JP2015004084A - Sealing liquid for anodic oxidation film of aluminum alloy - Google Patents
Sealing liquid for anodic oxidation film of aluminum alloy Download PDFInfo
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- JP2015004084A JP2015004084A JP2013128643A JP2013128643A JP2015004084A JP 2015004084 A JP2015004084 A JP 2015004084A JP 2013128643 A JP2013128643 A JP 2013128643A JP 2013128643 A JP2013128643 A JP 2013128643A JP 2015004084 A JP2015004084 A JP 2015004084A
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- anionic surfactant
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- 238000007789 sealing Methods 0.000 title claims abstract description 145
- 229910000838 Al alloy Inorganic materials 0.000 title claims abstract description 47
- 239000007788 liquid Substances 0.000 title claims abstract description 33
- 230000003647 oxidation Effects 0.000 title abstract description 7
- 238000007254 oxidation reaction Methods 0.000 title abstract description 7
- -1 ethanolamine compound Chemical class 0.000 claims abstract description 37
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 29
- 239000000243 solution Substances 0.000 claims abstract description 25
- 239000007864 aqueous solution Substances 0.000 claims abstract description 19
- HZAXFHJVJLSVMW-UHFFFAOYSA-N monoethanolamine hydrochloride Natural products NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims abstract description 15
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 7
- 239000010407 anodic oxide Substances 0.000 claims description 5
- 125000001165 hydrophobic group Chemical group 0.000 claims description 5
- 150000008052 alkyl sulfonates Chemical class 0.000 claims description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 4
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 3
- 125000005037 alkyl phenyl group Chemical group 0.000 claims description 3
- 150000008051 alkyl sulfates Chemical class 0.000 claims description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 3
- 125000001624 naphthyl group Chemical group 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 229940077388 benzenesulfonate Drugs 0.000 claims description 2
- 238000003672 processing method Methods 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 abstract description 17
- 238000005260 corrosion Methods 0.000 abstract description 17
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 abstract description 14
- 229940078494 nickel acetate Drugs 0.000 abstract description 14
- 150000002815 nickel Chemical class 0.000 abstract description 12
- 238000012360 testing method Methods 0.000 description 23
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 238000004040 coloring Methods 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 150000002169 ethanolamines Chemical class 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 238000007743 anodising Methods 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000003429 antifungal agent Substances 0.000 description 2
- 229940121375 antifungal agent Drugs 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 125000001196 nonadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000006174 pH buffer Substances 0.000 description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- ZIWRUEGECALFST-UHFFFAOYSA-M sodium 4-(4-dodecoxysulfonylphenoxy)benzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCOS(=O)(=O)c1ccc(Oc2ccc(cc2)S([O-])(=O)=O)cc1 ZIWRUEGECALFST-UHFFFAOYSA-M 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 206010020751 Hypersensitivity Diseases 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- XOGDXEHHBLSVEM-UHFFFAOYSA-H S(=O)(=O)([O-])[O-].[Sn+4].[Ni+2].S(=O)(=O)([O-])[O-].S(=O)(=O)([O-])[O-] Chemical compound S(=O)(=O)([O-])[O-].[Sn+4].[Ni+2].S(=O)(=O)([O-])[O-].S(=O)(=O)([O-])[O-] XOGDXEHHBLSVEM-UHFFFAOYSA-H 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 1
- 208000026935 allergic disease Diseases 0.000 description 1
- 230000007815 allergy Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 238000002048 anodisation reaction Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000004512 die casting Methods 0.000 description 1
- WMYWOWFOOVUPFY-UHFFFAOYSA-L dihydroxy(dioxo)chromium;phosphoric acid Chemical compound OP(O)(O)=O.O[Cr](O)(=O)=O WMYWOWFOOVUPFY-UHFFFAOYSA-L 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- NVVZQXQBYZPMLJ-UHFFFAOYSA-N formaldehyde;naphthalene-1-sulfonic acid Chemical compound O=C.C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 NVVZQXQBYZPMLJ-UHFFFAOYSA-N 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- HKFZDVPCCOOGEV-UHFFFAOYSA-N nickel(3+);borate Chemical compound [Ni+3].[O-]B([O-])[O-] HKFZDVPCCOOGEV-UHFFFAOYSA-N 0.000 description 1
- DBJLJFTWODWSOF-UHFFFAOYSA-L nickel(ii) fluoride Chemical compound F[Ni]F DBJLJFTWODWSOF-UHFFFAOYSA-L 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Abstract
Description
本発明は、アルミニウム合金の陽極酸化皮膜用封孔処理方法、及び該封孔処理液を用いる封孔処理方法に関する。 The present invention relates to a sealing method for an anodized film of an aluminum alloy and a sealing method using the sealing solution.
アルミニウム合金の陽極酸化皮膜には、汚れ防止、耐食性の向上等を達成するため封孔処理を施すのが一般的である。封孔処理方法としては、沸騰水封孔、水蒸気封孔、常温封孔、酢酸ニッケル水溶液を用いて封孔処理を行う酢酸ニッケル封孔等が知られている（下記非特許文献１参照）。 The anodized film of an aluminum alloy is generally subjected to a sealing treatment in order to prevent contamination and improve corrosion resistance. Known sealing methods include boiling water sealing, water vapor sealing, room temperature sealing, nickel acetate sealing that performs sealing using a nickel acetate aqueous solution (see Non-Patent Document 1 below).
