EP4112772A1 - Organosulfur compound for corrosion protection coating of copper-containing metallic substrates - Google Patents
Organosulfur compound for corrosion protection coating of copper-containing metallic substrates Download PDFInfo
- Publication number
- EP4112772A1 EP4112772A1 EP21382567.2A EP21382567A EP4112772A1 EP 4112772 A1 EP4112772 A1 EP 4112772A1 EP 21382567 A EP21382567 A EP 21382567A EP 4112772 A1 EP4112772 A1 EP 4112772A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- water
- acidic aqueous
- soluble
- aqueous composition
- composition
- 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.)
- Withdrawn
Links
- 150000002898 organic sulfur compounds Chemical class 0.000 title claims abstract description 49
- 238000000576 coating method Methods 0.000 title claims abstract description 27
- 238000005260 corrosion Methods 0.000 title claims abstract description 27
- 239000011248 coating agent Substances 0.000 title claims abstract description 26
- 239000010949 copper Substances 0.000 title claims abstract description 26
- 239000000758 substrate Substances 0.000 title claims abstract description 21
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 230000007797 corrosion Effects 0.000 title abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 73
- 230000002378 acidificating effect Effects 0.000 claims abstract description 54
- 150000001875 compounds Chemical class 0.000 claims abstract description 43
- VOVUARRWDCVURC-UHFFFAOYSA-N thiirane Chemical compound C1CS1 VOVUARRWDCVURC-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 18
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 17
- 125000000524 functional group Chemical group 0.000 claims abstract description 13
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 6
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 claims abstract description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000007142 ring opening reaction Methods 0.000 claims abstract description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 7
- -1 1,4-bis(thiiran-2-ylmethoxy)-1,4-butanediol Chemical compound 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 239000003973 paint Substances 0.000 claims description 5
- 125000001302 tertiary amino group Chemical group 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 150000003335 secondary amines Chemical class 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- WOLKUPAHYFKKGJ-UHFFFAOYSA-N 2-[[2-methyl-3-(thiiran-2-ylmethoxy)-2-(thiiran-2-ylmethoxymethyl)propoxy]methyl]thiirane Chemical compound C1SC1COCC(COCC1SC1)(C)COCC1CS1 WOLKUPAHYFKKGJ-UHFFFAOYSA-N 0.000 claims description 2
- NADBOSDSDIWQFU-UHFFFAOYSA-N 2-[[3-(thiiran-2-ylmethoxy)-2,2-bis(thiiran-2-ylmethoxymethyl)propoxy]methyl]thiirane Chemical compound C1SC1COCC(COCC1SC1)(COCC1SC1)COCC1CS1 NADBOSDSDIWQFU-UHFFFAOYSA-N 0.000 claims description 2
- NJQACFVMBSAECJ-UHFFFAOYSA-N 2-methoxy-n-(2-methoxypropyl)propan-1-amine Chemical compound COC(C)CNCC(C)OC NJQACFVMBSAECJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000005265 dialkylamine group Chemical group 0.000 claims description 2
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims 1
- 238000005554 pickling Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 33
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 30
- 239000008367 deionised water Substances 0.000 description 16
- 229910021641 deionized water Inorganic materials 0.000 description 16
- 238000004809 thin layer chromatography Methods 0.000 description 16
- 150000002118 epoxides Chemical class 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- 239000012074 organic phase Substances 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 9
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910000838 Al alloy Inorganic materials 0.000 description 5
- 238000013019 agitation Methods 0.000 description 5
- 239000008399 tap water Substances 0.000 description 5
- 235000020679 tap water Nutrition 0.000 description 5
- 238000011282 treatment Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 229910000881 Cu alloy Inorganic materials 0.000 description 4
- WPPDFTBPZNZZRP-UHFFFAOYSA-N aluminum copper Chemical compound [Al].[Cu] WPPDFTBPZNZZRP-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 238000002203 pretreatment Methods 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 150000003553 thiiranes Chemical class 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000003570 air Substances 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000003518 caustics Substances 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 238000005238 degreasing Methods 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 238000002129 infrared reflectance spectroscopy Methods 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000550 scanning electron microscopy energy dispersive X-ray spectroscopy Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical class [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000002678 macrocyclic compounds Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 239000008363 phosphate buffer Substances 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- DXIGZHYPWYIZLM-UHFFFAOYSA-J tetrafluorozirconium;dihydrofluoride Chemical compound F.F.F[Zr](F)(F)F DXIGZHYPWYIZLM-UHFFFAOYSA-J 0.000 description 2
- 238000011179 visual inspection Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- NWLUZGJDEZBBRH-UHFFFAOYSA-N 2-(propan-2-yloxymethyl)oxirane Chemical compound CC(C)OCC1CO1 NWLUZGJDEZBBRH-UHFFFAOYSA-N 0.000 description 1
- AHIPJALLQVEEQF-UHFFFAOYSA-N 4-(oxiran-2-ylmethoxy)-n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound C1OC1COC(C=C1)=CC=C1N(CC1OC1)CC1CO1 AHIPJALLQVEEQF-UHFFFAOYSA-N 0.000 description 1
- FAUAZXVRLVIARB-UHFFFAOYSA-N 4-[[4-[bis(oxiran-2-ylmethyl)amino]phenyl]methyl]-n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound C1OC1CN(C=1C=CC(CC=2C=CC(=CC=2)N(CC2OC2)CC2OC2)=CC=1)CC1CO1 FAUAZXVRLVIARB-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical group 0.000 description 1
- UMGDCJDMYOKAJW-UHFFFAOYSA-N aminothiocarboxamide Natural products NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 150000002019 disulfides Chemical class 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical class [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/78—Pretreatment of the material to be coated
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/78—Pretreatment of the material to be coated
- C23C22/80—Pretreatment of the material to be coated with solutions containing titanium or zirconium compounds
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/82—After-treatment
- C23C22/83—Chemical after-treatment
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/16—Sulfur-containing compounds
- C23F11/161—Mercaptans
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/173—Macromolecular compounds
Definitions
- the present invention relates to an acidic aqueous composition for protecting against corrosion of metal surfaces, which contains at least one water-soluble organosulfur compound having at least two adhesion-promoting functional groups, each having a secondary thiol group and at least one vicinal secondary or tertiary amino group for this, and a Process for anti-corrosive coating of a metal surface using the acidic aqueous composition.
- Aluminum alloys are popular materials, especially in the aerospace industry, due to their light weight and strength. However, they have the disadvantage that they have to be protected against corrosion in order to retain their properties. This is currently still being done with highly toxic chromium(VI) compounds, for which alternatives have to be found due to the EU chemicals regulation REACH.
- EP2986678 a method for producing a coating material for anti-corrosion in which a macrocycle is selected as the anti-corrosion compound, the macrocycle being a cyclic molecule or a molecule having a cyclic moiety with six or more nuclear atoms in the cyclic backbone, the anti-corrosion compound containing at least two inhibitor groups wherein the inhibitor groups are each linked to the anticorrosive compound via a labile linkage each independently selected from the group consisting of a disulfide bond and a metal sulfide bond, each labile linkage being selected to dissociate in response to a corrosive stimulus to form a to generate a dissociated inhibitor group, further selecting a carrier adapted for coating a substrate, and mixing the anticorrosive compound and the carrier.
- EP3310837 relates to a flexible chrome-free anticorrosive primer composition containing a thiol-terminated urethane-containing polyether prepolymer, a polyepoxide, 5 to 9% by weight calcium carbonate and 3 to 7% by weight magnesium oxide.
- US2005/0186347 describes a method for coating a metal surface in which a solution containing an alkanethiol compound and a solvent is applied and a self-organizing layer is formed which is intended to ensure protection against corrosion.
- the alkanethiol compound has the general formula R(CH 2 ) n SH where R is methyl, carboxyl, hydroxyl, formyl or amide and n is an integer from 7-21.
- US2016/0168724 discloses compositions, coatings and methods for applying a corrosion inhibiting composition to a substrate.
- the corrosion inhibiting composition contains at least one resin, at least one Bronsted acid and at least one organosulfur corrosion inhibitor.
- US2016/0289537 relates to a method, composition and system for preventing corrosion of metal exposed to an acidic aqueous environment, the composition containing a thietane compound, a thiirane compound or a mixture of the two.
- an acidic aqueous composition which contains at least two adhesion-promoting functional groups which each have a secondary thiol group and at least one vicinal secondary or tertiary amino group for this.
- a first subject matter of the present invention is an acidic aqueous composition (A) for the anti-corrosion coating of a surface of a metallic substrate which is composed at least partially of copper, the acidic aqueous composition (A) containing at least one water-soluble organosulfur compound (A1), which contains at least two adhesion-promoting functional groups (FG), each of which has a secondary thiol group and at least one vicinal secondary or tertiary amino group for this.
- A1 water-soluble organosulfur compound
- FG adhesion-promoting functional groups
- organosulfur compound (A1) a high level of protection against corrosion can be achieved without the disadvantages associated with organosulfur compounds occurring.
- organosulfur compound forms a complex with the copper ions present in the metallic substrate to form a polymeric network thereby preventing pitting corrosion.
- corrosion protection measures based on zirconium oxide compounds as they are already known from the automotive industry, excellent protection of the metallic surface against corrosion could be achieved, which is in comparison to what is achieved with conventional Cr(VI)-based systems is reached.
