Classifications

• • 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
• • 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
  • C25D11/24—Chemical after-treatment

Definitions

• the present invention relates to a dye fixing treatment agent for an anodic oxide film of an aluminum alloy and a sealing treatment method.
• Sealing treatment is generally performed on the anodized film of the aluminum alloy in order to achieve prevention of contamination, improvement of corrosion resistance and the like.
• a sealing treatment method a boiling water sealing hole, a steam sealing hole, a normal temperature sealing hole, a nickel acetate sealing hole for sealing using a nickel acetate aqueous solution, and the like are known.
• the corrosion resistance of the film can be easily obtained compared to boiling water sealing, the working efficiency is superior compared to water vapor sealing, and nickel acetate sealing is possible because liquid management is easier to perform than normal temperature sealing, etc. Is particularly used.
• sealing treatment method at least one selected from the group consisting of a water-soluble divalent manganese salt, and a sulfonate-type anionic surfactant and a sulfate-ester-type anionic surfactant.
• a sealing treatment method using a sealing treatment solution for an anodic oxide film of an aluminum alloy consisting of an aqueous solution containing an anionic surfactant has been proposed (see Patent Document 1).
• the sealing method using the above-mentioned sealing solution is also an excellent sealing method, the fixing of the stain of the anodic oxide film of the aluminum alloy has not been studied.
• the anodized film is dyed by a dyeing process for the purpose of design and the like. The dyeing step is performed prior to the sealing treatment, the anodized film is dyed, and then the sealing treatment is performed. There is a problem that it is decolorized by the sealing treatment and the fixing property of the dyeing is lowered.
• the present invention has been made in view of the problems of the prior art described above, and even if the anodized film of an aluminum alloy is subjected to a staining treatment and then to a sealing treatment, the decolorization is suppressed and the fixability of the dyeing is
• An object of the present invention is to provide a dyeing and fixing means and a sealing method which can be improved.
• the present inventor has intensively studied to achieve the above-mentioned purpose.
• the dye-fixing treatment is performed using the dye fixing treatment agent for an anodic oxide film of an aluminum alloy containing a manganese salt and having a pH of 5.0 or less.
• the inventors have found that the above object can be achieved, and have completed the present invention.
• the present invention relates to the following dye fixing agent and sealing method.
• a dye fixing agent for an anodic oxide film of an aluminum alloy comprising a manganese salt and having a pH of 5.0 or less.
• the dye fixing agent according to item 1 further comprising an anionic surfactant.
• Item 3 The dye fixing agent according to item 1 or 2, further comprising a pH buffer. 4.
• Step 1 of dyeing an anodic oxide film of aluminum alloy
• Step 2 of immersing the dyed anodic oxide film in a dye fixing agent for dyeing and fixing treatment
• Step 3 of sealing the anodic oxide film subjected to the dyeing and fixing treatment
• a dye fixing agent contains a manganese salt, and the pH is 5.0 or less. 5.
• the sealing treatment method according to Item 4 wherein the temperature of the dye fixing agent is 55 to 95 ° C. 6.
• the sealing treatment method according to Item 4 or 5 wherein the immersion time in the dye fixing agent is 1 to 30 minutes. 7. 7.
• Item 8 The sealing treatment method according to any one of Items 4 to 7, wherein the pH of the sealing treatment liquid is 5.1 to 8.0. 9.
• the dye fixing treatment is carried out using the dye fixing agent after the dyeing treatment to obtain an excellent dye fixing property for the anodic oxide film of an aluminum alloy Can be applied, and the decoloring at the time of sealing the anodic oxide film in a later step is suppressed.
• the anodic oxide film of the aluminum alloy is dyed, dyed and fixed using a specific dye fixing treatment agent, and then the pore sealing treatment is carried out.
• staining excellent in the anodic oxide film of aluminum alloy can be provided, and the decoloring in sealing treatment is suppressed.
• the dye fixing treatment agent for anodic oxide film of the aluminum alloy of the present invention contains a manganese salt and has a pH of 5 .0 or less.
• the manganese salt is not particularly limited, and manganese acetate, manganese nitrate, manganese sulfate, manganese chloride, manganese borate, manganese carbonate and the like can be used. Among these, manganese acetate and manganese nitrate are preferable, and manganese acetate is more preferable, from the viewpoint that the dye-fixing property is further excellent.
• the manganese salts can be used singly or in combination of two or more.
