の外観不良をより一層十分に抑制することができる。 The content of the fluorine-free metal oxide salt in the surface treatment agent is not particularly limited, and is preferably 0.1 to 10 g / L, and more preferably 0.2 to 1 g / L. When the content of the metal oxide salt not containing fluorine is in the above-mentioned range, it is possible to more sufficiently suppress the appearance defect of the surface of the anodized film.
（ｐＨ緩衝剤）
　本発明の表面処理剤は、更に、ｐＨ緩衝剤を含有することが好ましい。ｐＨ緩衝剤を含有することにより、染色定着性がより一層向上し、且つ、陽極酸化皮膜の表面の粉吹きやカブリ外観不良を抑制することができる。 (PH buffer)
The surface treatment agent of the present invention preferably further contains a pH buffer. By containing the pH buffer, the dye fixation can be further improved, and powder blowing on the surface of the anodized film and fogging appearance defects can be suppressed.
　ｐＨ緩衝剤としては特に限定されず、従来公知のｐＨ緩衝剤を用いることができる。このようなｐＨ緩衝剤としては、例えば、アミノ酸、有機酸塩、アンモニウム塩、ホウ酸塩、アミン化合物、含窒素複素環式化合物等が挙げられる。これらの中でも、染色定着性がより一層向上し、且つ、陽極酸化皮膜の表面の粉吹きやカブリ外観不良を抑制することができる点で、アミノ酸が好ましい。 The pH buffer is not particularly limited, and conventionally known pH buffers can be used. Examples of such pH buffers include amino acids, organic acid salts, ammonium salts, borates, amine compounds, nitrogen-containing heterocyclic compounds and the like. Among these, amino acids are preferable in that they can further improve the dye-fixing property and can suppress powder blowing and fogging appearance defects on the surface of the anodized film.
　アミノ酸としては、グルタミン酸、グリシン、アラニン、アルギニン、システイン、ヒスチジン、イソロイシン、ロイシン、リシン、メチオニン、フェニルアラニン、プロリン、セリン、トレオニン、トリプトファン、チロシン、バリン、アスパラギン酸等やそれらの塩が挙げられる。これらの中でも、ｐＨ緩衝作用の点でグルタミン酸及びその塩、グリシン及びその塩、ヒスチジン及びその塩、アスパラギン酸及びその塩が好ましく、グリシン、グルタミン酸、アスパラギン酸及びそれらの塩がより好ましい。 Examples of amino acids include glutamic acid, glycine, alanine, arginine, cysteine, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, valine, aspartic acid and the like and salts thereof. Among these, glutamic acid and a salt thereof, glycine and a salt thereof, histidine and a salt thereof, and aspartic acid and a salt thereof are preferable in view of pH buffering action, and glycine, glutamic acid and aspartic acid and a salt thereof are more preferable.
　有機酸塩としては、カルボン酸やオキシカルボン酸の塩が挙げられる。上記カルボン酸、オキシカルボン酸の炭素数は４以下が好ましい。また、上記塩としては、ナトリウム塩、カリウム塩が挙げられる。 Examples of organic acid salts include salts of carboxylic acids and oxycarboxylic acids. The carbon number of the above-mentioned carboxylic acid and oxycarboxylic acid is preferably 4 or less. Moreover, sodium salt and potassium salt are mentioned as said salt.
　アンモニウム塩としては有機酸のアンモニウム塩、無機酸のアンモニウム塩が挙げられる。有機酸のアンモニウム塩としては、カルボン酸やオキシカルボン酸のアンモニウム塩が挙げられる。上記カルボン酸、オキシカルボン酸の炭素数は４以下が好ましい。また、無機酸のアンモニウム塩としては、硫酸アンモニウム塩、硝酸アンモニウム塩、スルファミン酸アンモニウム塩等が挙げられる。 Ammonium salts include ammonium salts of organic acids and ammonium salts of inorganic acids. Examples of ammonium salts of organic acids include ammonium salts of carboxylic acids and oxycarboxylic acids. The carbon number of the above-mentioned carboxylic acid and oxycarboxylic acid is preferably 4 or less. Moreover, as an ammonium salt of inorganic acid, ammonium sulfate, ammonium nitrate, ammonium sulfamate and the like can be mentioned.
　ホウ酸塩としては、ホウ酸ナトリウム、ホウ酸カリウム、ホウ酸アンモニウム等が挙げられる。 As the borate, sodium borate, potassium borate, ammonium borate and the like can be mentioned.
　アミン化合物としては、モノエタノールアミン、ジエタノールアミン、トリエタノールアミンであるエタノールアミンが挙げられ、また、アルキルアミン、芳香族アミンや、尿素等の水溶性カルボニルアミン等が挙げられる。 Examples of the amine compound include monoethanolamine, diethanolamine, and ethanolamine which is triethanolamine, and further, alkylamines, aromatic amines, water-soluble carbonylamines such as urea, and the like.
　含窒素複素環式化合物としては、ヘテロ原子として少なくとも１つの窒素原子を含む複素環式化合物、ヘテロ原子として少なくとも１つの窒素原子及び少なくとも１つの酸素原子を含む複素環式化合物が挙げられる。 The nitrogen-containing heterocyclic compound includes 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.
　上記含窒素複素環式化合物としては、エチレンイミン環、アジリン環、アゼチジン環、アゼト環、ピロリジン環、ピロール環、ピペリジン環、ピリジン環、ヘキサメチレンイミン環、アザトロピリデン環、イミダゾール環、ピラゾール環、オキサゾール環、イミダゾリン環、ピラジン環、モルホリン環、プテリジン環、プリン環等を含む含窒素複素環式化合物が挙げられる。これらの中でも、ピロリジン環、ピロール環、ピペリジン環、ピリジン環、ヘキサメチレンイミン環、アザトロピリデン環、イミダゾール環、ピラゾール環、オキサゾール環、イミダゾリン環、ピラジン環、モルホリン環、プテリジン環、プリン環等を含む含窒素複素環式化合物が好ましい。 Examples of the nitrogen-containing heterocyclic compound include ethyleneimine ring, azirine ring, azetidine ring, azeto ring, pyrrolidine ring, pyrrole ring, piperidine ring, pyridine ring, hexamethyleneimine ring, azatropylidene ring, imidazole ring, pyrazole ring, oxazole And nitrogen-containing heterocyclic compounds containing a ring, an imidazoline ring, a pyrazine ring, a morpholine ring, a pteridine ring, a purine ring and the like. Among these, pyrrolidine ring, pyrrole ring, piperidine ring, pyridine ring, hexamethyleneimine ring, azatropylidene ring, imidazole ring, pyrazole ring, oxazole ring, imidazoline ring, pyrazine ring, morpholine ring, pteridine ring, purine ring and the like are included. Nitrogen-containing heterocyclic compounds are preferred.