- water-soluble organosulphur compounds (A1) with a higher functionality, since in these cases the typical odor of sulfur-containing compounds can be further reduced. Therefore, an embodiment is preferred in which the water-soluble organosulfur compound (A1) has at least 3, but not more than 8, preferably not more than 6 and particularly preferably 4 adhesion-promoting functional groups. In a particularly preferred embodiment, the water-soluble organosulfur compound (A1) is aliphatic and particularly preferably aliphatic and saturated.
- the water-soluble organosulfur compound (A1) has the following structural unit (I) as an adhesion-promoting functional group: wherein the radicals R 1 and R 2 are selected from hydrogen or an aliphatic alkyl group having no more than 6 carbon atoms, preferably no more than 4 carbon atoms and more preferably two carbon atoms; wherein at least one R 1 or R 2 is selected from an aliphatic alkyl group having no more than 6 carbon atoms; wherein the radicals R 3 and R 4 in every nth unit (-HCR 3 -CHR 4 -O-) are independently selected from hydrogen or a methyl group; wherein the radicals R 3 and R 4 within an nth unit (-HCR 3 -CHR 4 -O-) cannot both be selected from a methyl group; where n is zero or a natural number less than 6, preferably less than 4.
- the water-soluble organosulfur compound (A1) corresponds to the following structural formula (II): where m is a natural number in the range from 1 to 8, preferably from 1 to 6 and more preferably equal to 1; wherein the radicals R 5 , R 6 and R 7 are selected from hydrogen, an aliphatic alkyl group having not more than 6 carbon atoms, the radical -FG or the radical -CHR 1 -FG; where at least one of the radicals R 5 , R 6 and R 7 , preferably all radicals R 5 , R 6 and R 7 , is either a radical -FG or a group -CHR 1 -FG, preferably a group -CHR 1 -FG, where the groups R 1 and R 2 are selected from hydrogen or an aliphatic alkyl group with not more than 6 carbon atoms, preferably not more than 4 carbon atoms and more preferably two carbon atoms and wherein at least one radical R 1 or R 2 is selected from an aliphatic alkyl group
- the water-soluble organosulfur compound (A1) can be obtained by ring-opening reaction of a polyfunctional thiirane, which is preferably tetrafunctional and particularly preferably aliphatic, with a secondary amine.
- the secondary amine is preferably monofunctional, more preferably aliphatic and especially selected from bis(2-methoxypropyl)amine, bis(2-hydroxypropyl)amine and/or dialkylamines having not more than 4 carbon atoms in the N-substituted alkyl chain, especially diethylamine .
- the thiirane used is preferably selected from 1,4-bis(thiiran-2-ylmethoxy)-1,4-butanediol), 1-(thiiran-2-ylmethoxy)-2,2-bis(thiiran-2-ylmethoxymethyl)propane or 2-[[3-(thiiran-2-ylmethoxy)-2,2-bis(thiiran-2-ylmethoxymethyl)propoxy]methyl]thiirane.
- the water-soluble organosulfur compound (A1) has a molar mass of less than 2000 g/mol, preferably less than 1400 g/mol, particularly preferably less than 1000 g/mol.
- the proportion of the water-soluble organosulfur compound (A1) in the composition (A) according to the invention, based in each case on the acidic aqueous composition (A), is at least 0.01 g/kg, preferably at least 0.05 g/kg , particularly preferably at least 0.1 g/kg and very particularly preferably at least 0.2 g/kg, but preferably not exceeding a proportion of 5 g/kg, particularly preferably 3 g/kg, very particularly preferably 1 g/kg will.
- the corrosion protection could be further increased by the composition according to the invention if it additionally contains free fluoride. Therefore an embodiment is preferred in which the acidic aqueous composition (A) further contains free fluoride, preferably in an amount of at least 5 mg/kg, preferably at least 20 mg/kg, but preferably not more than 400 mg/kg, more preferred not more than 200 mg/kg.
- the free fluoride is calculated as F - in each case, with the total fluoride content (TISAB) preferably not exceeding 1 g/kg, particularly preferably 500 g/kg, calculated as NaF, in a particularly preferred embodiment.
- the composition according to the invention can be combined with other anti-corrosion measures in order to further improve the protective performance.
- the acidic aqueous composition (A) therefore additionally contains at least one water-soluble compound of one or more of the elements Zr, Ti and Si, preferably water-soluble compounds of oxo and/or fluoro complexes of these elements.
- the total proportion of these water-soluble compounds is preferably at least 0.05 mmol/kg, particularly preferably at least 0.1 mmol/kg, very particularly preferably at least 0.5 mmol/kg based on the respective elements Zr, Ti and Si, but preferably not more than 5 mmol/kg based on the respective elements Zr, Ti and Si.
- a further increase in the protective performance due to the composition according to the invention was observed above all in those cases in which the acidic aqueous composition (A) also contains copper ions. Without being bound by any particular theory, it is believed that this aids in the formation of the protective film on the surface of the metal substrate.
- a further embodiment of the acidic aqueous composition (A) is therefore preferred in which the acidic aqueous composition (A) additionally contains at least one water-soluble compound of the element Cu, the proportion of these water-soluble compounds in total preferably being at least 0.1 mmol/kg, particularly preferably at least 0.5 mmol/kg, very particularly preferably at least 1 mmol/kg, based on the element Cu, but preferably does not exceed 5 mmol/kg based on the element Cu.
- the metal substrates are subjected to various pre-treatments before the corrosion protection is applied, which are usually carried out in an acidic environment.
- the acidic aqueous composition according to the invention develops its effect above all when it has a similar pH. Accordingly, the composition (A) according to the invention therefore has a pH which is less than 6.0, preferably less than 5.0, particularly preferably less than 4.5, but which is preferably not less than 1.0, particularly preferably is not less than 2.0, and most preferably not less than 3.0.
- composition according to the invention is particularly suitable as a corrosion protection for aluminum-copper alloys. Therefore, another object of the present invention is a method for anti-corrosive coating of a surface of a metallic substrate composed at least partially of copper, comprising contacting the surface of the metallic substrate with an acidic aqueous composition (A) according to the present Invention.
- the metallic substrate is copper-alloyed aluminum, which preferably contains at least 1% by weight, particularly preferably at least 3% by weight, but preferably less than 6% by weight, of copper.
- the metallic substrate can be subjected to further treatment steps. Therefore, an embodiment is preferred in which the contacting with the acidic aqueous composition (A) is followed by contacting the surface of the metallic substrate with an acidic aqueous composition (B) which comprises at least one water-soluble compound of one or several of the elements Zr, Ti and Si, preferably containing oxo and/or fluoro complexes of these elements.
- the proportion of these water-soluble compounds in the acidic aqueous composition (B) is preferably at least 0.05 mmol/kg, particularly preferably at least 0.1 mmol/kg, based on the respective elements Zr, Ti and Si, but preferably 5 mmol/kg. kg based on the respective elements Zr, Ti and Si.
- the contacting of the acidic aqueous compositions (A) and (B) can be carried out with or without an intermediate rinsing and/or drying step, as required.
- the acidic aqueous composition (B) preferably contains no water-soluble organosulfur compounds (A1) in such an amount as the mass-related Ratio to the amount of water-soluble organosulfur compound (A1) in the acidic aqueous composition (A) exceeds the value 0.1, preferably the value 0.05.
- the method according to the invention comprises a step of acidic desmutting of the surface of the metallic substrate before it is brought into contact with the acidic aqueous composition (A).
- the method according to the invention therefore preferably comprises immediately before contacting with the acidic aqueous composition (A) - with or without an intermediate rinsing step - acidic desmutting of the surface of the metallic substrate, preferably by contacting with an acidic aqueous composition with a pH below 2.0 containing at least one strong acid with a pK a below 1.5, preferably sulfuric acid.
- the metallic surface can be coated with a lacquer for further protection.
- the paint can be applied after it has been brought into contact with the composition according to the invention, without this having a negative effect on the coating quality. Therefore, an embodiment is preferred in which the contacting with the acidic aqueous composition (A) and optionally after the contacting with the acidic aqueous composition (B) - with or without intermediate rinsing and / or Drying step - the coating is done with a paint, which is preferably a powder paint.
- Step 1 Preparation of the thiirane
- Ammonium thiocyanate (19.27, 2 eq.) was dissolved in 60 mL of water. The solution was kept in a water bath and glycidyl isopropyl ether (15 g, 1 eq.) was added. The reaction was stopped after 20 hours when no more epoxide was detectable by thin layer chromatography (TLC). The product was extracted 3 times with 40 ml of dichloromethane, then washed 2 times with 40 ml of deionized water, the organic phase was dried over MgSO 4 and the solvent was removed at 800 mbar and 40.degree. The product obtained was stored under a nitrogen atmosphere at room temperature.
- Ammonium thiocyanate (18.95, 2 eq.) was dissolved in 120 mL of water. The solution was kept in a water bath and ethylene glycol dicyclocidyl ether (15 g, 1 eq.) was added. The reaction was stopped after 6.5 hours when no more epoxide was detectable by thin layer chromatography (TLC). The product was extracted 4 times with 50 ml of dichloromethane, then washed 3 times with 50 ml of deionized water, the organic phase was dried over MgSO 4 and the solvent was removed at 800 mbar and 40.degree. The product obtained was stored under a nitrogen atmosphere at 4°C.