• the content of the manganese salt in the dye fixing agent is not particularly limited, and is preferably 0.1 to 10.0 g / L, and more preferably 0.2 to 2.0 g / L.
• the dye fixation is further improved.
• the upper limit of the content of the manganese salt is in the above range, it is excellent in the point of color loss suppression at the time of the dyeing and fixing process.
• the dye fixing agent of the present invention has a pH of 5.0 or less.
• the pH is preferably 4.5 or less, more preferably 4.0 or less.
• 2.0 or more are preferable, 3.0 or more are more preferable, and 3.5 or more are still more preferable.
• the lower limit of the pH is in the above range, the dye fixation is further improved.
• the dye fixing 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 phosphorus surfactant or 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 surfactant examples include compounds in which a plurality of phenyl sulfonates such as diphenyl ether disulfonate are ether-bonded, and further, the compound has an alkyl group, a polyoxyethylene group and the like. And compounds in which a polyoxyethylene alkyl ether group or the like is substituted.
• aromatic sulfonate surfactants include alkyl diphenyl ether disulfonate, alkyl diphenyl ether disulfosuccinate and the like.
• 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 dye fixing 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 dye fixing 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, histidine and a salt thereof, aspartic acid and a salt thereof are preferable in view of pH buffering action, and 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 dye fixing agent is not particularly limited, 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 range, the dye fixing treatment agent can exhibit excellent bufferability of pH, and the appearance defect of the surface of the treated product caused by the concentration of the pH buffer being too high (Drying stains) and color stains of dyed products are suppressed.
• the dye fixing 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 adjusting the dye fixing agent to the acid 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.
• pH adjusters for adjusting the dye fixing agent to the alkaline side include aqueous ammonia, aqueous sodium hydroxide solution, aqueous potassium hydroxide solution and the like.
• sodium hydroxide aqueous solution is preferable at the point which dyeing
• 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 dye fixing 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.
• the dye fixing agent of the present invention contains, as necessary, additive components such as a fungicide and a complexing agent in order to further improve the dye fixing property and the practicality of using the dye fixing agent. It is also good.
• additive components such as a fungicide and a complexing agent in order to further improve the dye fixing property and the practicality of using the dye fixing agent. It is also good.
• the additive include fungicides such as benzoic acid and benzoate; and 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 dye fixing agent of the present invention is not particularly limited as long as it contains a manganese salt, but is preferably an aqueous solution containing the above-mentioned components.
• the dye fixing agent of the present invention preferably contains no metal salt other than the manganese salt.
• metal salts other than such a manganese salt metal salts, such as Ni, Co, Fe, and Cr, are mentioned, Among these, it is more preferable not to contain a nickel-type metal salt.
• the sealing method of the present invention is a method of sealing an anodic oxide film of an aluminum alloy, which comprises (1) step 1 of dyeing an anodic oxide film of an aluminum alloy, and (2) dyeing Step 2 includes immersing the anodized film in a dye fixing agent and performing dye fixing treatment, and (3) step 3 of sealing anodized film subjected to dye fixing treatment, and the dye fixing agent is a manganese salt And the pH is 5.0 or less.
• Step 1 is a step of dyeing an anodized film of an aluminum alloy. It does not specifically limit as a dyeing
• the method of immersing an anodic oxide film in conventionally well-known dye aqueous solution is mentioned.
• a dye what is marketed as a dye for aluminum alloy anodic oxide film can be used, For example, anionic dye etc. are 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 the aluminum alloy is dyed in step 1 described above.
• Step 2 is a step of immersing the dyed anodic oxide film in a dye fixing agent to carry out a dye fixing treatment.
• a dye fixing agent the dye fixing agent described above may be used.
• the aluminum alloy in which the anodized film is partially formed may be dipped in the dye fixing treatment agent.
• the aluminum alloy is joined to another member to form an article, the article may be immersed in the dye fixing agent.
• the temperature of the dye fixing agent when immersing the anodized film in the dye fixing agent is preferably 55 to 95 ° C., more preferably 60 to 90 ° C., and still more preferably 70 to 80 ° C. When the temperature of the dye fixing agent is in the above range, the dye fixation of the anodized film is further improved.