　上記含窒素複素環式化合物としては、エチレンイミン、アジリン、アゼチジン、アゼト、ピロリジン、ピロール、ピペリジン、ピリジン、ヘキサメチレンイミン、アザトロピリデン、イミダゾール、ピラゾール、オキサゾール、イミダゾリン、ピラジン、モルホリン、プテリジン、プリン等が挙げられ、これらの骨格にアミノ基やメチル基が付加した化合物を用いることができる。これらの中でも環状構成原子に一つまたは二つの窒素原子をヘテロ原子としてもち、炭素または一つのヘテロ原子酸素と炭素からなる環状５員～７員環の複素環式化合物が好ましく、具体的にはピロリジン、ピロール、ピペリジン、ピリジン、ヘキサメチレンイミン、アザトロピリデン、イミダゾール、ピラゾール、オキサゾール、イミダゾリン、ピラジン、モルホリン等の化合物とその環状骨格を基本構造とした化合物群が挙げられる。また、重多環構造をもちヘテロ原子窒素を４つ以上もつもの、例えばプリン、プテリジン等の化合物とその多重環状骨格を基本構造とした化合物群も好ましい。中でも、５～６員環のものが更に好ましく、ピロリジン、ピロール、ピペリジン、ピリジン、イミダゾール、ピラゾール、オキサゾール、イミダゾリン、ピラジン、モルホリン等の化合物とその環状骨格を基本構造とした化合物群が挙げられる。この中でも環内に二重結合を持つピロール、ピリジン、イミダゾール、ピラゾール、オキサゾール、イミダゾリン、ピラジン等の化合物とその環状骨格を基本構造とした化合物群が特に好ましい。これらの化合物群を構成する置換基としてはアミノ基やメチル基等が挙げられ、これらの置換基が付加した化合物群を用いてもよい。例えば２－アミノピリジン、４－アミノピリジン等のアミノピリジン等や、２－メチルイミダゾール等のメチルイミダゾール等が特に好ましいものとして挙げられる。中でも、ピリジン、イミダゾール、アミノピリジン、メチルイミダゾール等が最も好ましい。 Examples of the nitrogen-containing heterocyclic compounds include ethyleneimine, azirine, azetidine, azeto, pyrrolidine, pyrrole, piperidine, pyridine, hexamethyleneimine, azatropiridene, imidazole, pyrazole, oxazole, imidazoline, pyrazine, morpholine, pteridine, purine and the like. And compounds in which an amino group or a methyl group is added to these skeletons can be used. Among them, a cyclic 5- or 7-membered heterocyclic compound having one or two nitrogen atoms as hetero atoms in the ring constituting atoms and consisting of carbon or one hetero oxygen and carbon is preferable, and specifically Compounds such as pyrrolidine, pyrrole, piperidine, pyridine, hexamethyleneimine, azatropiridene, imidazole, pyrazole, oxazole, imidazoline, pyrazine, morpholine and the like and compounds having a cyclic structure as a basic structure can be mentioned. In addition, compounds having a heavy polycyclic structure and four or more heteroatom nitrogens, for example, compounds such as purine and pteridine and a compound group having a multicyclic skeleton as a basic structure are also preferable. Among them, 5- to 6-membered rings are more preferable, and compounds such as pyrrolidine, pyrrole, piperidine, pyridine, imidazole, pyrazole, oxazole, imidazoline, pyrazine, morpholine and compounds having a cyclic structure as a basic structure can be mentioned. Among these, compounds such as pyrrole, pyridine, imidazole, pyrazole, oxazole, imidazoline, pyrazine and the like having a double bond in the ring and compounds having a cyclic structure as a basic structure are particularly preferable. As a substituent which comprises these compound groups, an amino group, a methyl group, etc. are mentioned, You may use the compound group which these substituents added. For example, aminopyridines such as 2-aminopyridine, 4-aminopyridine and the like, methylimidazole such as 2-methylimidazole and the like are mentioned as particularly preferable ones. Among them, pyridine, imidazole, aminopyridine, methylimidazole and the like are most preferable.
　上記ｐＨ緩衝剤は、一種単独で又は二種以上を混合して用いることができる。 The above pH buffers can be used singly or in combination of two or more.
　表面処理剤中のｐＨ緩衝剤の濃度は特に限定されず、０．１～２０ｇ／Ｌが好ましく、０．２～５ｇ／Ｌがより好ましい。ｐＨ緩衝剤の濃度が上記範囲であることにより、表面処理剤が優れたｐＨの緩衝性を示すことができ、且つ、ｐＨ緩衝剤の濃度が高過ぎることにより発生する染色品の色ヌケが抑制される。 The concentration of the pH buffer in the surface treatment agent is not particularly limited, and is preferably 0.1 to 20 g / L, and more preferably 0.2 to 5 g / L. When the concentration of the pH buffer is in the above-mentioned range, the surface treatment agent can exhibit excellent pH bufferability, and color stains of the dyed product generated due to the concentration of the pH buffer being too high are suppressed. Be done.
（アニオン系界面活性剤）
　本発明の表面処理剤は、更に、アニオン系界面活性剤を含有することが好ましい。アニオン系界面活性剤を含有することにより、染色定着性がより一層向上し、且つ、陽極酸化皮膜の表面の粉吹きやカブリ外観不良を抑制することができる。 (Anionic surfactant)
The surface treatment agent of the present invention preferably further contains an anionic surfactant. By containing the anionic surfactant, the dye fixation can be further improved, and powder blowing on the surface of the anodized film and fogging appearance defects can be suppressed.
　アニオン系界面活性剤としては特に限定されず、硫酸塩系界面活性剤、スルホン酸塩系界面活性剤、スルホコハク酸系界面活性剤、リン系界面活性剤等を用いることができる。 The anionic surfactant is not particularly limited, and a sulfate surfactant, a sulfonate surfactant, a sulfosuccinic acid surfactant, a phosphorus surfactant and the like can be used.
　硫酸塩系界面活性剤としては、芳香族硫酸塩系界面活性剤、脂肪族硫酸塩系界面活性剤等が挙げられる。 As a sulfate type surfactant, aromatic sulfate type surfactant, aliphatic sulfate type surfactant, etc. are mentioned.
　上記芳香族硫酸塩系界面活性剤としては、例えばポリオキシエチレンアルキルフェニルエーテル硫酸塩が挙げられる。また、脂肪族硫酸塩系界面活性剤としては、例えばポリオキシエチレンアルキルエーテル硫酸塩が挙げられる。 Examples of the aromatic sulfate surfactant include polyoxyethylene alkyl phenyl ether sulfate. Moreover, as an aliphatic sulfate type surfactant, a polyoxyethylene alkyl ether sulfate is mentioned, for example.
　スルホン酸塩系界面活性剤としては、芳香族スルホン酸塩系界面活性剤等が挙げられる。 As a sulfonate surfactant, an aromatic sulfonate surfactant and the like can be mentioned.