- Ammonium thiocyanate (28.55 g, 2 eq.) was dissolved in 90 mL of water and 30 mL of isopropyl alcohol. The solution was kept in a water bath and trimethylolethane triglycidyl ether (30 g, 1 eq.). was added. The reaction was stopped after 24 hours when epoxide was no longer detectable by thin layer chromatography (TLC). The product was extracted 4 times with 40 ml of dichloromethane, then washed 3 times with 30 ml of deionized water, the organic phase was dried over MgSO 4 and the solvent was removed at 800 mbar and 40.degree. The product obtained was stored under a nitrogen atmosphere at 4°C.
- Ammonium thiocyanate (15.5 g, 2 eq.) was dissolved in a mixture of 10 ml water, 30 ml acetonitrile and 10 g N,N-diglycidyl-4-glycidyloxyaniline. The solution was kept in a water bath and the reaction stopped after 16 hours when no more epoxide was detectable by thin layer chromatography (TLC). After phase separation, 25 ml of dichloromethane were added to the thiirane phase and the organic phase was washed 4 times with 20 ml of deionized water each time, dried over MgSO 4 and the solvent was removed at 800 mbar and 40.degree. The product obtained was stored under a nitrogen atmosphere at 4°C.
- Ammonium thiocyanate (28.02 g, 2 eq.) was dissolved in a mixture of 60 ml water and 60 ml acetonitrile and pentaerythritol polyglycidyl ether (30 g, 1 eq.) was added. The solution was kept in a water bath and the reaction stopped after 24 hours when no more epoxide was detectable by thin layer chromatography (TLC). The product was separated from the aqueous phase and treated with 40 ml of dichloromethane. This organic phase was washed 5 times with 40 ml of deionized water each time, dried over MgSO 4 and the solvent was removed at 800 mbar and 40.degree. The product obtained was stored under a nitrogen atmosphere at 4°C.
- Ammonium thiocyanate (44.56 g, 2 eq.) was dissolved in a mixture of 60 ml water and 60 ml isopropanol and a tetrafunctionalized epoxy resin based on meta-xylenediamine (30 g, 1 eq.) was added. The solution was kept in a water bath and the reaction after 18 Hours stopped when no more epoxide was detectable by thin layer chromatography (TLC). The product was extracted 3 times with 40 ml of dichloromethane and the organic phase was washed 3 times with 40 ml of deionized water, dried over MgSO 4 and the solvent was removed at 800 mbar and 40.degree. The product obtained was stored under a nitrogen atmosphere at 4°C.
- Ammonium thiocyanate (13.24 g, 2 eq.) was dissolved in a mixture of 10 ml water, 30 ml acetonitrile and 10 g 4,4'-methylene-bis-( N,N -diglycidylaniline) (30 g, 1 eq.) added.
- the solution was kept in a water bath and the reaction stopped after 5.5 hours when no more epoxide was detectable by thin layer chromatography (TLC). After phase separation, 20 ml of dichloromethane were added and the organic phase was washed 3 times with 40 ml of deionized water each time, dried over MgSO 4 and the solvent was removed at 800 mbar and 40.degree.
- the product obtained was stored under a nitrogen atmosphere at 4°C.
- Ammonium thiocyanate (25.37 g, 2 eq.) was dissolved in 108 ml water and 12 ml isopropanol and sorbitol glycidyl ether (30 g, 1 eq.) added. The solution was kept in a water bath and the pH adjusted to 7 with 37% HCl. The reaction was stopped after 6 hours when epoxide was no longer detectable by thin layer chromatography (TLC). The product was extracted with 40 ml of dichloromethane and the organic phase was washed 3 times with 30 ml of deionized water each time, dried over MgSO 4 and the solvent was removed at 800 mbar and 40.degree. The product obtained was stored under a nitrogen atmosphere at 4°C.
- the thiiranes obtained can each be stirred with an excess of diethylamine at room temperature until the thiirane IR band at 617 cm -1 disappears.
- Excess amine can be removed by addition of dichloromethane followed by washing with phosphate buffer to pH 7.
- the organic phase can be washed with deionized water, dried over MgSO 4 and the excess solvent removed. Thereafter, the viscous liquid obtained can be transferred to an aqueous acidic medium such as 5% HCl (w/v) and the pH can be adjusted using aqueous ammonia (30%).
- Example 3 The thiirane (2 g, 1 eq.) obtained in Example 3 was mixed with diethylamine (4.16 g, 5 eq.) at room temperature for 3 hours until the thiirane IR band at 617 cm -1 disappeared. The viscous liquid thus obtained was transferred into an aqueous acidic medium such as 5% HCl (w/v).
- the thiirane (5 g, 1 eq.) obtained in Example 5 was mixed with diethylamine (10.22 g, 5 eq.) at room temperature for 5 hours until the thiirane IR band at 617 cm -1 disappeared. Excess amine was removed by adding 160 ml dichloromethane and then washing with 160 ml phosphate buffer (pH 7) to pH 7. The organic phase was washed with 160 ml deionized water, dried over MgSO 4 and the excess solvent removed.
- Example 11 Coating of a Cu specimen with the compound (A1 9 ) according to Example 9
- a copper specimen (Rocholl, 10 ⁇ 2.5 cm) was first cleaned with acetone and then immersed in a bath containing 4 g/L of the compound (A1 9 ) according to Example 9 in 5% HCl (w/v) contained. The specimen was left in the bath without agitation for 30 minutes and then washed with tap water and deionized water and dried in a stream of air. After this treatment, the specimen appeared whitish on visual inspection and a polymer network could be detected by SEM.
- Example 12 Coating of a Cu specimen with the compound (A1 10 ) according to Example 10
- a copper specimen (Rocholl, 15 ⁇ 15 cm) was first cleaned with acetone and then immersed in a bath containing 5 g/L of the compound (A1 10 ) according to Example 10 in 5% HCl (w/v). The specimen was left in the bath without agitation for 10 minutes and then washed with tap water and deionized water and dried in a stream of air. After this treatment, the specimen appeared whitish on visual inspection and a polymer network could be detected by SEM.
- Example 13 Coating of an Al/Cu specimen with the compound (A1 10 ) according to Example 10
- Table 1 test c(A1 10 ) [g/L] c(NaF) [mg/L] c(CuSO 4 ) [mg/L] 1 0.10 500 0 2 0.10 500 100 3 0.25 250 0 4 0.25 250 50 5 0.25 250 100 6 0.25 250 200 7 0.25 250 300 8th 0.25 500 0 9 0.25 500 100 10 0.25 500 200 11 0.25 500 300 12 0.5 50 0 13 0.5 100 0 14 0.5 250 0 15 0.5 250 50 16 0.5 250 100 17 0.5 250 200 18 0.5 250 300 19 0.5 500 0 20 0.5 500 100 21 0.5 500 200 22 0.5 500 300 23 0.75 500 0 24 0.75 500 100 25 1.00 50 0 26 1.00 100 0 27 1.00 250 0 30 1.00 250 50 31 1.00 250 100 32 1.00 250 200 33 1.00 250 300 34 1.00 500 0 35 1.00 500 100 36 1.00 500 200 37 1.00 500 300 38 2.00 250 0 40 2.00 250 50 41 2.00 250 100 42 2.00 250 200 43 2
- Example 14 Coating of an Al/Cu specimen with the compound (A1 10 ) according to Example 10 and treatment with a Zr fluorocomplex in a bath
- the coating was analyzed by XRF and an increase of up to 46% was observed for cases where the coating bath contained compound (A1 10 ). Potentiometric polarization studies also showed a cathodic potential shift compared to the specimens treated with Zr only.
- Table 3 test c(A1 10 ) (g/L) c(NaF) (mg/L) Zr deposition (mg/m 2 ) 55 (Bathroom 1) 0.10 500 42 55 (Bathroom 2) 0 0 56 (Bathroom 1) 0.25 500 78 56 (Bathroom 2) 0 0
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Abstract
Die vorliegende Erfindung betrifft eine saure wässrige Zusammensetzung zur Beschichtung von kupferhaltigen metallischen Substraten enthaltend mindestens eine wasserlösliche schwefelorganische Verbindung (A1), die mindestens zwei haftungsvermittelnde funktionale Gruppen enthält, und insbesondere aus der ringöffnenden Addition eines sekundären Amins an ein polyfunktionelles Thiiran hervorgeht. Derartige Zusammensetzungen eignen sich insbesondere für die korrosionsschützende Vorbehandlung von kupferlegiertem Aluminium, insbesondere in Anwesenheit wasserlöslicher Verbindungen der Elemente Zr, Ti und/oder Si erfolgt eine rasche Ausbildung einer vor Korrosion schützenden Konversionsschicht. Weiterhin betrifft die Erfindung ein Verfahren zur korrosionsschützenden Beschichtung unter Verwendung saurer wässriger Zusammensetzungen enthaltend die wasserlösliche schwefelorganische Verbindung (A1).The present invention relates to an acidic aqueous composition for coating copper-containing metallic substrates containing at least one water-soluble organosulfur compound (A1) which contains at least two adhesion-promoting functional groups and in particular results from the ring-opening addition of a secondary amine to a polyfunctional thiirane. Such compositions are particularly suitable for the anti-corrosion pretreatment of copper-alloyed aluminum; in particular, in the presence of water-soluble compounds of the elements Zr, Ti and/or Si, a conversion layer protecting against corrosion is rapidly formed. Furthermore, the invention relates to a method for anti-corrosion coating using acidic aqueous compositions comprising the water-soluble organosulfur compound (A1).
