EP0555244A1 - Additif de l'electrolyte d'un bain colorant pour l'aluminium et procede de teinture de l'aluminium. - Google Patents
Additif de l'electrolyte d'un bain colorant pour l'aluminium et procede de teinture de l'aluminium.Info
- Publication number
- EP0555244A1 EP0555244A1 EP91918011A EP91918011A EP0555244A1 EP 0555244 A1 EP0555244 A1 EP 0555244A1 EP 91918011 A EP91918011 A EP 91918011A EP 91918011 A EP91918011 A EP 91918011A EP 0555244 A1 EP0555244 A1 EP 0555244A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- amount
- coloring
- antioxidant
- improver
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000004040 coloring Methods 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 23
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 22
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 239000002000 Electrolyte additive Substances 0.000 title claims abstract description 21
- 230000008569 process Effects 0.000 title claims description 18
- 239000004411 aluminium Substances 0.000 title 2
- 239000003086 colorant Substances 0.000 title 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 16
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 8
- YCPXWRQRBFJBPZ-UHFFFAOYSA-N 5-sulfosalicylic acid Chemical compound OC(=O)C1=CC(S(O)(=O)=O)=CC=C1O YCPXWRQRBFJBPZ-UHFFFAOYSA-N 0.000 claims description 13
- WNKQDGLSQUASME-UHFFFAOYSA-N 4-sulfophthalic acid Chemical compound OC(=O)C1=CC=C(S(O)(=O)=O)C=C1C(O)=O WNKQDGLSQUASME-UHFFFAOYSA-N 0.000 claims description 11
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 claims description 11
- IUTCEZPPWBHGIX-UHFFFAOYSA-N tin(2+) Chemical compound [Sn+2] IUTCEZPPWBHGIX-UHFFFAOYSA-N 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- YDSWCNNOKPMOTP-UHFFFAOYSA-N mellitic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(O)=O)=C(C(O)=O)C(C(O)=O)=C1C(O)=O YDSWCNNOKPMOTP-UHFFFAOYSA-N 0.000 claims description 6
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 5
- AUFZRCJENRSRLY-UHFFFAOYSA-N 2,3,5-trimethylhydroquinone Chemical compound CC1=CC(O)=C(C)C(C)=C1O AUFZRCJENRSRLY-UHFFFAOYSA-N 0.000 claims description 4
- -1 alkali metal salts Chemical class 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- ZMPRRFPMMJQXPP-UHFFFAOYSA-N 2-sulfobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1S(O)(=O)=O ZMPRRFPMMJQXPP-UHFFFAOYSA-N 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 238000003892 spreading Methods 0.000 claims description 3
- 230000007480 spreading Effects 0.000 claims description 3
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 3
- TZBROGJRQUABOK-UHFFFAOYSA-N 4-hydroxynaphthalene-2,7-disulfonic acid Chemical compound OS(=O)(=O)C1=CC=C2C(O)=CC(S(O)(=O)=O)=CC2=C1 TZBROGJRQUABOK-UHFFFAOYSA-N 0.000 claims description 2
- 239000005711 Benzoic acid Substances 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 2
- 235000010233 benzoic acid Nutrition 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 abstract description 18
- 239000000975 dye Substances 0.000 abstract description 11
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 abstract description 8
- 238000004043 dyeing Methods 0.000 abstract description 8
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract 1
- 230000000996 additive effect Effects 0.000 abstract 1
- 235000006708 antioxidants Nutrition 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000243 solution Substances 0.000 description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 6
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 5
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- 238000007743 anodising 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
- 239000000463 material Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 description 2
- WXHLLJAMBQLULT-UHFFFAOYSA-N 2-[[6-[4-(2-hydroxyethyl)piperazin-1-yl]-2-methylpyrimidin-4-yl]amino]-n-(2-methyl-6-sulfanylphenyl)-1,3-thiazole-5-carboxamide;hydrate Chemical compound O.C=1C(N2CCN(CCO)CC2)=NC(C)=NC=1NC(S1)=NC=C1C(=O)NC1=C(C)C=CC=C1S WXHLLJAMBQLULT-UHFFFAOYSA-N 0.000 description 2
- SDGNNLQZAPXALR-UHFFFAOYSA-N 3-sulfophthalic acid Chemical compound OC(=O)C1=CC=CC(S(O)(=O)=O)=C1C(O)=O SDGNNLQZAPXALR-UHFFFAOYSA-N 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric Acid Chemical compound [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 229940037003 alum Drugs 0.000 description 2