中でも、沸騰水封孔に比べて皮膜の耐食性が得られやすく、水蒸気封孔に比べて作業効率に優れており、常温封孔に比べて液管理がしやすい等の理由により、酢酸ニッケル封孔が特に用いられている。 Among them, nickel acetate sealing is easy because the corrosion resistance of the film can be easily obtained compared to boiling water sealing, the work efficiency is superior to water vapor sealing, and liquid management is easier than normal temperature sealing. Is particularly used.
しかしながら、近年、ニッケルアレルギーや微粉末性のニッケル塩の有毒性が問題になっていることから、ニッケル塩を用いない封孔処理方法によって、酢酸ニッケル封孔と同程度の耐食性、封孔度等の封孔性能を有する陽極酸化皮膜を製造することが望まれている。 However, in recent years, nickel allergy and toxicity of finely powdered nickel salts have become a problem, so the sealing treatment method that does not use nickel salts has the same degree of corrosion resistance, sealing degree, etc. as nickel acetate sealing. It is desired to produce an anodic oxide film having a sealing performance of
また、酢酸ニッケル封孔は、通常、９０℃以上の高温の封孔浴を用いて行われており、省エネルギー、封孔浴の高温に対する安全性等の観点から比較的低い温度で封孔可能な封孔処理方法も望まれている。 Nickel acetate sealing is usually performed using a high-temperature sealing bath of 90 ° C. or higher, and can be sealed at a relatively low temperature from the viewpoint of energy saving, safety against the high temperature of the sealing bath, and the like. A sealing treatment method is also desired.
以前から、ニッケル塩を用いない封孔処理方法が提案されている（下記特許文献１等参照）。特許文献１には、マグネシウム等のアルカリ土類金属を含む封孔処理液を用いた封孔処理方法が記載されているが、酢酸ニッケル封孔の場合と同様に高温の封孔浴を用いて行われる封孔処理である。 A sealing treatment method that does not use nickel salt has been proposed (see Patent Document 1 below). Patent Document 1 describes a sealing treatment method using a sealing treatment liquid containing an alkaline earth metal such as magnesium, but using a high-temperature sealing bath as in the case of nickel acetate sealing. This is a sealing process to be performed.
また、比較的低温での封孔としては常温封孔があるが、常温封孔はフッ化ニッケルなどのニッケル塩を用いて行うものであるためニッケルフリーの封孔処理ではないという問題点がある。 Moreover, although there is room temperature sealing as a relatively low temperature sealing, there is a problem that room temperature sealing is performed using a nickel salt such as nickel fluoride and is not nickel-free sealing. .
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、その主な目的は、ニッケル塩を含有しない封孔処理液であって、ニッケル塩を含有する封孔処理液を用いた場合と同程度の耐食性、封孔度等の封孔性能を付与することができ、しかも、酢酸ニッケル封孔を行う場合に比べ、比較的低温で封孔処理を行うことが可能な新規なアルミニウム合金の陽極酸化皮膜の封孔処理液及び封孔処理方法を提供することである。 The present invention has been made in view of the above-mentioned problems of the prior art, and its main purpose is a sealing treatment liquid not containing a nickel salt, which uses a sealing treatment liquid containing a nickel salt. It is possible to provide a sealing performance such as corrosion resistance and sealing degree comparable to that of the case where it was present, and it is possible to perform a sealing process at a relatively low temperature compared to the case where nickel acetate sealing is performed. An object of the present invention is to provide a sealing treatment liquid and a sealing treatment method for an anodized film of an aluminum alloy.
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、アルミニウム合金の陽極酸化皮膜をエタノールアミン化合物及び特定のアニオン系界面活性剤を含有する封孔処理液に浸漬することによって、ニッケル塩を含有する封孔処理液を用いた場合と同程度の耐食性、封孔度等の封孔性能を付与することができ、しかも酢酸ニッケル封孔を行う場合に比べ、比較的低い温度で封孔処理を行うことが可能となることを見出し、ここに本発明を完成するに至った。 The present inventor has intensively studied to achieve the above-described object. As a result, by immersing the anodized film of an aluminum alloy in a sealing treatment solution containing an ethanolamine compound and a specific anionic surfactant, the same degree as when using a sealing treatment solution containing a nickel salt It is found that sealing performance such as corrosion resistance, sealing degree, etc. can be imparted, and that sealing treatment can be performed at a relatively low temperature compared to nickel acetate sealing. The present invention has been completed.