Description
Die vorliegende Erfindung betrifft ein saure wässrige Zusammensetzung zum Schutz vor Korrosion von Metalloberflächen, die mindestens eine wasserlösliche schwefelorganische Verbindung mit mindestens zwei haftungsvermittelnden funktionalen Gruppen enthält, die jeweils eine sekundäre Thiol-Gruppe und zu dieser mindestens eine vicinale sekundäre oder tertiäre Aminogruppe aufweisen, und ein Verfahren zur korrosionsschützenden Beschichtung einer Metalloberfläche unter Verwendung der sauren wässrigen Zusammensetzung.The present invention relates to an acidic aqueous composition for protecting against corrosion of metal surfaces, which contains at least one water-soluble organosulfur compound having at least two adhesion-promoting functional groups, each having a secondary thiol group and at least one vicinal secondary or tertiary amino group for this, and a Process for anti-corrosive coating of a metal surface using the acidic aqueous composition.
Aluminiumlegierungen sind aufgrund ihres geringen Gewichts und ihrer Festigkeit beliebte Materialien, insbesondere in der Luftfahrtindustrie. Sie weisen allerdings den Nachteil auf, dass sie zum Erhalt ihrer Eigenschaften gegen Korrosion geschützt werden müssen. Dies erfolgt zur Zeit noch mit hochgiftigen Chrom(VI)-Verbindungen, für die jedoch aufgrund der EU-Chemikalienverordnung REACH Alternativen gefunden werden müssen.Aluminum alloys are popular materials, especially in the aerospace industry, due to their light weight and strength. However, they have the disadvantage that they have to be protected against corrosion in order to retain their properties. This is currently still being done with highly toxic chromium(VI) compounds, for which alternatives have to be found due to the EU chemicals regulation REACH.
Im Stand der Technik werden eine Reihe von Lösungen vorgeschlagen, die insbesondere auf die Verwendung von schwefelhaltigen Verbindungen abzielen.A number of solutions are proposed in the prior art, aimed in particular at the use of sulphur-containing compounds.
In diesem Zusammenhang beschreibt
Gerade die im Stand der Technik beschriebenen Thiole weisen jedoch den Nachteil hoher Kosten und aufwendiger Herstellungsverfahren sowie eine Oxidationsneigung zu Disulfiden auf.However, the thiols described in the prior art in particular have the disadvantage of high costs and complex production processes and a tendency to oxidize to form disulfides.
Es ist daher die Aufgabe der vorliegenden Erfindung eine Alternative zu den herkömmlichen Verfahren zum Schutz von Aluminiumlegierungen vor Korrosion zur Verfügung zu stellen.It is therefore the object of the present invention to provide an alternative to the conventional methods for protecting aluminum alloys from corrosion.
Es wurde überraschend gefunden, dass diese Aufgabe durch eine saure wässrige Zusammensetzung gelöst wird, die mindestens zwei haftungsvermittelnde funktionale Gruppen enthält, die jeweils eine sekundäre Thiol-Gruppe und zu dieser zumindest eine vicinale sekundäre oder tertiäre Amino-Gruppe aufweisen.Surprisingly, it was found that this object is achieved by an acidic aqueous composition which contains at least two adhesion-promoting functional groups which each have a secondary thiol group and at least one vicinal secondary or tertiary amino group for this.
Daher ist ein erster Gegenstand der vorliegenden Erfindung eine saure wässrige Zusammensetzung (A) zur korrosionsschützenden Beschichtung einer Oberfläche eines metallischen Substrates, das zumindest teilweise aus Kupfer zusammengesetzt ist, wobei die saure wässrige Zusammensetzung (A) mindestens eine wasserlösliche schwefelorganische Verbindung (A1) enthält, die mindestens zwei haftungsvermittelnde funktionale Gruppen (FG) enthält, die jeweils eine sekundäre Thiol-Gruppe und zu dieser zumindest eine vicinale sekundäre oder tertiäre Amino-Gruppe aufweisen.Therefore, a first subject matter of the present invention is an acidic aqueous composition (A) for the anti-corrosion coating of a surface of a metallic substrate which is composed at least partially of copper, the acidic aqueous composition (A) containing at least one water-soluble organosulfur compound (A1), which contains at least two adhesion-promoting functional groups (FG), each of which has a secondary thiol group and at least one vicinal secondary or tertiary amino group for this.
Es wurde überraschend gefunden, dass durch den Einsatz der speziellen schwefelorganischen Verbindung (A1) ein hoher Korrosionsschutz erreicht werden kann, ohne dass die mit schwefelorganischen Verbindungen assoziierten Nachteile auftraten. Ohne an eine bestimmte Theorie gebunden zu sein, wird davon ausgegangen, dass die schwefelorganische Verbindung mit dem im metallischen Substrat anwesenden Kupferionen einen Komplex ausbildet und so ein polymeres Netzwerk entsteht, wodurch der Korrosion durch Lochfraß vorgebeugt wird. Insbesondere in Kombination mit Korrosionsschutzmaßnahmen auf Basis von Zirkoniumoxidverbindungen, wie sie bereits aus der Autoindustrie bekannt sind, konnte so ein exzellenter Schutz der metallischen Oberfläche gegen Korrosion erreicht werden, der im Vergleich zu dem steht, was mit den herkömmlichen Cr(VI)-basierten Systemen erreicht wird.Surprisingly, it was found that by using the special organosulfur compound (A1), a high level of protection against corrosion can be achieved without the disadvantages associated with organosulfur compounds occurring. Without being bound by any particular theory, it is believed that the organosulfur compound forms a complex with the copper ions present in the metallic substrate to form a polymeric network thereby preventing pitting corrosion. Especially in combination with corrosion protection measures based on zirconium oxide compounds, as they are already known from the automotive industry, excellent protection of the metallic surface against corrosion could be achieved, which is in comparison to what is achieved with conventional Cr(VI)-based systems is reached.
Im Rahmen der vorliegenden Erfindung hat es sich als vorteilhaft erwiesen, höher funktionale wasserlösliche schwefelorganische Verbindungen (A1) einzusetzen, da in diesen Fällen der typische Geruch von schwefelhaltigen Verbindungen weiter reduziert werden konnte. Daher ist eine Ausführungsform bevorzugt, in der die wasserlösliche schwefelorganische Verbindung (A1) mindestens 3, jedoch nicht mehr als 8, vorzugsweise nicht mehr als 6 und besonders bevorzugt 4 haftungsvermittelnde funktionale Gruppen aufweist. In einer besonders bevorzugten Ausführungsform ist die wasserlösliche schwefelorganische Verbindung (A1) aliphatisch und besonders bevorzugt aliphatisch und gesättigt.In the context of the present invention, it has proven advantageous to use water-soluble organosulphur compounds (A1) with a higher functionality, since in these cases the typical odor of sulfur-containing compounds can be further reduced. Therefore, an embodiment is preferred in which the water-soluble organosulfur compound (A1) has at least 3, but not more than 8, preferably not more than 6 and particularly preferably 4 adhesion-promoting functional groups. In a particularly preferred embodiment, the water-soluble organosulfur compound (A1) is aliphatic and particularly preferably aliphatic and saturated.
In einer weiterhin bevorzugten Ausführungsform weist die wasserlösliche schwefelorganische Verbindung (A1) die folgende Struktureinheit (I) als haftungsvermittelnde funktionale Gruppe auf:
wobei mindestens ein Rest R1 oder R2 aus einer aliphatischen Alkyl-Gruppe mit nicht mehr als 6 Kohlenstoff-Atomen ausgewählt ist;
wobei die Reste R3 und R4 in jeder n-ten Einheit (-HCR3-CHR4-O-) unabhängig voneinander ausgewählt sind aus Wasserstoff oder einer Methyl-Gruppe;
wobei die Reste R3 und R4 innerhalb einer n-ten Einheit (-HCR3-CHR4-O-) nicht beide aus einer Methyl-Gruppe ausgewählt sein können;
wobei n gleich Null oder eine natürliche Zahl kleiner 6, vorzugsweise kleiner als 4 ist.In a further preferred embodiment, the water-soluble organosulfur compound (A1) has the following structural unit (I) as an adhesion-promoting functional group:
wherein at least one R 1 or R 2 is selected from an aliphatic alkyl group having no more than 6 carbon atoms;
wherein the radicals R 3 and R 4 in every nth unit (-HCR 3 -CHR 4 -O-) are independently selected from hydrogen or a methyl group;
wherein the radicals R 3 and R 4 within an nth unit (-HCR 3 -CHR 4 -O-) cannot both be selected from a methyl group;
where n is zero or a natural number less than 6, preferably less than 4.