- 238000002048 anodisation reaction Methods 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- 229920000159 gelatin Polymers 0.000 description 2
- 239000008273 gelatin Substances 0.000 description 2
- 235000019322 gelatine Nutrition 0.000 description 2
- 235000011852 gelatine desserts Nutrition 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229940044654 phenolsulfonic acid Drugs 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- OBBXFSIWZVFYJR-UHFFFAOYSA-L tin(2+);sulfate Chemical compound [Sn+2].[O-]S([O-])(=O)=O OBBXFSIWZVFYJR-UHFFFAOYSA-L 0.000 description 2
- SYRHIZPPCHMRIT-UHFFFAOYSA-N tin(4+) Chemical class [Sn+4] SYRHIZPPCHMRIT-UHFFFAOYSA-N 0.000 description 2
- 229910000375 tin(II) sulfate Inorganic materials 0.000 description 2
- QXQAPNSHUJORMC-UHFFFAOYSA-N 1-chloro-4-propylbenzene Chemical compound CCCC1=CC=C(Cl)C=C1 QXQAPNSHUJORMC-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- AUMLONZWTOQAIR-UHFFFAOYSA-N 2-tert-butylbenzene-1,4-diol Chemical compound C(C)(C)(C)C1=C(O)C=CC(=C1)O.C(C)(C)(C)C1=C(O)C=CC(=C1)O AUMLONZWTOQAIR-UHFFFAOYSA-N 0.000 description 1
- BZOVBIIWPDQIHF-UHFFFAOYSA-N 3-hydroxy-2-methylbenzenesulfonic acid Chemical compound CC1=C(O)C=CC=C1S(O)(=O)=O BZOVBIIWPDQIHF-UHFFFAOYSA-N 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920002307 Dextran Polymers 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-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
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000010407 anodic oxide Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003411 electrode reaction Methods 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
- 229940074391 gallic acid Drugs 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 235000013882 gravy Nutrition 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229960001553 phloroglucinol Drugs 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- ZFACJPAPCXRZMQ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O.OC(=O)C1=CC=CC=C1C(O)=O ZFACJPAPCXRZMQ-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- VXPDAXLODHMVDJ-UHFFFAOYSA-L sulfuric acid tin(2+) sulfate Chemical compound [Sn+2].OS(O)(=O)=O.[O-]S([O-])(=O)=O VXPDAXLODHMVDJ-UHFFFAOYSA-L 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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
- C25D11/12—Anodising more than once, e.g. in different baths
-
- 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
- C25D11/20—Electrolytic after-treatment
- C25D11/22—Electrolytic after-treatment for colouring layers
Definitions
- the invention describes a new electrolyte additive for a sulfuric, tin (II) -containing dye bath for alternating current coloring of anodized aluminum surfaces, which consists of a synergistic mixture of at least one antioxidant of one of the general formulas I to IV and at least one scattering improver of the general formula V and there is a method for alternating current coloring of anodized aluminum surfaces using the electrolyte additives according to the invention.
- a sulfuric, tin (II) -containing dye bath for alternating current coloring of anodized aluminum surfaces which consists of a synergistic mixture of at least one antioxidant of one of the general formulas I to IV and at least one scattering improver of the general formula V and there is a method for alternating current coloring of anodized aluminum surfaces using the electrolyte additives according to the invention.
- aluminum is known to be coated with a natural oxide layer, the layer thickness of which is generally less than 0.1 ⁇ m (Wemick, Pinner, Zurbrügg, Weiner;
- Electrolyte is preferably used as sulfuric acid, chromic acid or phosphoric acid.
- Organic acids such as oxalic, maleic, phthalic, salicylic, sulfosalicylic, sulfophthalic, tartaric or citric acid are also used in some processes.
- the anodization is generally carried out in 10 to 20% sulfuric acid with a current density of 1.5 A / mm and a temperature of 18 to 22 ° C. within 15 to 60 minutes, depending on the desired layer thickness and intended use.
- the oxide layers produced in this way have a high absorption capacity for a large number of organic and inorganic substances or dyes.
- Electrolytic dyeing processes have been known since the mid-1930s, in which anodized aluminum can be colored in heavy metal salt solutions by treatment with alternating current.