即ち、本発明は、下記のアルミニウム合金の陽極酸化皮膜用封孔処理液、及び該封孔処理液を用いる封孔処理方法を提供するものである。
項１． エタノールアミン化合物、並びにスルホン酸塩型アニオン性界面活性剤及び硫酸エステル塩型アニオン性界面活性剤からなる群より選ばれた少なくとも１種のアニオン性界面活性剤を含有する水溶液からなるアルミニウム合金の陽極酸化皮膜用封孔処理液。
項２． エタノールアミン化合物を０．１〜５０ｇ／Ｌ、アニオン性界面活性剤を０．０１〜３０ｇ／Ｌ含有するｐＨ７．５〜９．８の水溶液である上記項１に記載のアルミニウム合金の陽極酸化皮膜用封孔処理液。
項３． エタノールアミン化合物が、モノエタノールアミン、ジエタノールアミン及びトリエタノールアミンからなる群より選ばれた少なくとも１種である上記項１又は２に記載のアルミニウム合金の陽極酸化皮膜用封孔処理液。
項４． アニオン性界面活性剤が、疎水基として、アルキル基、フェニル基、アルキルフェニル基、ナフチル基、アルキルナフチル基、又はこれらの基が互いにエーテル結合若しくはエステル結合で結合した基を有するものである上記項１〜３のいずれかに記載のアルミニウム合金の陽極酸化皮膜用封孔処理液。
項５． アニオン性界面活性剤が、アルキルスルホン酸塩、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、アルキルジフェニルエーテルジスルホン酸塩、アルキルエーテル硫酸エステル塩及びアルキル硫酸エステル塩からなる群より選ばれた少なくとも１種である上記項１〜４のいずれかに記載のアルミニウム合金の陽極酸化皮膜用封孔処理液。
項６． 上記項１〜５のいずれかに記載のアルミニウム合金の陽極酸化皮膜用封孔処理液中に、アルミニウム合金の陽極酸化皮膜を有する物品を浸漬することを特徴とするアルミニウム合金の陽極酸化皮膜の封孔処理方法。
項７． 封孔処理液の液温が６５〜１００℃である上記項６に記載のアルミニウム合金の陽極酸化皮膜の封孔処理方法。
項８． 上記項６又は７に記載の方法により封孔処理された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 provides the following sealing treatment solution for an anodized film of an aluminum alloy and a sealing treatment method using the sealing treatment solution.
Item 1. An aluminum alloy anode comprising an ethanolamine compound, and an aqueous solution containing at least one anionic surfactant selected from the group consisting of a sulfonate anionic surfactant and a sulfate ester anionic surfactant Sealing solution for oxide film.
Item 2. Item 2. The anodized film of aluminum alloy according to Item 1, which is an aqueous solution having a pH of 7.5 to 9.8 and containing 0.1 to 50 g / L of an ethanolamine compound and 0.01 to 30 g / L of an anionic surfactant. Sealing treatment liquid.
Item 3. Item 3. The sealing solution for anodized film of aluminum alloy according to Item 1 or 2, wherein the ethanolamine compound is at least one selected from the group consisting of monoethanolamine, diethanolamine, and triethanolamine.
Item 4. The above item wherein the anionic surfactant has an alkyl group, a phenyl group, an alkylphenyl group, a naphthyl group, an alkylnaphthyl group, or a group in which these groups are bonded to each other by an ether bond or an ester bond as a hydrophobic group. A sealing solution for an anodized film of an aluminum alloy according to any one of 1 to 3.
Item 5. The anionic surfactant is at least one selected from the group consisting of alkyl sulfonate, alkyl benzene sulfonate, alkyl naphthalene sulfonate, alkyl diphenyl ether disulfonate, alkyl ether sulfate, and alkyl sulfate. A sealing treatment solution for an anodized film of an aluminum alloy according to any one of Items 1 to 4.
Item 6. The sealing of the anodized film of an aluminum alloy characterized by immersing an article having an anodized film of an aluminum alloy in the sealing solution for anodized film of an aluminum alloy according to any one of the above items 1 to 5. Hole processing method.
Item 7. Item 7. The method for sealing an aluminum oxide anodized film according to Item 6, wherein the temperature of the sealing solution is 65 to 100 ° C.
Item 8. An article having an anodized film of an aluminum alloy sealed by the method according to Item 6 or 7.
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.
封孔処理液
本発明の封孔処理液は、エタノールアミン化合物、並びにスルホン酸塩型アニオン性界面活性剤及び硫酸エステル塩型アニオン性界面活性剤からなる群より選ばれた少なくとも１種のアニオン系界面活性剤を含有する水溶液からなるものである。
Sealing treatment liquid The sealing treatment liquid of the present invention comprises at least one anionic system selected from the group consisting of ethanolamine compounds, sulfonate type anionic surfactants and sulfate ester type anionic surfactants. It consists of an aqueous solution containing a surfactant.
エタノール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、及びトリエタノールアミンの各種エタノールアミン化合物を使用できる。中でも、トリエタノールアミンが好ましい。これらのエタノールアミン化合物は、一種単独又は二種以上混合して用いることができる。 As the ethanolamine compound, various ethanolamine compounds such as monoethanolamine, diethanolamine, and triethanolamine can be used. Of these, triethanolamine is preferable. These ethanolamine compounds can be used singly or in combination of two or more.
本発明の封孔処理液では、エタノールアミン化合物の濃度が低すぎる場合には、十分な耐食性及び封孔度が得られないので好ましくない。また、濃度が高すぎる場合には、シミ状ムラなどの外観不良が発生しやすく、やはり好ましくない。よって、このような観点からエタノールアミン化合物の濃度は、０．１〜５０ｇ／Ｌ程度とすることが好ましく、０．３〜２０ｇ／Ｌ程度とすることがより好ましい。 In the sealing treatment liquid of the present invention, when the concentration of the ethanolamine compound is too low, it is not preferable because sufficient corrosion resistance and sealing degree cannot be obtained. On the other hand, when the concentration is too high, appearance defects such as spot-like unevenness tend to occur, which is also not preferable. Therefore, from such a viewpoint, the concentration of the ethanolamine compound is preferably about 0.1 to 50 g / L, and more preferably about 0.3 to 20 g / L.