In einer besonders bevorzugten Ausführungsform entspricht die wasserlösliche schwefelorganische Verbindung (A1) der folgenden Strukturformel (II):
wobei die Reste R5, R6 und R7 ausgewählt sind aus Wasserstoff, einer aliphatischen Alkyl-Gruppe mit nicht mehr als 6 Kohlenstoff-Atomen, dem Rest-FG oder dem Rest-CHR1-FG; wobei mindestens einer der Reste R5, R6 und R7, vorzugsweise alle Reste R5, R6 und R7, entweder einen Rest -FG oder einen Rest -CHR1-FG, vorzugsweise einen Rest -CHR1-FG darstellen, wobei die Reste R1 und R2 ausgewählt sind aus Wasserstoff oder einer aliphatischen Alkyl-Gruppe mit nicht mehr als 6 Kohlenstoff-Atomen, vorzugsweise nicht mehr als 4 Kohlenstoff-Atomen und besonders bevorzugt zwei Kohlenstoffatomen und wobei mindestens ein Rest R1 oder R2 aus einer aliphatischen Alkyl-Gruppe mit nicht mehr als 6 Kohlenstoff-Atomen ausgewählt ist.In a particularly preferred embodiment, the water-soluble organosulfur compound (A1) corresponds to the following structural formula (II):
wherein the radicals R 5 , R 6 and R 7 are selected from hydrogen, an aliphatic alkyl group having not more than 6 carbon atoms, the radical -FG or the radical -CHR 1 -FG; where at least one of the radicals R 5 , R 6 and R 7 , preferably all radicals R 5 , R 6 and R 7 , is either a radical -FG or a group -CHR 1 -FG, preferably a group -CHR 1 -FG, where the groups R 1 and R 2 are selected from hydrogen or an aliphatic alkyl group with not more than 6 carbon atoms, preferably not more than 4 carbon atoms and more preferably two carbon atoms and wherein at least one radical R 1 or R 2 is selected from an aliphatic alkyl group with not more than 6 carbon atoms.
Dem Fachmann sind verschiedene Verfahren zur Herstellung von Thiiranen bekannt. So beschreiben beispielsweise
Ein alternativer Herstellungsweg ist von
Im Rahmen der vorliegenden Erfindung wurden die bekannten Verfahren weiterentwickelt, so dass eine bessere Nachhaltigkeit und eine einfachere Aufarbeitung erreicht werden konnten. Daher ist eine Ausführungsform der vorliegenden Erfindung bevorzugt, in der die wasserlösliche schwefelorganische Verbindung (A1) durch ringöffnende Umsetzung eines polyfunktionellen Thiirans, das vorzugsweise tetrafunktionell und besonders bevorzugt aliphatisch ist, mit einem sekundären Amin erhältlich ist. Das sekundäre Amin ist vorzugsweise monofunktionell, besonders bevorzugt aliphatisch und insbesondere ausgewählt aus Bis(2-methoxypropyl)amin, Bis(2-hydroxypropyl)amin und/oder Dialkylaminen mit nicht mehr als 4 Kohlenstoffatomen in der N-substituierten Alkyl-Kette, insbesondere Diethylamin. Das eingesetzte Thiiran ist vorzugsweise ausgewählt aus 1,4-Bis(thiiran-2-ylmethoxy)-1,4-butandiol), 1-(Thiiran-2-ylmethoxy)-2,2-bis(thiiran-2-ylmethoxymethyl)propan oder 2-[[3-(Thiiran-2-ylmethoxy)-2,2-bis(thiiran-2-ylmethoxymethyl)propoxy]methyl]thiiran.Within the scope of the present invention, the known methods were further developed so that better sustainability and simpler processing could be achieved. An embodiment of the present invention is therefore preferred in which the water-soluble organosulfur compound (A1) can be obtained by ring-opening reaction of a polyfunctional thiirane, which is preferably tetrafunctional and particularly preferably aliphatic, with a secondary amine. The secondary amine is preferably monofunctional, more preferably aliphatic and especially selected from bis(2-methoxypropyl)amine, bis(2-hydroxypropyl)amine and/or dialkylamines having not more than 4 carbon atoms in the N-substituted alkyl chain, especially diethylamine . The thiirane used is preferably selected from 1,4-bis(thiiran-2-ylmethoxy)-1,4-butanediol), 1-(thiiran-2-ylmethoxy)-2,2-bis(thiiran-2-ylmethoxymethyl)propane or 2-[[3-(thiiran-2-ylmethoxy)-2,2-bis(thiiran-2-ylmethoxymethyl)propoxy]methyl]thiirane.
In einer bevorzugten Ausführungsform der vorliegenden Erfindung weist die wasserlösliche schwefelorganische Verbindung (A1) eine Molmasse von weniger als 2000 g/mol, vorzugsweise weniger als 1400 g/mol, besonders bevorzugt von weniger als 1000 g/mol auf.In a preferred embodiment of the present invention, the water-soluble organosulfur compound (A1) has a molar mass of less than 2000 g/mol, preferably less than 1400 g/mol, particularly preferably less than 1000 g/mol.
In einer weiterhin bevorzugten Ausführungsform beträgt der Anteil der wasserlöslichen schwefelorganischen Verbindung (A1) in der erfindungsgemäßen Zusammensetzung (A), jeweils bezogen auf die saure wässrige Zusammensetzung (A), mindestens 0,01 g/kg, vorzugsweise mindestens 0,05 g/kg, besonders bevorzugt mindestens 0,1 g/kg und ganz besonders bevorzugt mindestens 0,2 g/kg beträgt, wobei jedoch vorzugsweise ein Anteil von 5 g/kg, besonders bevorzugt 3 g/kg, ganz besonders bevorzugt 1 g/kg nicht überschritten wird.In a further preferred embodiment, the proportion of the water-soluble organosulfur compound (A1) in the composition (A) according to the invention, based in each case on the acidic aqueous composition (A), is at least 0.01 g/kg, preferably at least 0.05 g/kg , particularly preferably at least 0.1 g/kg and very particularly preferably at least 0.2 g/kg, but preferably not exceeding a proportion of 5 g/kg, particularly preferably 3 g/kg, very particularly preferably 1 g/kg will.
Es wurde weiterhin überraschend gefunden, dass der Korrosionsschutz durch die erfindungsgemäße Zusammensetzung weiterhin erhöht werden konnte, wenn diese zusätzlich freies Fluorid enthält. Daher ist eine Ausführungsform bevorzugt, in der die saure wässrige Zusammensetzung (A) weiterhin freies Fluorid, vorzugsweise in einer Menge von mindestens 5 mg/kg, vorzugsweise mindestens 20 mg/kg enthält, jedoch vorzugsweise nicht mehr als 400 mg/kg, besonders bevorzugt nicht mehr als 200 mg/kg. Das freie Fluorid ist jeweils als F- berechnet, wobei in einer besonders bevorzugten Ausführungsform der Gesamtfluorid-Gehalt (TISAB) vorzugsweise 1 g/kg, besonders bevorzugt 500 g/kg berechnet als NaF nicht überschreitet.It was also surprisingly found that the corrosion protection could be further increased by the composition according to the invention if it additionally contains free fluoride. Therefore an embodiment is preferred in which the acidic aqueous composition (A) further contains free fluoride, preferably in an amount of at least 5 mg/kg, preferably at least 20 mg/kg, but preferably not more than 400 mg/kg, more preferred not more than 200 mg/kg. The free fluoride is calculated as F - in each case, with the total fluoride content (TISAB) preferably not exceeding 1 g/kg, particularly preferably 500 g/kg, calculated as NaF, in a particularly preferred embodiment.
Wie bereits anfänglich erwähnt kann die erfindungsgemäße Zusammensetzung mit weiteren Korrosionsschutzmaßnahmen kombiniert werden, um die Schutzleistung nochmals zu verbessern. In einer weiteren bevorzugten Ausführungsform enthält die saure wässrige Zusammensetzung (A) daher zusätzlich mindestens eine wasserlösliche Verbindung eines oder mehrerer der Elemente Zr, Ti und Si, vorzugsweise wasserlösliche Verbindungen von Oxo- und/oder Fluorokomplexen dieser Elemente. Der Anteil dieser wasserlöslichen Verbindungen beträgt insgesamt vorzugsweise mindestens 0,05 mmol/kg, besonders bevorzugt mindestens 0,1 mmol/kg, ganz besonders bevorzugt mindestens 0,5 mmol/kg bezogen auf die jeweiligen Elemente Zr, Ti und Si beträgt, vorzugsweise jedoch nicht mehr als 5 mmol/kg bezogen auf die jeweiligen Elemente Zr, Ti und Si.As already mentioned at the outset, the composition according to the invention can be combined with other anti-corrosion measures in order to further improve the protective performance. In a further preferred embodiment, the acidic aqueous composition (A) therefore additionally contains at least one water-soluble compound of one or more of the elements Zr, Ti and Si, preferably water-soluble compounds of oxo and/or fluoro complexes of these elements. The total proportion of these water-soluble compounds is preferably at least 0.05 mmol/kg, particularly preferably at least 0.1 mmol/kg, very particularly preferably at least 0.5 mmol/kg based on the respective elements Zr, Ti and Si, but preferably not more than 5 mmol/kg based on the respective elements Zr, Ti and Si.