- the elements of the first transition row such as Cr, Mn, Fe, Co, Ni, Cu and in particular Sn, are used above all.
- the heavy eta11salze are mostly used as sulfates, whereby a pH of 0.1 to 2.0 is adjusted with sulfuric acid.
- the counter electrode can either consist of graphite or stainless steel or of the same material which is dissolved in the electrolyte.
- the heavy metal pigment is deposited in the pores of the anodic oxide layer in the half period of the alternating current, in which aluminum is the cathode, while in the second half period the aluminum oxide layer is further strengthened by anodic oxidation.
- the heavy metal is deposited on the bottom of the pores, causing the oxide layer to color.
- a problem with the coloring in tin electrolytes is the easy oxidizability of the tin, which leads to precipitations of basic tin (-IV) oxide hydrates (tin acid) when used and in some cases even when the Sn solutions are stored.
- Aqueous tin (II) sulfate solutions are known to be oxidized to tin (IV) compounds by the action of atmospheric oxygen or by reaction at the electrodes under current load. This is when staining in anodized tin electrolytes.
- phenol-like compounds such as phenolsulfonic acid, cresolsulfonic acid or sulfosalicylic acid (see for example in SA Pozzoli, F. Tegiacchi; Korros. Korro ⁇ sionstik Alum., Event. Eur. Foed. Korros., Vortr. 88th 1976. 139 -45 or in Japanese Patent Laid-Open JP-A-7813583, 78 18483, 77 135841, 76 147436, 7431614, 73 101331, 7120568, 75 26066, 76 122637, 54 097545, 56 081598 and in GB-C-1482390).
- polyfunctional phenols such as the diphenols hydroquinone, pyrocatechol and resorcinol (see in Japanese laid-open documents JP-A-58 113391, 57 200221 and in FR-C-23 84 037) and the triphenols phloroglucin (JP-A-58113391 ), Pyrogallol (SA Pozzoli, F. Tegiacchi; Corros. Corrosion Protection Alum., Veranstst. Eur. Foed. Korros., Vortr. 88th 1976. 139-45 or in Japanese published documents JP-A-58 113391 and 57200221) or gallic acid (JP-A-53 13583) have already been described in this connection.
- Another important problem with electrolytic coloring is the so-called scattering ability (deep scattering), which is the product property of coloring anodized aluminum parts that are at different distances from the counterelectrode with a uniform color.
- Good spreadability is particularly important if the aluminum parts used have a complicated shape (coloring of the depressions), if the aluminum parts are very large and if, for economic reasons, many aluminum parts are to be colored at the same time and medium shades are to be achieved. In application, therefore, a high spreadability is very desirable, since incorrect production is avoided and the optical quality of the colored aluminum parts is generally better.
- the process is more economical due to its good spreadability, since more parts can be colored in one operation.
- the term spreadability is not identical to the term uniformity and must be strictly differentiated from this.
- the uniformity concerns a coloring with the least possible local disturbances in the color (spotty coloring). Poor uniformity is mostly due to impurities such as nitrate or process errors in the anodization. A good color Under no circumstances should beelectrolyte impair the uniformity of the coloring.
- a dyeing process can achieve good uniformity and still have poor spreading power; the reverse is also possible.
- the uniformity is generally only influenced by the chemical composition of the electrolyte, while the scattering ability also depends on electrical and geometric parameters, such as the shape of the workpiece or its position and size.
- DE-A-26 09 146 describes a process for coloring in tin electrolytes, in which the scatterability is set by the special circuit and voltage arrangement.
- DE-A-2428635 describes the use of a combination of tin (II) and zinc salts with the addition of sulfuric acid and additional boric acid as well as aromatic carboxylic and sulfonic acids (sulfophthalic acid or sulfosalicylic acid) in the electrolytic gray coloring of anodically oxidized Objects made of aluminum.
- excellent scattering of the dyeing effect should be achieved when the pH is between 1 and 1.5.
- the setting of the pH to 1 to 1.5 is a basic prerequisite for good electrolytic coloring. It is not described whether the added organic acids have an effect on the spreadability. The spreadability achieved is also not quantified.
- DE-C-32 46 704 describes a process for electrolytic coloring in which good scattering capacity is ensured by using a special geometry in the dye bath.
- cresol and phenol sulfonic acid, organic substances such as dextran trin and / or thiourea and / or gelatin ensure an even coloration.