アニオン性界面活性剤としては、親水基がスルホン酸塩であるスルホン酸塩型アニオン性界面活性剤、又は親水基が硫酸エステル塩である硫酸エステル塩型アニオン性界面活性剤であれば特に限定なく使用できる。このようなアニオン性界面活性剤としては、疎水基としてアルキル基、フェニル基、アルキルフェニル基、ナフチル基、アルキルナフチル基等を有するスルホン酸塩型アニオン性界面活性剤、同様の疎水基を有する硫酸エステル塩型アニオン性界面活性剤等が例示される。これらの疎水基は、互いにエーテル結合又はエステル結合で結合したものであってもよい。 The anionic surfactant is not particularly limited as long as it is a sulfonate anionic surfactant whose hydrophilic group is a sulfonate, or a sulfate ester type anionic surfactant whose hydrophilic group is a sulfate salt. Can be used. Examples of such anionic surfactants include sulfonate type anionic surfactants having an alkyl group, a phenyl group, an alkylphenyl group, a naphthyl group, an alkylnaphthyl group or the like as a hydrophobic group, and sulfuric acid having a similar hydrophobic group. Examples include ester salt type anionic surfactants. These hydrophobic groups may be bonded to each other through an ether bond or an ester bond.
また、このようなアニオン性界面活性剤としては、アルキルスルホン酸塩、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、アルキルジフェニルエーテルジスルホン酸塩等のスルホン酸塩型アニオン性界面活性剤；アルキルエーテル硫酸エステル塩、アルキル硫酸エステル塩等の硫酸エステル塩型アニオン性界面活性剤が好ましい。 Such anionic surfactants include sulfonate type anionic surfactants such as alkyl sulfonates, alkyl benzene sulfonates, alkyl naphthalene sulfonates, and alkyl diphenyl ether disulfonates; alkyl ether sulfates. Sulfate ester type anionic surfactants such as salts and alkyl sulfate esters are preferred.
アルキルスルホン酸塩、アルキルエーテル硫酸エステル塩やアルキル硫酸エステル塩等に含まれるアルキル基としては、炭素数６〜３０程度の直鎖又は分岐の高級アルキル基が挙げられる。このような高級アルキル基の具体例としては、ヘキシル、ヘプチル、オクチル、ノニル、デシル、ウンデシル、ドデシル、トリデシル、テトラデシル、ペンタデシル、ヘキサデシル、ヘプタデシル、オクタデシル、ノナデシル、イコサニル、トリアコンタニル等が挙げられる。 Examples of the alkyl group contained in the alkyl sulfonate, alkyl ether sulfate, alkyl sulfate, and the like include linear or branched higher alkyl groups having about 6 to 30 carbon atoms. Specific examples of such higher alkyl groups include hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosanyl, triacontanil and the like.
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やアルキルジフェニルエーテルジスルホン酸塩等における置換基として含まれるアルキル基としては、炭素数１〜２０程度の直鎖又は分岐のアルキル基が挙げられる。このようなアルキル基の具体例としては、メチル、エチル、プロピル、イソプロピル、ブチル、イソブチル、ｔｅｒｔ−ブチル、ｓｅｃ−ブチル、ペンチル、ヘキシル、ヘプチル、オクチル、ノニル、デシル、ウンデシル、ドデシル、トリデシル、テトラデシル、ペンタデシル、ヘキサデシル、ヘプタデシル、オクタデシル、ノナデシル、イコサニル等が挙げられる。 Examples of the alkyl group contained as a substituent in alkylbenzene sulfonate, alkylnaphthalene sulfonate, alkyl diphenyl ether disulfonate, and the like include linear or branched alkyl groups having about 1 to 20 carbon atoms. Specific examples of such alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, sec-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl. Pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosanyl and the like.
また、塩の形態としては、水溶性の塩であれば特に限定されないが、ナトリウム塩、カリウム塩等のアルカリ金属塩、アンモニウム塩、アミン塩などが挙げられる。これらのアニオン性界面活性剤は、一種単独又は二種以上混合して用いることができる。 The salt form is not particularly limited as long as it is a water-soluble salt, and examples thereof include alkali metal salts such as sodium salt and potassium salt, ammonium salt, and amine salt. These anionic surfactants can be used singly or in combination of two or more.
本発明の封孔処理液では、アニオン性界面活性剤の濃度が低すぎる場合には、十分な耐汚染性及び封孔度が得られないので好ましくない。また、濃度が高すぎる場合には、シミ状ムラなどの外観不良が発生しやすく、やはり好ましくない。よって、このような観点からアニオン性界面活性剤の濃度は、０．０１〜３０ｇ／Ｌ程度とすることが好ましく、０．０５〜２０ｇ／Ｌ程度とすることがより好ましい。 In the sealing treatment liquid of the present invention, if the concentration of the anionic surfactant is too low, it is not preferable because sufficient stain resistance and sealing degree cannot be obtained. On the other hand, when the concentration is too high, appearance defects such as spot-like unevenness tend to occur, which is also not preferable. Therefore, from such a viewpoint, the concentration of the anionic surfactant is preferably about 0.01 to 30 g / L, and more preferably about 0.05 to 20 g / L.