Eine weitere Steigerung der Schutzleistung durch die erfindungsgemäße Zusammensetzung wurde vor allem in den Fällen beobachtet, in denen die saure wässrige Zusammensetzung (A) weiterhin Kupferionen enthält. Ohne an eine bestimmte Theorie gebunden zu sein, wird davon ausgegangen, dass dadurch die Ausbildung des schützenden Films auf der Oberfläche des Metallsubstrats unterstützt wird. Daher ist eine weitere Ausführungsform der sauren wässrigen Zusammensetzung (A) bevorzugt, in der die saure wässrige Zusammensetzung (A) zusätzlich mindestens eine wasserlösliche Verbindung des Elements Cu enthält, wobei der Anteil dieser wasserlöslichen Verbindungen insgesamt vorzugsweise mindestens 0,1 mmol/kg, besonders bevorzugt mindestens 0,5 mmol/kg, ganz besonders bevorzugt mindestens 1 mmol/kg bezogen auf das Element Cu beträgt, jedoch vorzugsweise 5 mmol/kg bezogen auf das Element Cu nicht überschreitet.A further increase in the protective performance due to the composition according to the invention was observed above all in those cases in which the acidic aqueous composition (A) also contains copper ions. Without being bound by any particular theory, it is believed that this aids in the formation of the protective film on the surface of the metal substrate. A further embodiment of the acidic aqueous composition (A) is therefore preferred in which the acidic aqueous composition (A) additionally contains at least one water-soluble compound of the element Cu, the proportion of these water-soluble compounds in total preferably being at least 0.1 mmol/kg, particularly preferably at least 0.5 mmol/kg, very particularly preferably at least 1 mmol/kg, based on the element Cu, but preferably does not exceed 5 mmol/kg based on the element Cu.
In vielen Fällen werden die Metallsubstrate vor dem Aufbringen des Korrosionsschutzes verschiedenen Vorbehandlungen unterzogen, die meist in einem sauren Milieu vorgenommen werden. Im Rahmen der vorliegenden Erfindung hat sich überraschender Weise herausgestellt, dass die erfindungsgemäße saure wässrige Zusammensetzung ihre Wirkung vor allem dann entfaltet, wenn sie einen ähnlichen pH-Wert aufweist. Entsprechend weist die erfindungsgemäße Zusammensetzung (A) daher einen pH-Wert auf, der kleiner ist als 6,0, vorzugsweise kleiner als 5,0, besonders bevorzugt kleiner als 4,5, der jedoch vorzugsweise nicht kleiner als 1,0, besonders bevorzugt nicht kleiner als 2,0 und ganz besonders bevorzugt nicht kleiner als 3,0 ist.In many cases, the metal substrates are subjected to various pre-treatments before the corrosion protection is applied, which are usually carried out in an acidic environment. In the context of the present invention, it has surprisingly been found that the acidic aqueous composition according to the invention develops its effect above all when it has a similar pH. Accordingly, the composition (A) according to the invention therefore has a pH which is less than 6.0, preferably less than 5.0, particularly preferably less than 4.5, but which is preferably not less than 1.0, particularly preferably is not less than 2.0, and most preferably not less than 3.0.
In einer besonders bevorzugten Ausführungsform enthält die saure wässrige Zusammensetzung (A) mit einem pH-Wert unterhalb von 5,0:
- a) mindestens eine wasserlösliche schwefelorganische Verbindung (A1), die mindestens zwei haftungsvermittelnde funktionale Gruppen enthält, die jeweils eine sekundäre Thiol-Gruppe und zu dieser zumindest eine vicinale sekundäre oder tertiäre Amino-Gruppe aufweist, vorzugsweise in einer Gesamtmenge von mindestens 0,01 g/kg bezogen auf die saure wässrige Zusammensetzung (A);
- b) mindestens eine Quelle für freies Fluorid, vorzugsweise mindestens 5 mg/kg, besonders bevorzugt mindestens 20 mg/kg freies Fluorid bezogen auf die saure wässrige Zusammensetzung und bestimmt als Menge F1-;
- c) ggf. mindestens eine wasserlösliche Verbindung eines oder mehrerer der Elemente Zr, Ti und Si, vorzugsweise des Elements Zr und besonders bevorzugt wasserlösliche Verbindungen von Oxo- und/oder Fluorokomplexen dieser Elemente enthält, vorzugsweise in einer Gesamtmenge von mindestens 0,05 mmol/kg bezogen auf die saure wässrige Zusammensetzung und berechnet als Menge der Elemente Zr, Ti und Si.
- a) at least one water-soluble organosulfur compound (A1) containing at least two adhesion-promoting functional groups, each having a secondary thiol group and at least one vicinal secondary or tertiary amino group for this, preferably in a total amount of at least 0.01 g /kg based on the acidic aqueous composition (A);
- b) at least one source of free fluoride, preferably at least 5 mg/kg, more preferably at least 20 mg/kg of free fluoride based on the acidic aqueous composition and determined as the amount F 1- ;
- c) optionally contains at least one water-soluble compound of one or more of the elements Zr, Ti and Si, preferably the element Zr and particularly preferably water-soluble compounds of oxo and/or fluoro complexes of these elements, preferably in a total amount of at least 0.05 mmol/ kg based on the acidic aqueous composition and calculated as the amount of the elements Zr, Ti and Si.
Die erfindungsgemäße Zusammensetzung ist insbesondere als Korrosionsschutz für Aluminium-Kupfer-Legierungen geeignet. Daher ist ein weiterer Gegenstand der vorliegenden Erfindung ein Verfahren zur korrosionsschützenden Beschichtung einer Oberfläche eines metallischen Substrats, das zumindest teilweise aus Kupfer zusammengesetzt ist, umfassend das In-Kontakt-Bringen der Oberfläche des metallischen Substrats mit einer sauren wässrigen Zusammensetzung (A) gemäß der vorliegenden Erfindung.The composition according to the invention is particularly suitable as a corrosion protection for aluminum-copper alloys. Therefore, another object of the present invention is a method for anti-corrosive coating of a surface of a metallic substrate composed at least partially of copper, comprising contacting the surface of the metallic substrate with an acidic aqueous composition (A) according to the present Invention.
In einer besonders bevorzugten Ausführungsform handelt es sich bei dem metallischen Substrat um kupferlegiertes Aluminium, das vorzugsweise mindestens 1 Gew.-%, besonders bevorzugt mindestens 3 Gew.-%, jedoch vorzugsweise weniger als 6 Gew.-% Kupfer enthält.In a particularly preferred embodiment, the metallic substrate is copper-alloyed aluminum, which preferably contains at least 1% by weight, particularly preferably at least 3% by weight, but preferably less than 6% by weight, of copper.
Um die Schutzwirkung des erfindungsgemäßen Verfahrens weiter zu verbessern, kann das metallische Substrat weiteren Behandlungsschritten unterzogen werden. Daher ist eine Ausführungsform bevorzugt, in der dem In-Kontakt-Bringen mit der sauren wässrigen Zusammensetzung (A) ein In-Kontakt-Bringen der Oberfläche des metallischen Substrats mit einer sauren wässrigen Zusammensetzung (B) nachfolgt, die mindestens eine wasserlösliche Verbindung eines oder mehrerer der Elemente Zr, Ti und Si, vorzugsweise von Oxo- und/oder Fluorokomplexen dieser Elemente enthält. Der Anteil dieser wasserlöslichen Verbindungen an der sauren wässrigen Zusammensetzung (B) liegt vorzugsweise bei insgesamt mindestens 0,05 mmol/kg, besonders bevorzugt mindestens 0,1 mmol/kg bezogen auf die jeweiligen Elemente Zr, Ti und Si, jedoch vorzugsweise 5 mmol/kg bezogen auf die jeweiligen Elemente Zr, Ti und Si nicht überschreitet.In order to further improve the protective effect of the method according to the invention, the metallic substrate can be subjected to further treatment steps. Therefore, an embodiment is preferred in which the contacting with the acidic aqueous composition (A) is followed by contacting the surface of the metallic substrate with an acidic aqueous composition (B) which comprises at least one water-soluble compound of one or several of the elements Zr, Ti and Si, preferably containing oxo and/or fluoro complexes of these elements. The proportion of these water-soluble compounds in the acidic aqueous composition (B) is preferably at least 0.05 mmol/kg, particularly preferably at least 0.1 mmol/kg, based on the respective elements Zr, Ti and Si, but preferably 5 mmol/kg. kg based on the respective elements Zr, Ti and Si.
Das In-Kontakt-Bringen der sauren wässrigen Zusammensetzungen (A) und (B) kann je nach Bedarf mit oder ohne dazwischenliegendem Spül- und/oder Trockenschritt erfolgen.The contacting of the acidic aqueous compositions (A) and (B) can be carried out with or without an intermediate rinsing and/or drying step, as required.
Vorzugsweise enthält die saure wässrige Zusammensetzung (B) keine wasserlöslichen schwefelorganischen Verbindungen (A1) in einer solchen Menge, die als massenbezogenes Verhältnis zur Menge an wasserlöslicher schwefelorganischer Verbindung (A1) in der sauren wässrigen Zusammensetzung (A) den Wert 0,1, vorzugsweise den Wert 0,05 überschreitet.The acidic aqueous composition (B) preferably contains no water-soluble organosulfur compounds (A1) in such an amount as the mass-related Ratio to the amount of water-soluble organosulfur compound (A1) in the acidic aqueous composition (A) exceeds the value 0.1, preferably the value 0.05.