　上記芳香族スルホン酸塩系界面活性剤としては、ベンゼンスルホン酸塩、ナフタレンスルホン酸塩等の芳香族スルホン酸塩化合物や、ベンゼンスルホン酸塩、ナフタレンスルホン酸塩等の芳香族スルホン酸塩骨格に、アルキル基、ポリオキシエチレン基、ポリオキシエチレンアルキルエーテル基、カルボキシル基、カルボニル基、水酸基、アルコール基、ビニル基やアリル基等のアルキレン基や多重結合を持つ基、さらなるスルホン酸基が置換した化合物等が挙げられ、また、これらの化合物のホルマリン等での重縮合物、並びに共重合物等が挙げられる。このような芳香族スルホン酸塩系界面活性剤としては例えばアルキルベンゼンスルホン酸塩、アルキルナフタレンスルホン酸塩、ならびにそれらのホルマリン等重縮合物、ナフタレンスルホン酸塩のホルマリン等重縮合物、アルキレンベンゼンスルホン酸塩やアルキレンナフタレンスルホン酸塩等からの共重合物等が挙げられる。 Examples of the aromatic sulfonate surfactant include aromatic sulfonate compounds such as benzene sulfonate and naphthalene sulfonate, and aromatic sulfonate backbones such as benzene sulfonate and naphthalene sulfonate. Substituted by an alkyl group, a polyoxyethylene group, a polyoxyethylene alkyl ether group, a carboxyl group, a carbonyl group, a hydroxyl group, an alcohol group, an alkylene group such as a vinyl group or an allyl group or a group having multiple bonds, and a further sulfonic acid group Compounds and the like can be mentioned, and furthermore, polycondensation products of these compounds with formalin and the like, and copolymers and the like can be mentioned. Such aromatic sulfonate-based surfactants include, for example, alkylbenzene sulfonates, alkyl naphthalene sulfonates, polycondensates of formalins thereof, formalin such as polycondensates of naphthalene sulfonates, alkylene benzene sulfonates Examples thereof include salts and copolymers from alkylene naphthalene sulfonates and the like.
　上記芳香族スルホン酸塩系界面活性剤としては、ジフェニルエーテルジスルホン酸塩等の、複数個のフェニルスルホン酸塩がエーテル結合した化合物が挙げられ、また、当該化合物にアルキル基、ポリオキシエチレン基、ポリオキシエチレンアルキルエーテル基等が置換した化合物が挙げられる。このような芳香族スルホン酸塩系界面活性剤としては、例えば、アルキルジフェニルエーテルジスルホン酸塩等が挙げられる。 Examples of the aromatic sulfonate-based surfactant include compounds in which a plurality of phenyl sulfonates such as diphenyl ether disulfonates are ether-bonded, and the compounds may be selected from alkyl groups, polyoxyethylene groups, poly The compound which the oxyethylene alkyl ether group etc. substituted is mentioned. Examples of such aromatic sulfonate surfactants include alkyl diphenyl ether disulfonate and the like.
　スルホコハク酸系界面活性剤としてはスルホコハク酸にアルキル基や芳香族環が結合したものが挙げられる。具体的には、アルキルスルホコハク酸、ジアルキルスルホコハク酸、アルキルジフェニルエーテルジスルホコハク酸等とそれらの塩が挙げられる。 Examples of sulfosuccinic acid surfactants include those in which an alkyl group or an aromatic ring is bonded to sulfosuccinic acid. Specifically, alkyl sulfosuccinic acid, dialkyl sulfosuccinic acid, alkyl diphenyl ether disulfo succinic acid and the like and salts thereof can be mentioned.
　リン系界面活性剤としては、リン酸エステル系界面活性剤、リン酸エステル塩系界面活性剤等を用いることができる。具体的には、ポリオキシエチレンアルキルエーテルリン酸エステル、ポリオキシエチレンアルキレン化フェニルエーテルリン酸エステル、アルキルリン酸エステル等とそれらの塩が挙げられる。 As a phosphorus surfactant, a phosphate ester surfactant, a phosphate ester salt surfactant, etc. can be used. Specifically, polyoxyethylene alkyl ether phosphate, polyoxyethylene alkylenated phenyl ether phosphate, alkyl phosphate and the like and salts thereof can be mentioned.
　上記アニオン系界面活性剤としては、スルホン酸塩系界面活性剤が好ましい。 As the above-mentioned anionic surfactant, a sulfonate-based surfactant is preferable.
　上記アニオン系界面活性剤は、一種単独で又は二種以上を混合して用いることができる。 The said anionic surfactant can be used individually by 1 type or in mixture of 2 or more types.
　表面処理剤中のアニオン系界面活性剤の濃度は特に限定されず、１０ｍｇ／Ｌ～１０ｇ／Ｌが好ましく、２０ｍｇ／Ｌ～５ｇ／Ｌがより好ましい。界面活性剤の濃度が上記範囲であることにより、染色定着性がより一層向上する。 The concentration of the anionic surfactant in the surface treatment agent is not particularly limited, and 10 mg / L to 10 g / L is preferable, and 20 mg / L to 5 g / L is more preferable. When the concentration of the surfactant is in the above range, the dye fixation is further improved.
（ｐＨ調整剤）
　本発明の表面処理剤は、更に、ｐＨ調整剤を含んでいてもよい。ｐＨ調整剤としては特に限定されず、従来公知のｐＨ調整剤を用いることができる。 (PH adjuster)
The surface treatment agent of the present invention may further contain a pH adjuster. The pH adjuster is not particularly limited, and conventionally known pH adjusters can be used.
　表面処理剤を低下させて酸性側に調整するためのｐＨ調整剤としては、例えば、酢酸、スルファミン酸、硫酸、硝酸、有機スルホン酸等の希釈水溶液が挙げられる。これらの中でも、染色定着性がより一層向上する点で、硝酸が好ましい。 Examples of pH adjusters for reducing the surface treatment agent to adjust to the acidic side include dilute aqueous solutions of acetic acid, sulfamic acid, sulfuric acid, nitric acid, organic sulfonic acid and the like. Among these, nitric acid is preferable in that the dye fixation is further improved.
　表面処理剤のｐＨを上げるためのｐＨ調整剤としては、例えば、アンモニア水、水酸化ナトリウム水溶液、水酸化カリウム水溶液等が挙げられる。これらの中でも、染色定着性がより一層向上する点で、アンモニア水が好ましい。 Examples of the pH adjuster for raising the pH of the surface treatment agent include aqueous ammonia, aqueous sodium hydroxide solution, aqueous potassium hydroxide solution and the like. Among these, ammonia water is preferable in that the dye fixation is further improved.
　上記ｐＨ調整剤は、一種単独で又は二種以上を混合して用いることができる。 The said pH adjuster can be used individually by 1 type or in mixture of 2 or more types.
　表面処理剤中のｐＨ調整剤の濃度は特に限定されず、０～２０ｇ／Ｌが好ましく、０～１０ｇ／Ｌがより好ましく、０～５ｇ／Ｌが更に好ましい。ｐＨ調整剤の濃度が上記範囲であることにより、染色定着性がより一層向上する。 The concentration of the pH adjuster in the surface treatment agent is not particularly limited, and is preferably 0 to 20 g / L, more preferably 0 to 10 g / L, and still more preferably 0 to 5 g / L. When the concentration of the pH adjusting agent is in the above range, the dye fixation is further improved.
（その他の成分）
　本発明の表面処理剤は、染色定着性のさらなる向上や表面処理剤の使用実用性を向上させるために、必要に応じて防カビ剤、錯化剤等の添加剤成分を含んでいてもよい。添加剤としては、例えば、安息香酸、安息香酸塩等の防カビ剤；クエン酸、クエン酸塩等の錯化剤等が挙げられる。また、防カビ剤としては市販の防カビ剤、例えば「ＴＡＣカビコロン」（奥野製薬工業株式会社製）を添加してもよい。 (Other ingredients)
The surface treatment agent of the present invention may optionally contain an additive component such as an antifungal agent and a complexing agent in order to further improve the dye fixing property and the practicality of using the surface treatment agent. . Examples of the additive include fungicides such as benzoic acid and benzoate; and complexing agents such as citric acid and citrate. Moreover, as a fungicide, a commercially available fungicide, for example, "TAC mold colon" (manufactured by Okuno Pharmaceutical Co., Ltd.) may be added.