本発明の封孔処理液は、ｐＨが７．５〜９．８程度の範囲内にあることが好ましく、８．０〜９．５程度の範囲内にあることがより好ましい。ｐＨがこの範囲内にある場合には、後述する条件で封孔処理を行うことによって、陽極酸化皮膜の外観を損なうことなく、耐食性、封孔度等の封孔性能を向上させることができる。これに対してｐＨが低すぎると、十分な耐汚染性、耐食性、封孔度等が得られないので好ましくない。一方、ｐＨが高すぎる場合には、シミ状ムラなどの外観不良が発生しやすく、やはり好ましくない。封孔処理液のｐＨは、例えば、酢酸、硝酸、硫酸等の酸類の水溶液；アンモニア水、炭酸ナトリウム、水酸化ナトリウム等のアルカリ類の水溶液を用いて上記ｐＨ範囲となるように調整すればよい。 The sealing solution of the present invention preferably has a pH in the range of about 7.5 to 9.8, and more preferably in the range of about 8.0 to 9.5. When the pH is within this range, the sealing performance such as corrosion resistance and the sealing degree can be improved without impairing the appearance of the anodized film by performing the sealing treatment under the conditions described later. On the other hand, if the pH is too low, sufficient contamination resistance, corrosion resistance, sealing degree, etc. cannot be obtained, which is not preferable. On the other hand, when the pH is too high, appearance defects such as spot-like unevenness tend to occur, which is also not preferable. The pH of the sealing treatment liquid may be adjusted to be within the above pH range using, for example, an aqueous solution of acids such as acetic acid, nitric acid, sulfuric acid; .
本発明の封孔処理液は、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、ｐＨ緩衝剤、ｐＨ調整剤、分散剤、防かび剤、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、酢酸、酢酸塩、硝酸、硝酸塩、アンモニア、アンモニウム塩等のｐＨ緩衝剤又はｐＨ調整剤；ナフタレ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；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などが挙げられる。 The sealing treatment liquid of the present invention is added with a pH buffer, a pH adjuster, a dispersant, an antifungal agent, a complexing agent, etc., if necessary, in order to improve the sealing performance and practical use of the liquid. An agent component may be included. Examples of additives include pH buffers or pH adjusters such as acetic acid, acetate, nitric acid, nitrate, ammonia, and ammonium salts; sulfonic acid-based dispersants such as sodium salt of naphthalenesulfonic acid formalin condensate; benzoic acid, benzoic acid Antifungal agents such as acid salts; complexing agents such as citric acid and citrate.
封孔処理方法
本発明の封孔処理方法では、処理対象物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。
Sealing treatment method In the sealing treatment method of the present invention, the object to be treated is an article having an anodized film of an aluminum alloy.
処理対象とする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アルミニウム合金の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 the aluminum alloy to be processed may be an anodized film of an aluminum alloy obtained by applying a known anodizing method using sulfuric acid, oxalic acid or the like to a general aluminum alloy. The aluminum alloy is not particularly limited, and various aluminum-based alloys can be an object of anodization. Specific examples of aluminum alloys include JIS-A 1000 series to 7000 series wrought alloy alloys, cast materials, die casting materials, etc. Examples include various alloy groups mainly composed of aluminum.
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 the aluminum alloy, for example, an aqueous solution having a sulfuric acid concentration of about 100 g / L to 400 g / L is used, and a liquid temperature is set to about 0 to 30 ° C., and about 0.5 to 4 A / dm 2 . A method of performing electrolysis at the anode current density is mentioned.
また、本発明の封孔処理方法においては、アルミニウム合金の陽極酸化皮膜に電解着色を施したものを処理対象としてもよい。 In the sealing treatment method of the present invention, an anodic oxide film of aluminum alloy that has been subjected to electrolytic coloring may be treated.
電解着色方法としては、公知の着色技術の方法を採用できる。例えば、陽極酸化を行った後、電解着色浴に浸漬し、二次電解を行うことにより陽極酸化皮膜に着色を施すことができる。電解着色浴としては、ニッケル塩−ホウ酸浴、ニッケル塩−スズ塩−硫酸浴などを例示できる。 As the electrolytic coloring method, a known coloring technique can be employed. For example, after anodizing, the anodized film can be colored by dipping in an electrolytic coloring bath and performing secondary electrolysis. Examples of the electrolytic coloring bath include a nickel salt-boric acid bath and a nickel salt-tin salt-sulfuric acid bath.