- the disadvantage of this method is the high investment that is required for the creation of the mechanical devices.
- deposition inhibitors such as dextrin, thiourea and gelatin has only a slight influence on the scatterability, since the deposition process in electrolytic dyeing differs significantly from that in galvanic tinning. A possibility of measuring the improvements in the spreadability is also not given here.
- the object of the present invention was to provide a new electrolyte additive for a sulfuric acid, tin (II) -containing dye bath for AC coloring of anodized aluminum surfaces, which provides the problems known from the above-mentioned prior art, how to ensure lasting dye bath stability, avoidance of Sn (II) oxidation and at the same time guarantee good spreading power.
- the present invention accordingly relates to an electrolyte additive for a sulfuric acid, tin (II) -containing dye bath for AC coloring of anodized aluminum surfaces.
- Chen containing at least one antioxidant and at least one litter improver, characterized in that the electrolyte additive a) as antioxidant, at least one compound of one of the general formulas I to IV,
- Rl and R2 represent hydrogen, alkyl, aryl, alkylaryl, alkylarylsulfonic acid, alkylsulfonic acid each having 1 to 22 carbon atoms and their alkali metal salts
- R3 represents one or more hydrogen and / or alkyl, aryl, Alkylaryl radicals having 1 to 22 carbon atoms are at least one of the radicals R, R2 and R3 being a radical not equal to hydrogen, and b) at least one aromatic carboxylic acid of the general formula V as a scattering improver
- R * to R5 represent hydrogen, hydroxyl, carboxyl and / or sulfonic acid residues.
- Another object of the present invention is a process for AC coloring of anodized aluminum surfaces in a sulfuric acid, tin (II) -containing dye bath, characterized in that an electrolyte additive according to the above definition is used at a pH of 0. 1 to 2.0, at a temperature of 10 to 30 ° C and at an alternating voltage with a frequency of 50 to 60 Hz and a terminal voltage of 10 to 25 V for electrolytic coloring in the sulfuric acid, tin (II) containing dye bath.
- An essential advantage of the electrolyte additive according to the invention is the use of oxidation-stable, water-soluble scatter improvers.
- p-toluenesulfonic acid known from the teaching of EP-A-354365, develops malodorous vapors by oxidizing the methyl group, which makes long dyebath use intolerable.
- it is therefore particularly important to equip the scatter improver with oxidation-stable, functional groups, such as carboxyl, hydroxyl and / or sulfonic acid groups.
- the functional groups mentioned also ensure the required water solubility.
- the electrolyte additive contains at least one of the compounds of the general formulas I to IV in an amount of 0.01 to 2 g / l as an antioxidant and at least one of the compounds of the general formula V in an amount of 0.1 to 30 g / 1 - each based on the dye bath - as a litter improver.
- the antioxidants of the general formulas I to IV in the above concentrations are in particular 2-tert-butyl-1,4-dihydroxybenzene (tert-butylhydroquinone), methylhydroquinone, trimethylhydroquinone, 4-hydroxy-2, 7-naphthalene disulfonic acid and / or p-hydroxyanisole used.
- 5-sulfosalicylic acid 4-sulfophthalic acid, 2-sulfobenzoic acid, benzoic acid and / or benzene hexacarboxylic acid are used in particular as a scatter improver of the general formula V.
- the combination of 5-sulfosalicylic acid and 4-sulfophthalic acid has proven to be particularly effective in the sense of a synergistic effect.
- the electrolyte additive according to the invention accordingly contains, in each case based on the total volume of the dyebath:
- the electrolyte additive according to the invention - in each case based on the total volume of the dyebath - contains in particular: a) as an antioxidant t-butylhydroquinone in an amount of 0.1 to 0.5, preferably 0.2 to 0, 3 g / 1 and b) as a scattering improver 5-sulfosalicylic acid in an amount of 1 to 3 g / 1, preferably 1.5 to 2.5 g / 1 and 4-sulfophthalic acid in an amount of 8 to 12 g / 1, preferably 10 g / 1.
- the dyeing is usually carried out with the aid of a tin (II) sulfate solution which contains about 3 to 20 g, preferably 7 to 16 g, of tin (II) per liter.
- Coloring is preferably carried out at a pH of 0.1 to 2.0, corresponding to 16 to 22 g of sulfuric acid per liter, at a temperature of about 14 to 30 ° C.