　本発明の表面処理剤は、フッ化ジルコニウム塩を含有していればその他の成分は特に限定されないが、上述の各成分を含有する水溶液であることが好ましい。 Although the other components are not particularly limited as long as the surface treatment agent of the present invention contains a zirconium fluoride salt, it is preferably an aqueous solution containing the above-mentioned components.
２．表面処理方法
　本発明の表面処理方法は、染色された、アルミニウム又はアルミニウム合金の陽極酸化皮膜の表面処理方法であって、（１）アルミニウム又はアルミニウム合金の陽極酸化皮膜を染色処理する工程１、及び、（２）染色された陽極酸化皮膜を表面処理剤に浸漬して表面処理を行う工程２を有し、表面処理剤はフッ化ジルコニウム塩を含有し、且つ、ｐＨが３．４以下である表面処理方法である。 2. Surface treatment method The surface treatment method of the present invention is a surface treatment method of dyed anodized film of aluminum or aluminum alloy, and (1) step 1 of dyeing anodized film of aluminum or aluminum alloy, and (2) Step 2 of immersing a dyed anodic oxide film in a surface treatment agent to perform surface treatment, the surface treatment agent containing a zirconium fluoride salt and having a pH of 3.4 or less It is a surface treatment method.
（工程１）
　工程１は、アルミニウム又はアルミニウム合金の陽極酸化皮膜を染色処理する工程である。 (Step 1)
Step 1 is a step of dyeing an anodized film of aluminum or an aluminum alloy.
　染色処理の処理対象であるアルミニウム又はアルミニウム合金の陽極酸化皮膜は、一般的なアルミニウム、アルミニウム合金に硫酸、シュウ酸等を用いた公知の陽極酸化法を適用して得られた陽極酸化皮膜であればよい。アルミニウム合金としては特に限定的ではなく、各種のアルミニウム主体の合金を陽極酸化の対象とすることができる。アルミニウム合金の具体例としては、ＪＩＳに規定されているＪＩＳ－Ａ　１千番台～７千番台で示される展伸材系合金、ＡＣ、ＡＤＣの各番程で示される鋳物材、ダイカスト材等を代表とするアルミニウム主体の各種合金群等が挙げられる。 The anodized film of aluminum or aluminum alloy to be subjected to the dyeing process may be an anodized film obtained by applying a known anodizing method using sulfuric acid, oxalic acid or the like to general aluminum or aluminum alloy. Just do it. The aluminum alloy is not particularly limited, and various aluminum-based alloys can be targets for anodic oxidation. Specific examples of the aluminum alloy include wrought alloys based on JIS-A series 1 to 7 specified in JIS, cast materials shown on each series of AC and ADC, and die cast materials. Examples include various aluminum-based alloy groups as a representative.
　アルミニウム又はアルミニウム合金に施される陽極酸化法としては、例えば、硫酸濃度が１００ｇ／Ｌ～４００ｇ／Ｌ程度の水溶液を用い、液温を０～３０℃程度として、０．５～４Ａ／ｄｍ２程度の陽極電流密度で電解を行う方法が挙げられる。 As an anodic oxidation method applied to aluminum or aluminum alloy, for example, an aqueous solution with a sulfuric acid concentration of about 100 g / L to about 400 g / L and a liquid temperature of about 0 to 30 ° C. and 0.5 to 4 A / dm 2 There is a method of performing electrolysis at a certain anodic current density.
　染色処理としては特に限定されず、染料による着色が挙げられる。染料による着色としては、従来公知の染料水溶液に陽極酸化皮膜を浸漬する方法が挙げられる。このような染料としては、アルミニウム又はアルミニウム合金の陽極酸化皮膜用染料として市販されているものを用いることができ、例えば、アニオン系染料等が挙げられる。上記染料水溶液の温度は、１０～７０℃が好ましく、２０～６０℃がより好ましい。また、上記染料水溶液中の染料の濃度及び浸漬時間は、要望される染色の色調、色の濃さに応じて適宜設定すればよい。 It does not specifically limit as a dyeing | staining process, The coloring by dye is mentioned. As coloring by dye, the method of immersing an anodic oxide film in conventionally well-known dye aqueous solution is mentioned. As such a dye, those marketed as dyes for anodic oxidation film of aluminum or aluminum alloy can be used, and, for example, anionic dyes and the like can be mentioned. The temperature of the aqueous dye solution is preferably 10 to 70 ° C., and more preferably 20 to 60 ° C. Further, the concentration of the dye in the aqueous dye solution and the immersion time may be appropriately set according to the desired color tone of the dye and the color depth.
　以上説明した工程１により、アルミニウム又はアルミニウム合金の陽極酸化皮膜が染色処理される。 The anodized film of aluminum or aluminum alloy is dyed in the step 1 described above.
（工程２）
　工程２は、染色された陽極酸化皮膜を表面処理剤に浸漬して表面処理を行う工程である。表面処理剤としては、上記に説明した表面処理剤を用いればよい。 (Step 2)
Step 2 is a step of immersing the dyed anodic oxide film in a surface treatment agent to carry out surface treatment. The surface treatment agent described above may be used as the surface treatment agent.
　表面処理剤に染色された陽極酸化皮膜を浸漬する際は、一部に陽極酸化皮膜が形成されたアルミニウム又はアルミニウム合金を表面処理剤に浸漬すればよい。また、当該アルミニウム又はアルミニウム合金が他の部材と接合されて物品を形成している場合は、当該物品ごと表面処理剤に浸漬すればよい。 In the case of immersing the anodized film dyed in the surface treatment agent, the aluminum or aluminum alloy in which the anodized film is partially formed may be dipped in the surface treatment agent. When the aluminum or aluminum alloy is joined to another member to form an article, the article may be immersed in the surface treatment agent.
　陽極酸化皮膜を表面処理剤に浸漬する際の表面処理剤の温度は、１０～７０℃が好ましく、３０～５０℃がより好ましい。表面処理剤の温度が上記範囲であることにより、陽極酸化皮膜の耐光性及び染色定着性がより一層向上する。 The temperature of the surface treatment agent at the time of immersing the anodized film in the surface treatment agent is preferably 10 to 70 ° C., and more preferably 30 to 50 ° C. When the temperature of the surface treatment agent is in the above range, the light resistance and dye fixation of the anodized film are further improved.
　陽極酸化皮膜を表面処理剤に浸漬する際の浸漬時間は、１～３０分が好ましく、２～１０分がより好ましい。浸漬時間の下限が上記範囲であることにより、陽極酸化皮膜の耐光性及び染色定着性がより一層向上する。また、浸漬時間の上限が上記範囲であることにより、生産効率に優れる。 The immersion time for immersing the anodized film in the surface treatment agent is preferably 1 to 30 minutes, and more preferably 2 to 10 minutes. When the lower limit of the immersion time is in the above range, the light resistance and dye fixation of the anodized film are further improved. Moreover, when the upper limit of immersion time is the said range, it is excellent in production efficiency.
　工程２では、工程１の染色処理の後で、アルミニウム又はアルミニウム合金の陽極酸化皮膜を十分に水洗し、乾燥させてから、上記表面処理剤に浸漬してもよい。これにより、陽極酸化皮膜の染色定着性がより一層向上する。 In step 2, after the dyeing process of step 1, the anodized film of aluminum or aluminum alloy may be thoroughly washed with water, dried and then dipped in the surface treatment agent. This further improves the dyeing and fixing properties of the anodized film.