• the immersion time for immersing the anodized film in the dye fixing 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 dyeing and fixing properties of the anodized film are further improved.
• the upper limit of immersion time is the said range, it is excellent in production efficiency.
• the anodized film of the aluminum alloy may be sufficiently washed with water and dried, and then dipped in the above-mentioned dye fixing agent. This further improves the dyeing and fixing properties of the anodized film.
• the anodized film is subjected to a dyeing and fixing process in step 2 described above.
• Step 3 is a step of sealing the dye-fixed anodized film.
• a sealing treatment method a method of immersing the anodized film subjected to the dyeing and fixing treatment in a sealing treatment solution is preferable.
• sealing solution a sealing solution for an anodic oxide film of an aluminum alloy containing a metal salt, a pH buffer and a surfactant is preferable.
• the sealing solution will be described.
• the sealing solution preferably contains a metal salt.
• metal salts are preferably at least one selected from the group consisting of alkali metal salts, alkaline earth metal salts and transition metal salts.
• the above-mentioned alkali metal salt, alkaline earth metal salt and transition metal salt are not particularly limited, and water-soluble ones are preferable, and carboxylate, sulfamate, sulfate, nitrate, organic sulfonate and the like can be mentioned.
• carboxylates, sulfamates, sulfates, and nitrates are preferable, and acetates, sulfamates, sulfates, and nitrates are preferable in that the anodic oxide film of the sealed aluminum alloy is excellent in the stain resistance. Is more preferred, acetate and nitrate are more preferred, and nitrate is particularly preferred.
• the said metal salt can be used individually by 1 type or in mixture of 2 or more types.
• 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 can be mentioned.
• metal salts of Na, Mg, K, Ca, Ba, and Mn are more preferable, and metal salts of Mg, Ca, and Mn, from the viewpoint that the anodic oxide film of the sealed aluminum alloy is excellent in contamination resistance. Is 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 anodic oxide film of the aluminum alloy sealed with the sealing solution has sufficient contamination resistance. Can be shown.
• the pH buffer is not particularly limited, and conventionally known pH buffers can be used.
• pH buffers include organic acid salts, ammonium salts, amino acids, borates, amine compounds, nitrogen-containing heterocyclic compounds, and the like.
• the stain-fixing property of the anodized film is further improved, and in addition, excellent stain resistance can be imparted to the anodized film of the aluminum alloy sealed with the sealing solution.
• Nitrogen-containing heterocyclic compounds are preferred.
• 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.
• amino acids examples include glycine, alanine, asparagine and the like and salts thereof.
• borate sodium borate, potassium borate, ammonium borate and the like can be mentioned.
• the amine compound examples 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.
• the nitrogen-containing heterocyclic compound is more preferably pyridine; aminopyridine such as 2-aminopyridine, 4-aminopyridine; imidazole; methylimidazole such as 2-methylimidazole; pyrazole; pteridine; oxazole and the like.
• the above pH buffers can be used singly or in combination of two or more.
• the concentration of the pH buffer in the sealing solution is not particularly limited, preferably 0.1 to 100 g / L, and more preferably 0.2 to 20 g / L.
• concentration of the pH buffer is in the above range, the pore-sealing solution can exhibit excellent bufferability of pH, the stain-fixing property of the anodic oxide film is further improved, and the concentration of the pH buffer is high. Defective appearance (dryness) of the surface of the treated product, which is generated due to the passage, is suppressed.
• the surfactant is not particularly limited, and conventionally known surfactants can be used. Examples of such surfactant include anionic surfactants, nonionic surfactants, and amphoteric surfactants.
• anionic surfactant sulfate surfactants, sulfonate surfactants, phosphorus surfactants 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 surfactant examples include compounds in which a plurality of phenyl sulfonates such as diphenyl ether disulfonate are ether-bonded, and further, the compound has an alkyl group, a polyoxyethylene group and the like. And compounds in which a polyoxyethylene alkyl ether group or the like is substituted.
• aromatic sulfonate surfactants include alkyl diphenyl ether disulfonate, alkyl diphenyl ether disulfosuccinate and the like.
• 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 nonionic surfactant capable of setting the cloud point to 85 ° C. or higher in the pore-sealing solution by adjusting the concentration in the pore-sealing solution or combining with another surfactant as the nonionic surfactant can be suitably used.