In einer bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens umfasst dieses einen Schritt der sauren Dekapierung der Oberfläche des metallischen Substrats bevor dieses mit der sauren wässrigen Zusammensetzung (A) in Kontakt gebracht wird. Vorzugsweise umfasst das erfindungsgemäße Verfahren daher unmittelbar vor dem In-Kontakt-Bringen mit der sauren wässrigen Zusammensetzung (A) - mit oder ohne dazwischenliegenden Spülschritt - eine saure Dekapierung der Oberfläche des metallischen Substrates, vorzugsweise durch In-Kontakt-Bringen mit einer sauren wässrigen Zusammensetzung mit einem pH-Wert unterhalb von 2,0 enthaltend mindestens eine starke Säure mit einen pKa-Wert unterhalb von 1,5, vorzugsweise Schwefelsäure.In a preferred embodiment of the method according to the invention, it comprises a step of acidic desmutting of the surface of the metallic substrate before it is brought into contact with the acidic aqueous composition (A). The method according to the invention therefore preferably comprises immediately before contacting with the acidic aqueous composition (A) - with or without an intermediate rinsing step - acidic desmutting of the surface of the metallic substrate, preferably by contacting with an acidic aqueous composition with a pH below 2.0 containing at least one strong acid with a pK a below 1.5, preferably sulfuric acid.
In einem finalen Schritt kann die metallische Oberfläche mit einem Lack zum weiteren Schutz mit einem Lack beschichtet werden. Hierbei hat sich überraschend gezeigt, dass das Aufbringen des Lacks nach dem In-Kontakt-Bringen mit der erfindungsgemäßen Zusammensetzung erfolgen kann, ohne dass sich dies negativ auf die Beschichtungsqualität auswirkt. Daher ist eine Ausführungsform bevorzugt, in der dem In-Kontakt-Bringen mit der sauren wässrigen Zusammensetzung (A) und ggf. nach dem In-Kontakt-Bringen mit der sauren wässrigen Zusammensetzung (B) - mit oder ohne dazwischenliegendem Spül- und/oder Trocknungsschritt - die Beschichtung mit einem Lack erfolgt, der vorzugsweise ein Pulverlack ist.In a final step, the metallic surface can be coated with a lacquer for further protection. Surprisingly, it was found here that the paint can be applied after it has been brought into contact with the composition according to the invention, without this having a negative effect on the coating quality. Therefore, an embodiment is preferred in which the contacting with the acidic aqueous composition (A) and optionally after the contacting with the acidic aqueous composition (B) - with or without intermediate rinsing and / or Drying step - the coating is done with a paint, which is preferably a powder paint.
Die vorliegende Erfindung wird anhand der folgenden Beispiele näher erläutert, wobei diese keinesfalls als Einschränkung des Erfindungsgedanken zu verstehen sind.The present invention is explained in more detail with the aid of the following examples, which are in no way to be understood as limiting the inventive concept.
Ammoniumthiocyanat (19,27, 2 Äq.) wurde in 60 ml Wasser gelöst. Die Lösung wurde in einem Wasserbad gehalten und Glycidylisopropylether (15 g, 1 Äq.) wurde dazugegeben. Die Reaktion wurde nach 20 Stunden gestoppt, als kein Epoxid mehr mittels Dünnschichtchromatographie (DC) nachweisbar war. Das Produkt wurde 3x mit je 40 ml Dichlormethan extrahiert, dann 2x mit je 40 ml deionisiertem Wasser gewaschen, die organische Phase über MgSO4 getrocknet und das Lösungsmittel bei 800 mbar und 40 °C entfernt. Das erhaltene Produkt wurde unter Stickstoffatmosphäre bei Raumtemperatur gelagert.Ammonium thiocyanate (19.27, 2 eq.) was dissolved in 60 mL of water. The solution was kept in a water bath and glycidyl isopropyl ether (15 g, 1 eq.) was added. The reaction was stopped after 20 hours when no more epoxide was detectable by thin layer chromatography (TLC). The product was extracted 3 times with 40 ml of dichloromethane, then washed 2 times with 40 ml of deionized water, the organic phase was dried over MgSO 4 and the solvent was removed at 800 mbar and 40.degree. The product obtained was stored under a nitrogen atmosphere at room temperature.
Ammoniumthiocyanat (18,95, 2 Äq.) wurde in 120 ml Wasser gelöst. Die Lösung wurde in einem Wasserbad gehalten und Ethylenglycoldicycidylether (15 g, 1 Äq.) wurde dazugegeben. Die Reaktion wurde nach 6,5 Stunden gestoppt, als kein Epoxid mehr mittels Dünnschichtchromatographie (DC) nachweisbar war. Das Produkt wurde 4x mit je 50 ml Dichlormethan extrahiert, dann 3x mit je 50 ml deionisiertem Wasser gewaschen, die organische Phase über MgSO4 getrocknet und das Lösungsmittel bei 800 mbar und 40 °C entfernt. Das erhaltene Produkt wurde unter Stickstoffatmosphäre bei 4 °C gelagert.Ammonium thiocyanate (18.95, 2 eq.) was dissolved in 120 mL of water. The solution was kept in a water bath and ethylene glycol dicyclocidyl ether (15 g, 1 eq.) was added. The reaction was stopped after 6.5 hours when no more epoxide was detectable by thin layer chromatography (TLC). The product was extracted 4 times with 50 ml of dichloromethane, then washed 3 times with 50 ml of deionized water, the organic phase was dried over MgSO 4 and the solvent was removed at 800 mbar and 40.degree. The product obtained was stored under a nitrogen atmosphere at 4°C.
Ammoniumthiocyanat (28,55 g, 2 Äq.) wurde in 90 ml Wasser und 30 ml Isopropylalkohol gelöst. Die Lösung wurde in einem Wasserbad gehalten und Trimethylolethantriglycidylether (30 g, 1 Äq.). wurde dazugegeben. Die Reaktion wurde nach 24 Stunden gestoppt, als kein Epoxid mehr mittels Dünnschichtchromatographie (DC) nachweisbar war. Das Produkt wurde 4x mit je 40 ml Dichlormethan extrahiert, dann 3x mit je 30 ml deionisiertem Wasser gewaschen, die organische Phase über MgSO4 getrocknet und das Lösungsmittel bei 800 mbar und 40 °C entfernt. Das erhaltene Produkt wurde unter Stickstoffatmosphäre bei 4 °C gelagert.Ammonium thiocyanate (28.55 g, 2 eq.) was dissolved in 90 mL of water and 30 mL of isopropyl alcohol. The solution was kept in a water bath and trimethylolethane triglycidyl ether (30 g, 1 eq.). was added. The reaction was stopped after 24 hours when epoxide was no longer detectable by thin layer chromatography (TLC). The product was extracted 4 times with 40 ml of dichloromethane, then washed 3 times with 30 ml of deionized water, the organic phase was dried over MgSO 4 and the solvent was removed at 800 mbar and 40.degree. The product obtained was stored under a nitrogen atmosphere at 4°C.
Ammoniumthiocyanat (15,5 g, 2 Äq.) wurde in einer Mischung aus 10 ml Wasser, 30 ml Acetonitril und 10 g N,N-Diglycidyl-4-glycidyloxyanilin gelöst. Die Lösung wurde in einem Wasserbad gehalten und die Reaktion nach 16 Stunden gestoppt, als kein Epoxid mehr mittels Dünnschichtchromatographie (DC) nachweisbar war. Nach der Phasentrennung wurden 25 ml Dichlormethan zu der Thiiran-Phase gegeben und die organische Phase 4x mit je 20 ml deionisiertem Wasser gewaschen, über MgSO4 getrocknet und das Lösungsmittel bei 800 mbar und 40 °C entfernt. Das erhaltene Produkt wurde unter Stickstoffatmosphäre bei 4 °C gelagert.Ammonium thiocyanate (15.5 g, 2 eq.) was dissolved in a mixture of 10 ml water, 30 ml acetonitrile and 10 g N,N-diglycidyl-4-glycidyloxyaniline. The solution was kept in a water bath and the reaction stopped after 16 hours when no more epoxide was detectable by thin layer chromatography (TLC). After phase separation, 25 ml of dichloromethane were added to the thiirane phase and the organic phase was washed 4 times with 20 ml of deionized water each time, dried over MgSO 4 and the solvent was removed at 800 mbar and 40.degree. The product obtained was stored under a nitrogen atmosphere at 4°C.
Ammoniumthiocyanat (28,02 g, 2 Äq.) wurde in einer Mischung aus 60 ml Wasser, und 60 ml Acetonitril gelöst und Pentaerythritolpolyglycidylether (30 g, 1 Äq.) hinzugegeben. Die Lösung wurde in einem Wasserbad gehalten und die Reaktion nach 24 Stunden gestoppt, als kein Epoxid mehr mittels Dünnschichtchromatographie (DC) nachweisbar war. Das Produkt wurde von der wässrigen Phase getrennt und mit 40 ml Dichlormethan versetzt. Diese organische Phase wurde 5x mit je 40 ml deionisiertem Wasser gewaschen, über MgSO4 getrocknet und das Lösungsmittel bei 800 mbar und 40 °C entfernt. Das erhaltene Produkt wurde unter Stickstoffatmosphäre bei 4 °C gelagert.Ammonium thiocyanate (28.02 g, 2 eq.) was dissolved in a mixture of 60 ml water and 60 ml acetonitrile and pentaerythritol polyglycidyl ether (30 g, 1 eq.) was added. The solution was kept in a water bath and the reaction stopped after 24 hours when no more epoxide was detectable by thin layer chromatography (TLC). The product was separated from the aqueous phase and treated with 40 ml of dichloromethane. This organic phase was washed 5 times with 40 ml of deionized water each time, dried over MgSO 4 and the solvent was removed at 800 mbar and 40.degree. The product obtained was stored under a nitrogen atmosphere at 4°C.