　以上説明した工程２により、陽極酸化皮膜が表面処理される。 The anodic oxide film is surface-treated by the process 2 described above.
３．封孔処理方法
　本発明の封孔処理方法は、上記表面処理方法により表面処理された陽極酸化皮膜を封孔処理する工程３を有する陽極酸化皮膜の封孔処理方法である。 3. Sealing Method The sealing method of the present invention is a method of sealing an anodic oxide film, which has a step 3 of sealing the anodic oxide film surface-treated by the surface treatment method.
　封孔処理としては特に限定されず、従来公知の封孔処理方法により処理すればよい。このような封孔処理方法としては、上記表面処理方法により表面処理されたアルミニウム又はアルミニウム合金の陽極酸化皮膜を封孔処理液に浸漬する方法が好ましい。 It does not specifically limit as a sealing process, What is necessary is just to process by the conventionally well-known sealing process method. As such a sealing treatment method, a method of immersing an anodic oxide film of aluminum or an aluminum alloy surface-treated by the above-mentioned surface treatment method in a sealing treatment solution is preferable.
　上記封孔処理液としては特に限定されず、金属塩を含有する封孔処理液が挙げられる。上記金属塩に含まれる金属としては、アルカリ金属、アルカリ土類金属及び遷移金属が好ましく、具体的には、Ｌｉ、Ｂｅ、Ｎａ、Ｍｇ、Ｋ、Ｃａ、Ｒｂ、Ｓｒ、Ｃｓ、Ｂａ、Ｆｒ、Ｒａ、Ｚｒ、Ｍｎ、Ｆｅ、Ｎｉ、Ｃｏが挙げられる。これらの中でも、封孔処理されたアルミニウム又はアルミニウム合金の陽極酸化皮膜が耐食性に優れる点で、Ｎａ、Ｍｇ、Ｋ、Ｃａ、Ｂａ、Ｍｎ、Ｎｉの金属塩がより好ましく、Ｍｇ、Ｃａ、Ｍｎ、Ｎｉの金属塩が更に好ましい。上記金属塩に含まれる金属は、一種単独で又は二種以上を混合して用いることができる。 It does not specifically limit as said sealing solution, The sealing solution containing metal salt is mentioned. The metal contained in the metal salt is preferably an alkali metal, an alkaline earth metal or a transition metal, and specifically, Li, Be, Na, Mg, K, Ca, Rb, Sr, Cs, Ba, Fr, Ra, Zr, Mn, Fe, Ni, Co can be mentioned. Among these, metal salts of Na, Mg, K, Ca, Ba, Mn and Ni are more preferable in that the anodic oxide film of sealed aluminum or aluminum alloy is excellent in corrosion resistance, Mg, Ca, Mn, Metal salts of Ni are more preferred. The metals contained in the metal salt can be used singly or in combination of two or more.
　封孔処理液中の金属塩の濃度は特に限定されず、０．００１～１モル／Ｌが好ましく、０．００３～０．３モル／Ｌがより好ましい。金属塩の濃度が上記範囲であることにより、封孔処理液が十分な封孔性能を示すことができ、封孔処理液により封孔処理されたアルミニウム又はアルミニウム合金の陽極酸化皮膜の耐食性がより一層向上する。 The concentration of the metal salt in the sealing solution is not particularly limited, and is preferably 0.001 to 1 mol / L, and more preferably 0.003 to 0.3 mol / L. When the concentration of the metal salt is in the above range, the sealing solution can exhibit sufficient sealing performance, and the corrosion resistance of the anodic oxide film of aluminum or aluminum alloy sealed by the sealing solution is more enhanced. Improve further.
　封孔処理液は、封孔性能（外観、耐食性等）を向上させるために、ｐＨ緩衝剤、界面活性剤等の添加剤成分を含んでもよい。添加剤として、例えば、酢酸、酢酸塩、硝酸、硝酸塩、安息香酸、安息香酸塩等のｐＨ緩衝剤又はｐＨ調整剤；ナフタリンスルホン酸ホルマリン縮合物ナトリウム塩等のスルホン酸系分散剤等が挙げられる。 The sealing solution may contain additive components such as a pH buffer and a surfactant in order to improve the sealing performance (appearance, corrosion resistance, etc.). Examples of additives include pH buffers or pH adjusters such as acetic acid, acetate, nitric acid, nitrate, benzoic acid and benzoate; and sulfonic acid-based dispersants such as naphthalene sulfonic acid formalin condensate sodium salt and the like. .
　封孔処理液のｐＨは、通常５．０～８．０であり、好ましくは５．３～６．０である。封孔処理液のｐＨは、例えば、酢酸、硝酸、安息香酸、硫酸等の酸類；水酸化ナトリウム、炭酸ナトリウム、アンモニア水等のアルカリ類を用いて上記ｐＨ範囲となるように調整すればよい。 The pH of the sealing solution is usually 5.0 to 8.0, preferably 5.3 to 6.0. The pH of the sealing solution may be adjusted to be in the above pH range using, for example, an acid such as acetic acid, nitric acid, benzoic acid or sulfuric acid; or an alkali such as sodium hydroxide, sodium carbonate or aqueous ammonia.
　封孔処理液の温度（処理温度）は通常８０℃～沸点程度であり、好ましくは８５℃～沸点程度である。浸漬時間は、通常１分～６０分程度であり、好ましくは３分～３０分程度である。処理温度及び浸漬時間を上記範囲にすることにより、封孔後の皮膜が粉吹き状態になるのを防ぐとともに、皮膜の耐汚染性を向上し、また耐食性を得ることができる。 The temperature of the sealing solution (processing temperature) is usually about 80 ° C. to boiling point, preferably about 85 ° C. to boiling point. The immersion time is usually about 1 minute to 60 minutes, preferably about 3 minutes to 30 minutes. By setting the treatment temperature and the immersion time in the above range, the film after sealing can be prevented from becoming powdery, the contamination resistance of the film can be improved, and corrosion resistance can be obtained.
　封孔処理液は、封孔性能や液の使用実用性を向上させるために、必要に応じて防カビ剤、錯化剤等の添加剤成分を含んでいてもよい。添加剤としては、例えば、安息香酸、安息香酸塩等の防カビ剤；クエン酸、クエン酸塩等の錯化剤等が挙げられる。また、防カビ剤としては市販の防カビ剤、例えば「ＴＡＣカビコロン」（奥野製薬工業株式会社製）を添加してもよい。 The sealing solution may contain additive components such as a mildewproofing agent and a complexing agent as needed in order to improve the sealing performance and the practicality of use of the solution. Examples of the additive include fungicides such as benzoic acid and benzoate; and complexing agents such as citric acid and citrate. Moreover, as a fungicide, a commercially available fungicide, for example, "TAC mold colon" (manufactured by Okuno Pharmaceutical Co., Ltd.) may be added.
　封孔処理液は、上述の金属塩、ｐＨ緩衝剤及び界面活性剤等を含有していればその他の成分は特に限定されないが、上述の各成分を含有する水溶液であることが好ましい。 Although the other components are not particularly limited as long as the sealing solution contains the above-mentioned metal salt, pH buffer, surfactant and the like, it is preferably an aqueous solution containing the above-mentioned components.