• nonionic surfactants include polyoxyethylene alkyl ether, glycerin ester polyoxyethylene ether, sorbitan ester, fatty acid alkanolamide and the like.
• the amphoteric surfactant includes alkyl betaine, fatty acid amide betaine, alkyl amine oxide and the like.
• anionic surfactant is preferable.
• sulfate surfactants, sulfonate surfactants and phosphorus surfactants are more preferable, and sulfonate surfactants are still more preferable.
• the above surfactants can be used singly or in combination of two or more.
• the nonionic surfactant may be selected so as not to lower the cloud point of the sealing solution. Moreover, when mixing and using nonionic surfactant and anionic surfactant, the cloud point of surfactant can be made high.
• an anionic surfactant a surfactant which does not cause turbidity by reacting with a contained metal or an amphoteric surfactant may be selected.
• the concentration of the surfactant in the sealing solution is not particularly limited, and is preferably 10 mg / L to 10 g / L, and more preferably 20 mg / L to 5 g / L.
• concentration of the surfactant is in the above range, the dyeing and fixing properties of the anodized film can be further improved, and the sealing solution can exhibit sufficient sealing performance, and the sealed anodic oxide film It is possible to suppress powder blowing on the surface and fogging appearance defects.
• the sealing solution 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 adjusting the pore treatment solution 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 terms of excellent sealing performance.
• aqueous ammonia for example, sodium hydroxide aqueous solution is preferable at the point which is excellent in sealing performance.
• 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 sealing solution 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 adjuster is in the above range, the sealing solution can exhibit sufficient sealing performance, and the decrease in the degree of sealing of the anodic oxide film sealed by the sealing solution is suppressed. can do.
• 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 total content of the metal salt, pH buffer and surfactant in the sealing solution is preferably 0.2 to 100 g / L, more preferably 0.3 to 50 g / L, and 0.5 to 30 g / L. L is more preferred.
• the dyeing and fixing properties of the anodized film can be further improved, and the sealing solution can exhibit sufficient sealing performance, and the sealing solution can be sealed by the sealing solution.
• the anodized film of the treated aluminum alloy can sufficiently exhibit contamination resistance, and powder blowing on the surface of the sealed anodized film and fogging appearance defects can be suppressed.
• the other components are not particularly limited as long as the sealing solution contains a metal salt, a pH buffer and a surfactant, it is preferably an aqueous solution containing the above-mentioned components.
• the sealing solution preferably contains no metal salt such as a nickel-based metal salt.
• metal salts such as Ni, Co, Fe, Cr, etc. are mentioned.
• the pH of the sealing solution is preferably 5.1 to 8.0, more preferably 5.3 to 7.0, and still more preferably 5.5 to 6.0.
• the sealing treatment liquid can show sufficient sealing performance, and the anodic oxide film of the aluminum alloy sealed by the sealing treatment liquid.
• the stain resistance can be sufficiently shown, and appearance defects (powdering, fogging) in which powdery deposits adhere to the surface of the object to be treated are suppressed.
• the temperature of the sealing solution is preferably 85 to 100 ° C., more preferably 88 to 98 ° C., and still more preferably 90 to 98 ° C.
• the sealing treatment time can usually be determined by the film thickness of the anodic oxide film to be treated. Specifically, it is preferable that the number obtained by multiplying the number ( ⁇ m) indicating the film thickness by 0.1 to 10 is the sealing treatment time (minute), and the number ( ⁇ m) indicating the film thickness is It is more preferable to use the number obtained by multiplying 0.2 to 5 as the sealing treatment time (minute), and the number obtained by multiplying the number ( ⁇ m) indicating the film thickness by 0.5 to 4 is preferably sealed. It is more preferable to set it as processing time (minute). For example, if the film thickness of the anodized film is 10 ⁇ m, it is more preferable to multiply 10 by 0.2 to 5 and set the immersion time to about 2 to 50 minutes.
• the sealing time By setting the sealing time to the above range, the dyeing and fixing properties are further improved, and the sealing solution can exhibit sufficient sealing performance, and the aluminum alloy sealed by the sealing solution is used.
• the anodized film can sufficiently show the stain resistance, and can suppress the deterioration of the appearance of the object to be treated due to the appearance defect such as powder blowing and fogging.