- the alternating voltage or alternating current superimposed on the direct current (50 to 60 Hz) is preferably set at 10 to 25 V, preferably 15 to 18 V, with an optimum of approximately 17 V + 3 V.
- alternating current coloring means either the coloring with pure alternating current or the coloring with "direct current superimposed alternating current” or "alternating current superimposed direct current”.
- the value of the terminal voltage is given in each case.
- the coloring begins at a current density of usually about 1 A / dm 2 , which then drops to a constant value of 0.2 to 0.5 A / dm 2 .
- the metal concentration in the dyebath and the dipping times different tones are obtained, which can vary between champagne-colored and various bronze tones to black.
- the method of the present invention is characterized in that the electrolyte contains further heavy metal salts in addition to tin, for example nickel, cobalt, copper and / or zinc (see Wernick et al, loc. Cit.).
- test 1 a) Quick test to assess the storage stability of the baths (test 1)
- An aqueous electrolyte was prepared, each containing 20 g / 1 sulfuric acid and 10 g / 1 Sn (II) ions, as well as corresponding amounts of an electrolyte additive.
- 1-1- solutions were stirred vigorously at room temperature with a magnetic stirrer and gassed with 12 l / h of pure oxygen over a glass frit.
- the content of Sn (II) ions after 4 hours was recorded iodometrically.
- the percentage decrease in Sn (II) concentration was recorded.
- an aqueous electrolyte which contained 20 g / 1 sulfuric acid, 10 g / 1 Sn (II) ions and corresponding amounts of an electrolyte additive.
- the permanent electrolysis (alternating current 50 Hz, voltage: 12 V) was carried out with stainless steel electrodes.
- the flowing amount of electricity was registered with an Ah counter.
- the characteristic behavior of the oxide layer to be colored was simulated by corresponding sinusoidal distortion of the alternating current at high capacitive loads.
- the amount of Sn (II) ions oxidized by electrode reactions was determined by continuous iodometric titration of the electrolyte and by gravi etric determination of the reductively deposited Sn and the difference from the suirane of these two values to the initial amount of dissolved Sn (II).
- the Ah value was chosen to have an antioxidant effect, at which a reduction in the Sn (II) concentration by 5 g / l can no longer be prevented.
- Test sheets measuring 50 mm x 460 mm x 1 mm made of the DIN material AI 99.5 were conventionally pretreated and then electrolytically colored in a dye bath with a suitable geometry (electrode at a distance of 1 to 5 cm from the counter electrodes).
- the dyebath also contained different amounts of the test substances (see examples and comparative examples).
- the standard dyeing was 16 V (alternating current 50 Hz) for 5 minutes.
- the "mean coloring" results from the individual measured values.
- the scatterability is determined from this as a measure of the correspondence of each measuring point with the mean value and is given as a process value.
- the Streuauch ⁇ mean speed of 100% r is that the test sheet over the entire length ein ⁇ uniformly colored. The closer the values come to 0%, the more differently the sheet ends are colored.
- Test sheets made of the DIN material AI 99.5 were conventionally pretreated (degreased, pickled, decapitated) and after the GS process (200 g / 1 sulfuric acid, 10 g / 1 Al (III), air flow rate, 1 , 5 A / dm 2 , 18 ° C) anodized for 60 minutes. This resulted in a layer structure of approximately 20 ⁇ m.
- the one so pretreated As described in the following examples, sheets were electrolytically colored with alternating current (50 Hz). The results are summarized in Table 1.
- Electrolyte 10.0 g / 1 Sn (II)
- Electrolyte 10.0 g / 1 Sn (II)
- Electrolyte 10.0 g / 1 Sn (II)
- Electrolyte 10.0 g / 1 Sn (lT)
- Electrolyte 10.0 g / 1 Sn (II)
- Electrolyte 10.0 g / 1 Sn (II)
- Tin (II) salt electrolytes such as storage stability, antioxidant activity and scatterability, were significantly improved compared to Comparative Examples 1 to 4.