　以上説明した封孔処理方法によれば、アルミニウム又はアルミニウム合金の陽極酸化皮膜が上記表面処理方法により表面処理されており、封孔処理前の陽極酸化皮膜に優れた染色定着性を付与することができ、且つ、封孔処理後の陽極酸化皮膜に光が照射された際の退色が抑制されて、優れた耐光性を示すことができる。 According to the sealing method described above, the anodized film of aluminum or aluminum alloy is surface-treated by the above-mentioned surface treatment method, and excellent dyeing fixability is imparted to the anodic oxide film before sealing treatment. In addition, it is possible to suppress fading when light is irradiated to the anodized film after sealing treatment, and to exhibit excellent light resistance.
４．物品
　本発明の物品は、上記封孔処理方法により封孔処理された、アルミニウム又はアルミニウム合金の陽極酸化皮膜を有する物品である。 4. Article The article of the present invention is an article having an anodized film of aluminum or aluminum alloy sealed by the above-mentioned sealing method.
　物品としては、上記封孔処理方法により封孔処理された、アルミニウム又はアルミニウム合金の陽極酸化皮膜を有していればその用途は特に限定されず、例えば、電子機器の外装、化粧製品の外装等が挙げられる。 The article is not particularly limited as long as it has an anodized film of aluminum or aluminum alloy sealed by the above-mentioned sealing method, and, for example, an exterior of an electronic device, an exterior of a cosmetic product, etc. Can be mentioned.
　本発明の物品は、上記表面処理方法により表面処理されたアルミニウム又はアルミニウム合金の陽極酸化皮膜が、上記封孔処理方法により封孔処理されているので、物品の陽極酸化皮膜が染色定着性に優れており、且つ、物品の陽極酸化皮膜に光が照射された際の退色が抑制されて、優れた耐光性を示すことができる。 In the article of the present invention, the anodic oxide film of aluminum or aluminum alloy surface-treated by the above-mentioned surface treatment method is sealed by the above-mentioned pore-sealing treatment method, so the anodic oxide film of the article is excellent in dyeing and fixing properties In addition, it is possible to suppress fading when the anodic oxide film of the article is irradiated with light and to exhibit excellent light resistance.
　以下に実施例及び比較例を示して本発明を具体的に説明する。但し、本発明は実施例に限定されない。 Hereinafter, the present invention will be specifically described by showing Examples and Comparative Examples. However, the present invention is not limited to the examples.
　以下の製造条件に従って、下記の実施例及び比較例に用いる陽極酸化及び染色を施したアルミニウム合金試験片を製造した。 Anodized and dyed aluminum alloy test pieces used in the following examples and comparative examples were manufactured according to the following manufacturing conditions.
　アルミニウム合金の試験片（ＪＩＳ　Ａ１０５０Ｐ板）を弱アルカリ性脱脂液（奥野製薬工業（株）製トップアルクリーン４０４（商品名）３０ｇ／Ｌの水溶液、浴温６０℃）に５分間浸漬して脱脂し、水洗した後、硫酸を主成分とする陽極酸化浴（遊離硫酸１８０ｇ／Ｌ及び溶存アルミ８．０ｇ／Ｌを含む）で陽極酸化（浴温２０℃±１℃、陽極電流密度：１ａ／ｄｍ２、電解時間：３０分間、膜厚：約１０μｍ）を行った。得られた陽極酸化皮膜を水洗し、水洗後に下記の染料の水溶液（浴温５５℃）に１分間浸漬して染色し、水洗することにより、陽極酸化及び染色を施したアルミニウム合金試験片（以下、「陽極酸化－染色済試験片」という）を得た。 A test piece of aluminum alloy (JIS A1050P plate) is degreased by immersing in a weak alkaline degreasing solution (Okino Pharmaceutical Industry Co., Ltd. Top Alclean 404 (trade name) 30 g / L aqueous solution, bath temperature 60 ° C.) for 5 minutes After washing with water, anodic oxidation is performed in an anodic oxidation bath (containing free sulfuric acid 180 g / L and dissolved aluminum 8.0 g / L) containing sulfuric acid as the main component (bath temperature 20 ° C. ± 1 ° C., anodic current density: 1 a / dm) 2 , electrolysis time: 30 minutes, film thickness: about 10 μm). The anodized film obtained is washed with water, then washed with water, dipped in an aqueous solution of the following dye (bath temperature 55 ° C.) for 1 minute to dye, and washed with water, anodized and dyed aluminum alloy test pieces ( , “Anodized-dyed test piece”) was obtained.
　なお、染色に用いた染料、並びに、当該染料を用いた際の濃度及び浸漬時間は、ＴＡＣ　ＢＬＡＣＫ－ＧＬＨ（５ｇ／Ｌ、３分間）；ＴＡＣ　ＲＥＤ－ＢＬＨ（５ｇ／Ｌ、３分間）；ＴＡＣ　ＹＥＬＬＯＷ－ＲＨＭ（５ｇ／Ｌ、３分間）；ＴＡＣ　ＯＲＡＮＧＥ－ＬＨ（５ｇ／Ｌ、３分間）；ＴＡＣ　ＹＥＬＬＯＲ－ＳＧＬ（１ｇ／Ｌ、１分間）である。なお、上記染料は、いずれも奥野製薬工業(株)製ＴＡＣ染料を用いた。 The dye used for dyeing, and the concentration and immersion time when using the dye are as follows: TAC BLACK-GLH (5 g / L, 3 minutes); TAC RED-BLH (5 g / L, 3 minutes); TAC YELLOW-RHM (5 g / L, 3 minutes); TAC ORANGE-LH (5 g / L, 3 minutes); TAC YELLOR-SGL (1 g / L, 1 minute). In addition, the said dye used the Okino pharmaceutical industry Co., Ltd. product TAC dye in all.
（実施例１～５）
　表１及び２に示す染料を用いて作製した各陽極酸化－染色済試験片を、ジルコンフッ化アンモニウム１．２ｇ／Ｌ、グリシン１ｇ／Ｌ、フッ素を含有しない金属酸化物塩０．４ｇ／Ｌを含み、硝酸でｐＨ２．５に調整した水溶液からなる表面処理剤（浴温４５℃）に３分間浸漬を行い、水洗して表面処理を行った。次いで、奥野製薬工業（株）製トップシールＨ－２９８を４０ｍｌ／Ｌ含むｐＨ５．７の水溶液からなる封孔処理剤（浴温９２℃）に１５分間浸漬を行い、水洗及び乾燥を行った。 (Examples 1 to 5)
Each anodized-stained test piece prepared using the dyes shown in Tables 1 and 2 was made of 1.2 g / L of ammonium ammonium fluoride, 1 g / L of glycine, and 0.4 g / L of metal oxide salt containing no fluorine. The substrate was immersed for 3 minutes in a surface treatment agent (bath temperature 45 ° C.) containing an aqueous solution adjusted to pH 2.5 with nitric acid, washed with water and surface treated. Subsequently, it was immersed in a sealing treatment agent (bath temperature 92 ° C.) consisting of an aqueous solution of pH 5.7 containing 40 ml / L of Top Seal H-298 manufactured by Okuno Pharmaceutical Co., Ltd. for 15 minutes, followed by washing with water and drying.