• the anodized film subjected to the dyeing and fixing treatment may be immersed while stirring the sealing solution.
• a stirring method circulation stirring, air stirring, gas stirring and rocking stirring are preferable. Among them, circulation stirring and gas stirring are preferable, and circulation stirring is more preferable.
• gas agitation gas agitation using an inert gas such as nitrogen gas or argon gas is preferable.
• the sealing treatment solution absorbs carbon dioxide in the air. May cause turbidity.
• circulation stirring is preferable as a stirring method, but when it is necessary to perform air stirring on equipment, it is possible to carry out gas stirring using the above-mentioned inert gas to make the sealing treatment liquid cloudy. It is preferable at the point which can be suppressed.
• a turbidity removal treatment may be performed to remove turbidity in the sealing solution.
• the above-mentioned turbidity removal treatment may be performed, for example, during standby until the dyeing and fixing-treated anodized film is immersed in the sealing solution, or while the line is at rest.
• the conventionally well-known removal method includes filtration and removal. Specifically, a part of the sealing solution is allowed to flow from a tank for sealing treatment to a spare tank such as a cushion tank which is a chemical replenishment / addition dissolving tank, and the temperature of the sealing solution is preferably 50 ° C. or less. It is cooled, filtered through a filter, and filtered back to be circulated back to the above-mentioned tank for sealing treatment. If the facility does not have a cushion tank, filtration may be performed by simple filtration circulation.
• the object to be treated is an anodized film of an aluminum alloy.
• the anodized film of the aluminum alloy is not particularly limited, and any anodized film of an aluminum alloy obtained by applying a known anodic oxidation method using sulfuric acid, oxalic acid or the like to a general aluminum alloy may be used.
• 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.
• anodic oxidation method applied to an aluminum alloy for example, using an aqueous solution having a sulfuric acid concentration of about 100 g / L to about 400 g / L and a liquid temperature of about -10 to 30 ° C., about 0.5 to 4 A / dm 2
• 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 was TAC YELLOW-SLH, TAC VIOLET-SLH, or TAC YELLOW-SGL (all are TAC dyes manufactured by Okuno Pharmaceutical Co., Ltd.).
• An aqueous solution of each dye was prepared respectively.
• the concentration of the dye in the aqueous solution of the dye was 1 g / L for each dye.
• Example 1 The anodized-stained test piece manufactured according to the above manufacturing conditions contains 1 g / L of manganese acetate, 1 g / L of sodium L-glutamate, and 0.5 g / L of formaldehyde condensate of naphthalene sulfonic acid, and the pH is adjusted to 4. Immersion was carried out for 5 minutes in a dye fixing agent made of an aqueous solution adjusted to 0 (bath temperature 75 ° C.), followed by washing with water to carry out a dyeing and fixing treatment.
• a dye fixing agent made of an aqueous solution adjusted to 0 (bath temperature 75 ° C.
• a sealing treatment solution bath temperature 95 ° C.
• a sealing treatment solution consisting of an aqueous solution of pH 5.7 containing 20 ml / L of Top Seal NIF manufactured by Okuno Pharmaceutical Co., Ltd., washed with water and dried to seal the hole did.
• Examples 2 to 7 The dyeing treatment, the dyeing and fixing treatment, and the pore sealing treatment were performed in the same manner as in Example 1 except that the treatment conditions were changed as shown in Tables 1 and 2.
• Dyeing Fixability Anodized-dyed test pieces produced using the above-mentioned dyes were measured for L *, a * and b * with a spectrocolorimeter (CM-3700A manufactured by Konica Minolta) and used as reference values. Next, L *, a *, b * of the test pieces obtained in the above-mentioned Examples and Comparative Examples were measured, and evaluated by the total amount of change ⁇ E * ab with respect to the above-mentioned reference value. The lower the ⁇ E * ab, the higher the dye fixation.
• CM-3700A manufactured by Konica Minolta

Landscapes

• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Electrochemistry (AREA)
• Materials Engineering (AREA)
• Metallurgy (AREA)
• Organic Chemistry (AREA)
• General Chemical & Material Sciences (AREA)
• Chemical Treatment Of Metals (AREA)

Priority Applications (2)

Applications Claiming Priority (2)

Publications (1)

Family

ID=65527385

Family Applications (1)

Country Status (4)

Cited By (1)

Families Citing this family (3)

Citations (2)

Family Cites Families (7)

• 2018
  • 2018-03-12 CN CN201880056257.5A patent/CN111032926B/zh active Active
  • 2018-03-12 JP JP2019538943A patent/JPWO2019044004A1/ja active Pending
  • 2018-03-12 WO PCT/JP2018/009435 patent/WO2019044004A1/ja active Application Filing
  • 2018-03-22 TW TW107109786A patent/TWI741166B/zh active

Patent Citations (2)

Also Published As

Similar Documents

Legal Events