- Comparative Example 5 an intensifying, malodorous odor occurs after only 15 minutes.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Cosmetics (AREA)
- Lubricants (AREA)
Abstract
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4034304 | 1990-10-29 | ||
DE4034304A DE4034304A1 (de) | 1990-10-29 | 1990-10-29 | Elektrolytzusatzmittel fuer ein faerbebad zur aluminiumeinfaerbung und verfahren zur einfaerbung von aluminium |
PCT/EP1991/001994 WO1992007976A1 (fr) | 1990-10-29 | 1991-10-21 | Additif de l'electrolyte d'un bain colorant pour l'aluminium et procede de teinture de l'aluminium |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0555244A1 true EP0555244A1 (fr) | 1993-08-18 |
EP0555244B1 EP0555244B1 (fr) | 1995-04-12 |
Family
ID=6417215
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP91918011A Expired - Lifetime EP0555244B1 (fr) | 1990-10-29 | 1991-10-21 | Additif de l'electrolyte d'un bain colorant pour l'aluminium et procede de teinture de l'aluminium |
Country Status (17)
Country | Link |
---|---|
US (1) | US5409592A (fr) |
EP (1) | EP0555244B1 (fr) |
JP (1) | JP2941055B2 (fr) |
KR (1) | KR0185157B1 (fr) |
CN (1) | CN1066496C (fr) |
AR (1) | AR245786A1 (fr) |
AT (1) | ATE121145T1 (fr) |
AU (1) | AU646508B2 (fr) |
CA (1) | CA2095247C (fr) |
CS (1) | CS327291A3 (fr) |
DE (2) | DE4034304A1 (fr) |
ES (1) | ES2070514T3 (fr) |
MX (1) | MX9101817A (fr) |
PT (1) | PT99342B (fr) |
WO (1) | WO1992007976A1 (fr) |
YU (1) | YU170691A (fr) |
ZA (1) | ZA918569B (fr) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4120415A1 (de) * | 1991-06-20 | 1992-12-24 | Henkel Kgaa | Konfektioniertes zinn(ii)sulfat-granulat zur elektrolytischen metallsalzeinfaerbung |
DE4244021A1 (de) * | 1992-12-24 | 1994-06-30 | Henkel Kgaa | Verfahren zur elektrolytischen Wechselstromeinfärbung von Aluminiumoberflächen |
CN1038856C (zh) * | 1993-01-16 | 1998-06-24 | 成都科技大学 | 铝及铝合金的复合着色方法 |
DE19852219C1 (de) * | 1998-11-12 | 2000-05-11 | Schloetter Fa Dr Ing Max | Wäßrige Lösung zur elektrolytischen Abscheidung von Zinn-Zink-Legierungen und Verwendung der Lösung |
CN104651905B (zh) * | 2015-01-28 | 2017-11-07 | 永保纳米科技(深圳)有限公司 | 一种阳极铝匀染缓染助剂及其操作液,和阳极铝匀染缓染处理工艺 |
CN107815716B (zh) * | 2017-09-12 | 2019-09-20 | 广东长盈精密技术有限公司 | 对工件的表面进行处理的方法 |
Family Cites Families (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR752359A (fr) * | 1933-09-20 | |||
GB1151460A (en) * | 1967-10-09 | 1969-05-07 | Motohiko Kanai | Improvements in and relating to the Electroplating of Tin-Lead Alloy |
JPS4931674A (fr) * | 1972-07-25 | 1974-03-22 | ||
JPS5245650B2 (fr) * | 1972-04-03 | 1977-11-17 | ||
AT324795B (de) * | 1973-07-02 | 1975-09-25 | Piesslinger Ind Baubedarf | Verfahren und färbeelektrolyt zum graufärben von anodisch oxydierten gegenständen aus aluminium oder dessen legierungen |
JPS5423664B2 (fr) * | 1975-03-06 | 1979-08-15 | ||
JPS51122637A (en) * | 1975-04-19 | 1976-10-26 | Riyouji Suzuki | Process for rapid coloring anodic coating of aluminum |
JPS51147436A (en) * | 1975-06-13 | 1976-12-17 | Aiden Kk | Process for coloring aluminum anodized coating |
GB1482390A (en) * | 1975-11-24 | 1977-08-10 | Norsk Hydro As | Process for colouring of anodised aluminium and aluminium alloys |