（実施例６）
　フッ素を含有しない金属酸化物塩を添加しなかった以外は実施例１～５と同様にして、陽極酸化－染色済試験片を表面処理し、封孔処理剤に浸漬し、水洗及び乾燥を行った。 (Example 6)
In the same manner as in Examples 1 to 5 except that the metal oxide salt not containing fluorine is not added, the anodized-stained specimen is surface-treated, immersed in a sealing agent, washed with water and dried. The
（実施例７）
　表面処理液のＰＨを３．０に調整した以外は実施例１～５と同様にして、陽極酸化－染色済試験片を表面処理し、封孔処理剤に浸漬し、水洗及び乾燥を行った。 (Example 7)
The anodized-stained specimen was surface-treated in the same manner as in Examples 1 to 5 except that the pH of the surface treatment solution was adjusted to 3.0, immersed in a sealing agent, washed with water and dried. .
（比較例１～４）
　陽極酸化－染色済試験片を表面処理しなかった以外は実施例１～５と同様にして、封孔処理剤に浸漬し、水洗及び乾燥を行った。 (Comparative Examples 1 to 4)
In the same manner as in Examples 1 to 5 except that the anodized-stained specimen was not surface-treated, it was immersed in a sealing agent, washed with water and dried.
（比較例５）
　表面処理液のＰＨを３．５に調整した以外は実施例１～５と同様にして、陽極酸化－染色済試験片を表面処理し、封孔処理剤に浸漬し、水洗及び乾燥を行った。 (Comparative example 5)
Anodized-stained test pieces were surface-treated in the same manner as in Examples 1 to 5 except that the pH of the surface treatment solution was adjusted to 3.5, and then immersed in a sealing agent, followed by washing with water and drying. .
　上記実施例及び比較例について、下記の試験方法により評価を行った。 The above-described Examples and Comparative Examples were evaluated by the following test methods.
耐光性
　上記実施例１～４、６及び比較例１～４で得られた封孔処理後の試験片のＬ*、ａ*、ｂ*を積分球分光測色計（Ｘ－ｒｉｔｅ社製　ＳＰ６４、光源Ｄ６５、視野１０度、正反射光を含む）により測定し、基準値とした。次いで、上記実施例１～４、６及び比較例１～４で得られた試験片に対し、キセノンランプを光源とした耐光性試験機（アトラス社製　サンテストＸＬＳ＋）を用いて、照射温度６５℃、放射照度５５０Ｗ／ｍ２の条件で最大４００時間光を照射した。照射後の試験片のＬ*、ａ*、ｂ*を上記積分球分光測色計により測定した。上記基準値に対する色差総変化量ΔＥ*ａｂにより耐光性を評価した。なお、ΔＥ*ａｂが低いほど、耐光性が高いことを示す。 Light resistance in Examples 1 to 4 and 6 and Comparative Examples 1 to specimen after sealing treatment obtained in 4 L *, a *, b * an integrating sphere spectrophotometer (X-rite Co. SP64 , A light source D65, a field of view of 10 degrees, and specular light), and these were used as reference values. Subsequently, the test pieces obtained in the above Examples 1 to 4 and 6 and Comparative Examples 1 to 4 were irradiated with an irradiation temperature of 65 using a light resistance tester (Suntest XLS + manufactured by Atlas Corporation) using a xenon lamp as a light source. The light was irradiated for up to 400 hours under the conditions of ° C. and an irradiance of 550 W / m 2 . L *, a *, b * of the test piece after irradiation were measured by the said integrating sphere spectrophotometer. The light resistance was evaluated by the total color difference change ΔE * ab with respect to the above reference value. The lower the ΔE * ab, the higher the light resistance.
染色定着性
　上記実施例５、７及び比較例５で得られた試験片のＬ*、ａ*、ｂ*を積分球分光測色計（Ｘ-ｒｉｔｅ社製ＳＰ６４、光源Ｄ６５、正反射光含む）により測定し、染色定着性を評価した。なお、ｂ*が高いほど、黄色の濃さが濃く、ＴＡＣ　ＹＥＬＬＯＷ－ＳＧＬの染色定着性が高いことを示している。 Dyeing Fixability L *, a *, b * of the test pieces obtained in the above Examples 5 and 7 and Comparative Example 5 are integrated sphere spectrophotometer (SP64 manufactured by X-rite Co., light source D65, containing regular reflection light) ) And the dye fixation was evaluated. The higher the b *, the darker the yellow color, indicating that the fixing ability of the TAC YELLOW-SGL is high.
　結果を表１及び２に示す。 The results are shown in Tables 1 and 2.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１から明らかなように、フッ化ジルコニウム塩を含有し、ｐＨが３．４以下である表面処理剤で表面処理を行った実施例１～４では、表面処理を行わなかった比較例１～４と比較して、耐光性試験後の色差ΔＥ*ａｂが低くなっており、高い耐光性を示すことができることが分かった。
　また、フッ素を含有しない金属酸化物塩を添加しなかった実施例６においても実施例１～５と同様に耐光性試験後の色差ΔＥ*ａｂが低くなっており、高い耐光性を示すことができることが分かった。 As is clear from Table 1, in Examples 1 to 4 in which the surface treatment was performed with a surface treatment agent containing a zirconium fluoride salt and having a pH of 3.4 or less, Comparative Examples 1 to 4 in which the surface treatment was not performed It was found that the color difference ΔE * ab after the light resistance test is lower than that of No. 4 and that high light resistance can be exhibited.
Further, also in Example 6 in which the metal oxide salt not containing fluorine is not added, the color difference ΔE * ab after the light resistance test is low as in Examples 1 to 5, and high light resistance is exhibited. It turned out that it can be done.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　表２から明らかなように、表面処理剤のｐＨが２．５及び３．０である実施例５及び７では、ｐＨが３．５である比較例５と比較して、色調での黄色の濃さを表すｂ*が高くなっており、高い染色定着性を示すことができることが分かった。 As apparent from Table 2, in Examples 5 and 7 in which the pH of the surface treatment agent is 2.5 and 3.0, the yellow color in the color tone is compared with Comparative Example 5 in which the pH is 3.5. It was found that b * representing the density was high, and it was possible to show high dye fixation.
　実施例３及び比較例３の耐光性試験における各照射時間後の試験片の写真を図１に示す。また、実施例４及び比較例４の耐光性試験における各照射時間後の試験片の写真を図２に示す。図１及び２から、表面処理を行った実施例３及び４では、４００時間後でも退色が抑制されており、耐光性に優れることが分かった。一方、表面処理を行わなかった比較例３及び４では、照射時間が長くなると退色が顕著となり、耐光性に劣ることが分かった。 The photograph of the test piece after each irradiation time in the light resistance test of Example 3 and Comparative Example 3 is shown in FIG. Moreover, the photograph of the test piece after each irradiation time in the light resistance test of Example 4 and Comparative Example 4 is shown in FIG. From FIGS. 1 and 2, in Examples 3 and 4 in which the surface treatment was performed, fading was suppressed even after 400 hours, and it was found that the light resistance was excellent. On the other hand, in Comparative Examples 3 and 4 in which the surface treatment was not performed, it was found that the fading becomes remarkable as the irradiation time becomes long, and the light resistance is inferior.