本発明の封孔処理方法では、上記したアルミニウム合金の陽極酸化皮膜を有する物品を被処理物として用い、前述した封孔処理液中に被処理物を浸漬すればよい。また、必要に応じて、アルミニウム合金の陽極酸化皮膜を有する物品に電解着色等を施した後、十分に水洗を行い、前述した封孔処理液中に被処理物を浸漬してもよい。これにより、被処理物のアルミニウム合金の陽極酸化皮膜の耐食性、封孔度等の封孔性能を大きく向上させることができる。 In the sealing treatment method of the present invention, an article having an anodized film of the above-described aluminum alloy may be used as an object to be processed, and the object to be processed may be immersed in the above-described sealing treatment liquid. In addition, if necessary, an article having an anodized film of an aluminum alloy may be subjected to electrolytic coloring and the like, and then sufficiently washed with water, and the object to be processed may be immersed in the sealing treatment liquid described above. Thereby, sealing performance, such as corrosion resistance of the anodized film of the aluminum alloy of a to-be-processed object and a sealing degree, can be improved significantly.
また、本発明の封孔処理方法では、前述した封孔処理液を用いることにより、酢酸ニッケル封孔を行う場合に比べ、比較的低温で封孔処理を行うことができる。封孔処理温度は酢酸ニッケル封孔を行う場合と同様に９０℃以上であってもよく、６５〜１００℃程度であることが好ましい。熱エネルギー削減、作業安全性、封孔性能等の観点から、７０〜８５℃程度であることがより好ましい。 Further, in the sealing treatment method of the present invention, the sealing treatment can be performed at a relatively low temperature by using the above-described sealing treatment liquid as compared with the case of performing nickel acetate sealing. The sealing treatment temperature may be 90 ° C. or higher as in the case of nickel acetate sealing, and is preferably about 65 to 100 ° C. From the viewpoints of thermal energy reduction, work safety, sealing performance, etc., it is more preferably about 70 to 85 ° C.
封孔処理時間は、通常、処理対象とする陽極酸化皮膜の膜厚により決定することができる。処理時間が極端に短い場合には十分な耐食性、封孔度、及び耐汚染性の向上が認められない。また、処理時間が極端に長い場合には、カブリなどの外観不良が生じ、陽極酸化皮膜の外観を損なうことがあるので好ましくない。このため、封孔処理時間は、通常、膜厚（μｍ）数×１〜５分程度の封孔処理時間とすればよく、膜厚（μｍ）数×１．５〜３分程度の封孔処理時間とすることが好ましい。例えば、陽極酸化皮膜の膜厚が１０μｍであるならば、浸漬時間は１５〜３０分程度とすることが好ましい。 The sealing treatment time can usually be determined by the film thickness of the anodized film to be treated. When the treatment time is extremely short, sufficient improvement in corrosion resistance, sealing degree, and contamination resistance is not recognized. Further, when the treatment time is extremely long, appearance defects such as fogging occur, and the appearance of the anodized film may be impaired, which is not preferable. For this reason, the sealing treatment time may normally be a sealing treatment time of about the number of film thickness (μm) × 1 to 5 minutes, and the sealing time of the film thickness (μm) number × about 1.5 to 3 minutes. The treatment time is preferred. For example, if the thickness of the anodized film is 10 μm, the immersion time is preferably about 15 to 30 minutes.
本発明の封孔処理液は、ニッケル塩を含有しない、エタノールアミン化合物及び特定のアニオン性界面活性剤を含有する封孔処理液であり、アルミニウム合金の陽極酸化皮膜に対して、ニッケル塩を含有する封孔処理液を用いた場合と同程度の耐食性、封孔度等の封孔性能を付与することができ、さらに酢酸ニッケル封孔を行う場合に比べ、比較的低い温度で封孔処理を行うことが可能となる。 The sealing treatment liquid of the present invention is a sealing treatment liquid containing an ethanolamine compound and a specific anionic surfactant that does not contain a nickel salt, and contains a nickel salt with respect to the anodized film of the aluminum alloy. The sealing performance such as the corrosion resistance and the sealing degree similar to the case of using the sealing treatment liquid to be used can be given, and the sealing treatment can be performed at a relatively low temperature compared to the case of nickel acetate sealing. Can be done.
よって、本発明の封孔処理液を用いて封孔処理を行うことによって、ニッケル塩を含有する封孔処理液を用いることなく、封孔性能に優れたアルミニウム合金の陽極酸化皮膜を形成することが可能となる。 Therefore, by performing a sealing treatment using the sealing treatment liquid of the present invention, an anodized film of an aluminum alloy having excellent sealing performance can be formed without using a sealing treatment liquid containing a nickel salt. Is possible.
以下、実施例を挙げて本発明を更に詳細に説明する。 Hereinafter, the present invention will be described in more detail with reference to 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を施したアルミニウム合金試験片を製造した。 In accordance with the following production conditions, anodized aluminum alloy test pieces used in the following examples and comparative examples were produced.
アルミニウム合金の試験片（ＪＩＳ Ａ１１００Ｐ板材）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１０１（商品名）の３０ｇ／Ｌ水溶液、浴温：６０℃）に３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）した。得られた陽極酸化皮膜を水洗し、９８％硫酸１００ｍＬ／Ｌを含む酸活性浴（浴温：室温）に１分間浸漬して酸活性し、水洗を行うことにより、陽極酸化を施したアルミニウム合金試験片（以下、「陽極酸化済試験片」という）を得た。 Degrease by immersing a test piece of aluminum alloy (JIS A1100P plate material) in a weak alkaline degreasing solution (Okuno Pharmaceutical Co., Ltd. Top Alclean 101 (trade name) 30 g / L aqueous solution, bath temperature: 60 ° C.) for 3 minutes. And washed with water and then anodized in an anodizing bath containing sulfuric acid as a main component (including free sulfuric acid 180 g / L and dissolved aluminum 8.0 g / L) (bath temperature: 20 ± 1 ° C., anode current density: 1 A / dm 2 , electrolysis time: 30 minutes, film thickness: about 10 μm). The anodized film thus obtained was washed with water, immersed in an acid activation bath (bath temperature: room temperature) containing 98% sulfuric acid 100 mL / L for 1 minute to activate the acid, and washed with water to perform an anodized aluminum alloy. A test piece (hereinafter referred to as “anodized test piece”) was obtained.