JPS6012437B2 (ja) * | 1976-05-10 | 1985-04-01 | 株式会社パイロット | アルミニウム又はその合金の電解着色法 |
JPS5318483A (en) * | 1976-08-04 | 1978-02-20 | Hitachi Denkaihaku Kenkyusho | Method of manufacturing aluminumminorganic aggregating agents |
FR2384037A1 (fr) * | 1977-03-17 | 1978-10-13 | Nice Anodisation Sa | Perfectionnement au procede de coloration electrolytique de l'aluminium et de ses alliages |
JPS5497545A (en) * | 1978-01-19 | 1979-08-01 | Sumitomo Light Metal Ind | Forming of colored skin of aluminium |
JPS6049138B2 (ja) * | 1981-06-05 | 1985-10-31 | 三菱マテリアル株式会社 | 錫塩酸性溶液における錫塩の加水分解防止法 |
JPS6026840B2 (ja) * | 1981-12-25 | 1985-06-26 | 三菱マテリアル株式会社 | Al又はAl金の電解着色法 |
DE3426704C2 (de) * | 1984-07-20 | 1987-03-26 | Oskar Krieger Maschinen- und Metallbau AG, Muttenz | Vorrichtung zum Zuführen von Feststoffen in einen Mischbehälter |
DE3824403A1 (de) * | 1988-07-19 | 1990-01-25 | Henkel KGaA, 4000 Düsseldorf | Verfahren zur elektrolytischen metallsalzeinfaerbung von anodisierten aluminiumoberflaechen |
-
1990
- 1990-10-29 DE DE4034304A patent/DE4034304A1/de not_active Withdrawn
-
1991
- 1991-10-21 ES ES91918011T patent/ES2070514T3/es not_active Expired - Lifetime
- 1991-10-21 WO PCT/EP1991/001994 patent/WO1992007976A1/fr active IP Right Grant
- 1991-10-21 JP JP3517050A patent/JP2941055B2/ja not_active Expired - Lifetime
- 1991-10-21 EP EP91918011A patent/EP0555244B1/fr not_active Expired - Lifetime
- 1991-10-21 AT AT91918011T patent/ATE121145T1/de not_active IP Right Cessation
- 1991-10-21 CA CA002095247A patent/CA2095247C/fr not_active Expired - Fee Related
- 1991-10-21 AU AU87439/91A patent/AU646508B2/en not_active Ceased
- 1991-10-21 US US08/050,038 patent/US5409592A/en not_active Expired - Fee Related
- 1991-10-21 KR KR1019930701249A patent/KR0185157B1/ko not_active IP Right Cessation
- 1991-10-21 DE DE59105203T patent/DE59105203D1/de not_active Expired - Fee Related
- 1991-10-25 PT PT99342A patent/PT99342B/pt not_active IP Right Cessation
- 1991-10-25 YU YU170691A patent/YU170691A/sh unknown
- 1991-10-28 ZA ZA918569A patent/ZA918569B/xx unknown
- 1991-10-28 CN CN91109996A patent/CN1066496C/zh not_active Expired - Fee Related
- 1991-10-29 AR AR91321017A patent/AR245786A1/es active
- 1991-10-29 CS CS913272A patent/CS327291A3/cs unknown
- 1991-10-29 MX MX9101817A patent/MX9101817A/es not_active IP Right Cessation
Non-Patent Citations (1)
Title |
---|
See references of WO9207976A1 * |
Also Published As
Publication number | Publication date |
---|---|
JP2941055B2 (ja) | 1999-08-25 |
WO1992007976A1 (fr) | 1992-05-14 |
ES2070514T3 (es) | 1995-06-01 |
EP0555244B1 (fr) | 1995-04-12 |
AU8743991A (en) | 1992-05-26 |
KR0185157B1 (ko) | 1999-04-01 |
KR930702556A (ko) | 1993-09-09 |
CA2095247A1 (fr) | 1992-04-30 |
ZA918569B (en) | 1992-07-29 |
PT99342A (pt) | 1992-09-30 |
CS327291A3 (en) | 1992-06-17 |
MX9101817A (es) | 1992-06-05 |
AU646508B2 (en) | 1994-02-24 |
YU170691A (sh) | 1994-01-20 |
DE59105203D1 (de) | 1995-05-18 |
AR245786A1 (es) | 1994-02-28 |
CA2095247C (fr) | 2002-01-01 |
CN1061056A (zh) | 1992-05-13 |
US5409592A (en) | 1995-04-25 |
ATE121145T1 (de) | 1995-04-15 |
DE4034304A1 (de) | 1992-04-30 |
JPH06502217A (ja) | 1994-03-10 |
CN1066496C (zh) | 2001-05-30 |
PT99342B (pt) | 1999-02-26 |
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