　実施例１と同様にして染色を行い、次いで、表面処理剤を用いて表面処理を行い、且つ、封孔処理を行っていないアルミニウム合金の陽極酸化皮膜のＦＥ-ＳＥＭ像を、日本電子社製ＪＳＭ－６３３５Ｆを用いて倍率５００００倍の条件で撮影した。図３に表面像を示し、図４に断面像を示す。図４から、陽極酸化皮膜の表面に、表面処理により皮膜が形成されていることが分かった。表面処理により形成された皮膜は、３０～１００ｎｍ程度の微粒子の集合体であり、当該皮膜の厚みは１００ｎｍ程度であった。 The dyeing is performed in the same manner as in Example 1, and then the surface treatment is performed using a surface treatment agent, and the FE-SEM image of the anodized film of the aluminum alloy not subjected to the pore sealing treatment is manufactured by Nippon Denshi Co., Ltd. Photographed under the condition of 50000 times magnification using JSM-6335F. The surface image is shown in FIG. 3 and the cross-sectional image is shown in FIG. It was found from FIG. 4 that a film was formed on the surface of the anodized film by surface treatment. The film formed by the surface treatment was an aggregate of fine particles of about 30 to 100 nm, and the thickness of the film was about 100 nm.
　実施例１と同様にして染色を行い、次いで、表面処理剤を用いて表面処理を行い、且つ、封孔処理を行っていないアルミニウム合金の陽極酸化皮膜のＸ線光電子分光法（ＸＰＳ）による元素深さ方向分析を、アルバックファイ社製ＥＳＣＡ－ＳＹＳＴＥＭ　ＥＳＣＡ５８００ｃｉ／ＳＡＭを用いてスパッタ速度　ＳｉＯ２換算３ｎｍ／ｍｉｎの条件で行った。図５に結果を示す。図５から、スパッタ時間が短い場合にＺｒ原子の濃度が高くなっており、且つ、Ｏ原子の濃度も高いので、表面処理により陽極酸化皮膜の表面に形成された皮膜は、ＺｒＯ２の皮膜であると考えられる。 Dyeing is carried out in the same manner as in Example 1, and then surface treatment is carried out using a surface treatment agent, and the anodic oxidation film of an aluminum alloy which has not been subjected to sealing treatment by X-ray photoelectron spectroscopy (XPS) the depth profiling was performed on the conditions of sputtering rate in terms of SiO 2 3 nm / min using a ULVAC-pHI Inc. ESCA-SYSTEM ESCA5800ci / SAM. The results are shown in FIG. As shown in FIG. 5, when the sputtering time is short, the concentration of Zr atoms is high, and the concentration of O atoms is also high. Therefore, the film formed on the surface of the anodic oxide film by the surface treatment is a ZrO 2 film. It is believed that there is.
　実施例１と同様にして染色を行い、次いで、表面処理剤を用いて表面処理を行い、且つ、封孔処理を行っていないアルミニウム合金の陽極酸化皮膜のＸ線光電子分光法（ＸＰＳ）によるナロースキャン分析を、アルバックファイ社製ＥＳＣＡ－ＳＹＳＴＥＭ　ＥＳＣＡ５８００ｃｉ／ＳＡＭを用いて行った。図６に結果を示す。図６から、ナロースキャン分析によるピークがＺｒＯ２の結合エネルギーのピークである１８２．３±０．３ｅｖと一致している。このことから、表面処理により陽極酸化皮膜の表面に形成された皮膜は、ＺｒＯ２の皮膜であることが分かった。 Dyeing is carried out in the same manner as in Example 1, then surface treatment is carried out using a surface treatment agent, and anodized film of aluminum alloy not subjected to pore sealing treatment is narrow by X-ray photoelectron spectroscopy (XPS). Scan analysis was performed using ULVAC-PHI ESCA-SYSTEM ESCA 5800 ci / SAM. The results are shown in FIG. From FIG. 6, the peak by narrow scan analysis is in agreement with 182.3 ± 0.3 ev which is a peak of the binding energy of ZrO 2 . From this, it was found that the film formed on the surface of the anodized film by the surface treatment was a ZrO 2 film.

Claims (11)

  1. 　染色された、アルミニウム又はアルミニウム合金の陽極酸化皮膜の表面処理剤であって、フッ化ジルコニウム塩を含有し、ｐＨが３．４以下であることを特徴とする、表面処理剤。 A surface treatment agent of a dyed anodized film of aluminum or aluminum alloy, wherein the surface treatment agent contains a zirconium fluoride salt and has a pH of 3.4 or less.
  2. 　ｐＨが２．３～２．８である、請求項１に記載の表面処理剤。 The surface treatment agent according to claim 1, wherein the pH is 2.3 to 2.8.
  3. 　更に、フッ素を含有しない金属酸化物塩を含む、請求項１又は２に記載の表面処理剤。 Furthermore, the surface treating agent of Claim 1 or 2 containing the metal oxide salt which does not contain a fluorine.
  4. 　更に、ｐＨ緩衝剤を含有する、請求項１～３のいずれかに記載の表面処理剤。 The surface treatment agent according to any one of claims 1 to 3, further comprising a pH buffer.
  5. 　更に、アニオン系界面活性剤を含有する、請求項１～４のいずれかに記載の表面処理剤。 The surface treatment agent according to any one of claims 1 to 4, further comprising an anionic surfactant.
  6. 　染色された、アルミニウム又はアルミニウム合金の陽極酸化皮膜の表面処理方法であって、
    （１）アルミニウム又はアルミニウム合金の陽極酸化皮膜を染色処理する工程１、及び、
    （２）染色された陽極酸化皮膜を表面処理剤に浸漬して表面処理を行う工程２を有し、
    　表面処理剤はフッ化ジルコニウム塩を含有し、且つ、ｐＨが３．４以下であることを特徴とする表面処理方法。     What is claimed is: 1. A method for surface treatment of a dyed anodized film of aluminum or aluminum alloy, comprising:
    (1) Step 1 of dyeing an anodic oxide film of aluminum or aluminum alloy, and
    (2) Step 2 of immersing the dyed anodic oxide film in a surface treatment agent to perform surface treatment;
    A surface treatment method comprising a zirconium fluoride salt and having a pH of 3.4 or less.
  7. 　表面処理剤のｐＨは２．３～２．８である、請求項６に記載の表面処理方法。 The surface treatment method according to claim 6, wherein the pH of the surface treatment agent is 2.3 to 2.8.
  8. 　表面処理剤の温度は１０～７０℃である、請求項６又は７に記載の表面処理方法。 The surface treatment method according to claim 6 or 7, wherein the temperature of the surface treatment agent is 10 to 70 属 C.
  9. 　表面処理剤への浸漬時間は１～３０分である、請求項６～８のいずれかに記載の表面処理方法。 The surface treatment method according to any one of claims 6 to 8, wherein the immersion time in the surface treatment agent is 1 to 30 minutes.
  10. 　請求項６～９のいずれかに記載の表面処理方法により表面処理された、アルミニウム又はアルミニウム合金の陽極酸化皮膜を封孔処理する工程３を有する、アルミニウム又はアルミニウム合金の陽極酸化皮膜の封孔処理方法。 The sealing treatment of the anodic oxide film of aluminum or aluminum alloy which has the process 3 of sealing the anodic oxidation film of aluminum or aluminum alloy surface-treated by the surface treatment method in any one of Claims 6-9 Method.
  11. 　請求項１０に記載の封孔処理方法により封孔処理された、アルミニウム又はアルミニウム合金の陽極酸化皮膜を有する物品。 An article having an anodized film of aluminum or aluminum alloy sealed by the sealing method according to claim 10.
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