実施例１
上記製造条件に従って製造した陽極酸化済試験片を、トリエタノールアミンを３ｇ／Ｌ、２−メチル−７−エチルウンデカン−４−硫酸エステルナトリウムを１ｇ／Ｌ含み、酢酸でｐＨ８．５に調整した水溶液からなる封孔処理液（浴温：７０℃）に２０分間浸漬して封孔処理を行い、その後、水洗及び乾燥を行った。
Example 1
An aqueous solution in which the anodized test piece produced according to the above production conditions contains 3 g / L of triethanolamine, 1 g / L of sodium 2-methyl-7-ethylundecane-4-sulfate, and is adjusted to pH 8.5 with acetic acid. It was immersed in a sealing treatment liquid (bath temperature: 70 ° C.) for 20 minutes for sealing treatment, and then washed with water and dried.
実施例２
上記製造条件に従って製造した陽極酸化済試験片を、トリエタノールアミンを３ｇ／Ｌ、ドデシルジフェニルエーテルジスルホン酸ナトリウムを１ｇ／Ｌ含み、酢酸でｐＨ８．５に調整した水溶液からなる封孔処理液（浴温：７０℃）に２０分間浸漬して封孔処理を行い、その後、水洗及び乾燥を行った。
Example 2
An anodized test piece produced according to the above production conditions was sealed with an aqueous solution containing 3 g / L triethanolamine and 1 g / L sodium dodecyldiphenyl ether disulfonate and adjusted to pH 8.5 with acetic acid (bath temperature). : 70 ° C.) for 20 minutes for sealing treatment, followed by washing with water and drying.
比較例１
上記製造条件に従って製造した陽極酸化済試験片を、酢酸ニッケル系封孔剤（奥野製薬工業（株）製 トップシールＨ−２９８（商品名））を４０ｍＬ／Ｌ含むｐＨ５．６の水溶液からなる封孔処理液（浴温：９０℃）に１０分間浸漬して封孔処理を行い、その後、水洗及び乾燥を行った。
Comparative Example 1
An anodized test piece manufactured according to the above manufacturing conditions was sealed with a pH 5.6 aqueous solution containing 40 mL / L of nickel acetate-based sealant (Okuno Pharmaceutical Co., Ltd. Top Seal H-298 (trade name)). It was immersed in a pore treatment liquid (bath temperature: 90 ° C.) for 10 minutes for sealing treatment, and then washed and dried.
比較例２
上記製造条件に従って製造した陽極酸化済試験片を、沸騰したイオン交換水からなる封孔処理液に１０分間浸漬して封孔処理を行い、その後、水洗及び乾燥を行った。
Comparative Example 2
The anodized test piece produced according to the above production conditions was immersed in a sealing treatment solution consisting of boiling ion-exchanged water for 10 minutes for sealing treatment, and then washed with water and dried.
比較例３
上記製造条件に従って製造した陽極酸化済試験片を、トリエタノールアミンを３ｇ／Ｌ含み、酢酸でｐＨ８．５に調整した水溶液からなる封孔処理液（浴温：７０℃）に２０分間浸漬して封孔処理を行い、その後、水洗及び乾燥を行った。
Comparative Example 3
The anodized test piece produced according to the above production conditions was immersed in a sealing treatment solution (bath temperature: 70 ° C.) consisting of an aqueous solution containing 3 g / L of triethanolamine and adjusted to pH 8.5 with acetic acid for 20 minutes. Sealing treatment was performed, followed by washing with water and drying.
比較例４
上記製造条件に従って製造した陽極酸化済試験片を、２−メチル−７−エチルウンデカン−４−硫酸エステルナトリウムを１ｇ／Ｌ含み、酢酸及び水酸化ナトリウム水溶液でｐＨ８．５に調整した水溶液からなる封孔処理液（浴温：７０℃）に２０分間浸漬して封孔処理を行い、その後、水洗及び乾燥を行った。
Comparative Example 4
An anodized test piece manufactured according to the above manufacturing conditions was made of an aqueous solution containing 1 g / L of sodium 2-methyl-7-ethylundecane-4-sulfate and adjusted to pH 8.5 with acetic acid and sodium hydroxide aqueous solution. It was immersed in a pore treatment solution (bath temperature: 70 ° C.) for 20 minutes for sealing treatment, and then washed with water and dried.
比較例５
上記製造条件に従って製造した陽極酸化済試験片を、ドデシルジフェニルエーテルジスルホン酸ナトリウムを１ｇ／Ｌ含み、酢酸及び水酸化ナトリウム水溶液でｐＨ８．５に調整した水溶液からなる封孔処理液（浴温：７０℃）に２０分間浸漬して封孔処理を行い、その後、水洗及び乾燥を行った。
Comparative Example 5
The anodized test piece produced according to the above production conditions was sealed with a sealing solution (bath temperature: 70 ° C.) comprising an aqueous solution containing 1 g / L of sodium dodecyldiphenyl ether disulfonate and adjusted to pH 8.5 with acetic acid and aqueous sodium hydroxide solution. ) For 20 minutes to perform sealing treatment, followed by washing with water and drying.
試験例
上記実施例１、２及び比較例１〜５で得られた試験片について、以下の方法で耐食性試験及び封孔度試験を行った。その結果を表１に示す。
１．耐食性試験
ＪＩＳ Ｈ ８６８１−１：１９９９（アルミニウム及びアルミニウム合金の陽極酸化皮膜の耐食性試験方法 第１部：耐アルカリ試験−アルカリ滴下試験）に準拠して、各試験片に水酸化ナトリウム水溶液を滴下し、アルミニウム合金の陽極酸化皮膜が溶け去るまでの時間を測定した。秒数が大きいほど、耐食性が高いことを示す。
２．封孔度試験
ＪＩＳ Ｈ ８６８３−２：１９９９（アルミニウム及びアルミニウム合金の陽極酸化皮膜の封孔度試験方法 第２部：リン酸−クロム酸水溶液浸漬試験）に準拠して、各試験片をリン酸−クロム酸水溶液に浸漬し、単位面積あたりの試験片の質量減少を測定した。数値が小さいほど、封孔度が良いことを示す。
Test Example About the test piece obtained in the said Example 1, 2 and Comparative Examples 1-5, the corrosion resistance test and the sealing degree test were done with the following method. The results are shown in Table 1.
1. Corrosion resistance test In accordance with JIS H 8681-1: 1999 (corrosion resistance test method for anodized films of aluminum and aluminum alloys, Part 1: Alkali resistance test-alkali dropping test), an aqueous sodium hydroxide solution was dropped on each test piece. The time until the anodized film of the aluminum alloy was melted was measured. The larger the number of seconds, the higher the corrosion resistance.
2. Sealing degree test Each test piece was phosphoric acid in accordance with JIS H 8683-2: 1999 (Method for testing the degree of sealing of anodized film of aluminum and aluminum alloy Part 2: Phosphoric acid-chromic acid aqueous solution immersion test) -It immersed in chromic acid aqueous solution, and the mass reduction | decrease of the test piece per unit area was measured. The smaller the numerical value, the better the sealing degree.
表１から明らかなように、実施例１及び２のエタノールアミン化合物及びアニオン性界面活性剤を含有する封孔処理液を用いて封孔処理を行った場合には、比較例１の酢酸ニッケルを含有する封孔処理液を用いて封孔処理した場合に比べて比較的低い温度で封孔処理を行ったにもかかわらず、比較例１と同程度の良好な耐食性及び封孔度を示すことが確認できた。 As is apparent from Table 1, when the sealing treatment was performed using the sealing treatment liquid containing the ethanolamine compounds of Examples 1 and 2 and the anionic surfactant, the nickel acetate of Comparative Example 1 was used. Despite performing sealing treatment at a relatively low temperature compared to the case of sealing treatment using the contained sealing treatment liquid, it exhibits good corrosion resistance and sealing degree comparable to those of Comparative Example 1. Was confirmed.
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| CN105200492A (en) * | 2015-09-24 | 2015-12-30 | 马鞍山杰创塑胶科技有限公司 | Aluminum alloy anode oxide film nickel-free hole sealing agent modified by nanometer rare earth and preparing method thereof |
| CN105200485A (en) * | 2015-09-24 | 2015-12-30 | 马鞍山杰创塑胶科技有限公司 | Aluminum alloy anode oxide film nickel-free sealant high in thermal stability and preparation method thereof |
| CN105239130A (en) * | 2015-09-24 | 2016-01-13 | 马鞍山杰创塑胶科技有限公司 | High-antiseptic aluminum alloy anode oxide film non-nickel sealant and preparation method thereof |
| CN106757271A (en) * | 2016-12-30 | 2017-05-31 | 华东理工大学 | A kind of preparation method of aluminium alloy anode oxide surface slip hole sealing agent |
| CN106757272A (en) * | 2016-12-30 | 2017-05-31 | 华东理工大学 | A kind of preparation method of aluminium alloy anode oxide surface hydrophobicity hole sealing agent |
| CN106757270A (en) * | 2016-12-30 | 2017-05-31 | 华东理工大学 | A kind of preparation method of the middle temperature hole sealing agent of aluminium alloy anode oxide |
| CN109972185A (en) * | 2019-04-17 | 2019-07-05 | 邓华斌 | A kind of aluminium alloy is without nickel environmental protection hole sealing agent and preparation method thereof |
| CN114990666A (en) * | 2022-06-17 | 2022-09-02 | 重庆臻宝实业有限公司 | Hole sealing liquid and hole sealing method for metal surface chemical treatment |
| CN114990666B (en) * | 2022-06-17 | 2023-09-05 | 重庆臻宝科技股份有限公司 | Hole sealing method for metal surface chemical treatment |
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