Ammoniumthiocyanat (44,56 g, 2 Äq.) wurde in einer Mischung aus 60 ml Wasser, und 60 ml Isopropanol gelöst und ein tetrafunktionalisiertes Epoxidharz auf Basis von meta-Xylendiamin (30 g, 1 Äq.) hinzugegeben. Die Lösung wurde in einem Wasserbad gehalten und die Reaktion nach 18 Stunden gestoppt, als kein Epoxid mehr mittels Dünnschichtchromatographie (DC) nachweisbar war. Das Produkt wurde 3x mit je 40 ml Dichlormethan extrahiert und die organische Phase wurde 3x mit je 40 ml deionisiertem Wasser gewaschen, über MgSO4 getrocknet und das Lösungsmittel bei 800 mbar und 40 °C entfernt. Das erhaltene Produkt wurde unter Stickstoffatmosphäre bei 4 °C gelagert.Ammonium thiocyanate (44.56 g, 2 eq.) was dissolved in a mixture of 60 ml water and 60 ml isopropanol and a tetrafunctionalized epoxy resin based on meta-xylenediamine (30 g, 1 eq.) was added. The solution was kept in a water bath and the reaction after 18 Hours stopped when no more epoxide was detectable by thin layer chromatography (TLC). The product was extracted 3 times with 40 ml of dichloromethane and the organic phase was washed 3 times with 40 ml of deionized water, dried over MgSO 4 and the solvent was removed at 800 mbar and 40.degree. The product obtained was stored under a nitrogen atmosphere at 4°C.
Ammoniumthiocyanat (13,24 g, 2 Äq.) wurde in einer Mischung aus 10 ml Wasser, 30 ml Acetonitril und 10 g 4,4'-Methylen-bis-(N,N-diglycidylanilin) (30 g, 1 Äq.) hinzugegeben. Die Lösung wurde in einem Wasserbad gehalten und die Reaktion nach 5,5 Stunden gestoppt, als kein Epoxid mehr mittels Dünnschichtchromatographie (DC) nachweisbar war. Nach der Phasentrennung wurden 20 ml Dichlormethan hinzugegeben und die organische Phase wurde 3x mit je 40 ml deionisiertem Wasser gewaschen, über MgSO4 getrocknet und das Lösungsmittel bei 800 mbar und 40 °C entfernt. Das erhaltene Produkt wurde unter Stickstoffatmosphäre bei 4 °C gelagert.Ammonium thiocyanate (13.24 g, 2 eq.) was dissolved in a mixture of 10 ml water, 30 ml acetonitrile and 10 g 4,4'-methylene-bis-( N,N -diglycidylaniline) (30 g, 1 eq.) added. The solution was kept in a water bath and the reaction stopped after 5.5 hours when no more epoxide was detectable by thin layer chromatography (TLC). After phase separation, 20 ml of dichloromethane were added and the organic phase was washed 3 times with 40 ml of deionized water each time, dried over MgSO 4 and the solvent was removed at 800 mbar and 40.degree. The product obtained was stored under a nitrogen atmosphere at 4°C.
Ammoniumthiocyanat (25,37 g, 2 Äq.) wurde in 108 ml Wasser und 12 ml Isopropanol gelöst und Sorbitolglycidylether (30 g, 1 Äq.) hinzugegeben. Die Lösung wurde in einem Wasserbad gehalten und der pH-Wert mit 37%iger HCl auf 7 eingestellt. Die Reaktion wurde nach 6 Stunden gestoppt, als kein Epoxid mehr mittels Dünnschichtchromatographie (DC) nachweisbar war. Das Produkt wurde mit 40 ml Dichlormethan extrahiert und die organische Phase wurde 3x mit je 30 ml deionisiertem Wasser gewaschen, über MgSO4 getrocknet und das Lösungsmittel bei 800 mbar und 40 °C entfernt. Das erhaltene Produkt wurde unter Stickstoffatmosphäre bei 4 °C gelagert.Ammonium thiocyanate (25.37 g, 2 eq.) was dissolved in 108 ml water and 12 ml isopropanol and sorbitol glycidyl ether (30 g, 1 eq.) added. The solution was kept in a water bath and the pH adjusted to 7 with 37% HCl. The reaction was stopped after 6 hours when epoxide was no longer detectable by thin layer chromatography (TLC). The product was extracted with 40 ml of dichloromethane and the organic phase was washed 3 times with 30 ml of deionized water each time, dried over MgSO 4 and the solvent was removed at 800 mbar and 40.degree. The product obtained was stored under a nitrogen atmosphere at 4°C.
Allgemein können die erhaltenen Thiirane jeweils mit einem Überschuss Diethylamin bei Raumtemperatur gerührt werden, bis die Thiiran-IR-Bande bei 617 cm-1 verschwindet. Überschüssiges Amin kann durch Zugabe von Dichlormethan und anschließendem Waschen mit Phosphatpuffer bis zu einem pH von 7 entfernt werden. Die organische Phase kann mit deionisiertem Wasser gewaschen, über MgSO4 getrocknet und das überschüssige Lösungsmittel entfernt werden. Danach kann die erhaltene viskose Flüssigkeit in ein wässriges saures Medium wie 5% ige HCl (w/V) überführt werden und der pH-Wert kann mit Hilfe von wässrigem Ammoniak (30%ig) eingestellt werden.In general, the thiiranes obtained can each be stirred with an excess of diethylamine at room temperature until the thiirane IR band at 617 cm -1 disappears. Excess amine can be removed by addition of dichloromethane followed by washing with phosphate buffer to pH 7. The organic phase can be washed with deionized water, dried over MgSO 4 and the excess solvent removed. Thereafter, the viscous liquid obtained can be transferred to an aqueous acidic medium such as 5% HCl (w/v) and the pH can be adjusted using aqueous ammonia (30%).
Das in Beispiel 3 erhaltene Thiiran (2 g, 1 Äq.) wurde 3 Stunden bei Raumtemperatur mit Diethylamin (4,16 g, 5 Äq.) gemischt bis die Thiiran-IR-Bande bei 617 cm-1 verschwunden war. Die so erhaltene viskose Flüssigkeit wurde in ein wässriges saures Medium wie 5%ige HCl (w/V) überführt.The thiirane (2 g, 1 eq.) obtained in Example 3 was mixed with diethylamine (4.16 g, 5 eq.) at room temperature for 3 hours until the thiirane IR band at 617 cm -1 disappeared. The viscous liquid thus obtained was transferred into an aqueous acidic medium such as 5% HCl (w/v).
Das in Beispiel 5 erhaltene Thiiran (5 g, 1 Äq.) wurde 5 Stunden bei Raumtemperatur mit Diethylamin (10,22 g, 5 Äq.) gemischt bis die Thiiran-IR-Bande bei 617 cm-1 verschwunden war. Überschüssiges Amin wurde durch Zugabe von 160 ml Dichlormethan und anschließendem Waschen mit 160 ml Phosphatpuffer (pH 7) bis zu einem pH von 7 entfernt werden. Die organische Phase wurde mit 160 ml deionisiertem Wasser gewaschen, über MgSO4 getrocknet und das überschüssige Lösungsmittel entfernt.The thiirane (5 g, 1 eq.) obtained in Example 5 was mixed with diethylamine (10.22 g, 5 eq.) at room temperature for 5 hours until the thiirane IR band at 617 cm -1 disappeared. Excess amine was removed by adding 160 ml dichloromethane and then washing with 160 ml phosphate buffer (pH 7) to pH 7. The organic phase was washed with 160 ml deionized water, dried over MgSO 4 and the excess solvent removed.
Ein Probenkörper aus Kupfer (Rocholl, 10 x 2,5 cm) wurde zunächst mit Aceton gereinigt und dann in ein Bad getaucht, das 4 g/L der Verbindung (A19) gemäß Beispiel 9 in 5%iger HCl (w/V) enthielt. Der Probenkörper wurde für 30 Minuten ohne Rühren in dem Bad gelassen und danach mit Leitungswasser und deionisiertem Wasser gewaschen und in einem Luftstrom getrocknet. Nach dieser Behandlung erschien der Probenkörper bei optischer Prüfung weißlich und ein Polymernetzwerk konnte mit Hilfe von SEM nachgewiesen werden.A copper specimen (Rocholl, 10×2.5 cm) was first cleaned with acetone and then immersed in a bath containing 4 g/L of the compound (A1 9 ) according to Example 9 in 5% HCl (w/v) contained. The specimen was left in the bath without agitation for 30 minutes and then washed with tap water and deionized water and dried in a stream of air. After this treatment, the specimen appeared whitish on visual inspection and a polymer network could be detected by SEM.
Ein Probenkörper aus Kupfer (Rocholl, 15 x 15 cm) wurde zunächst mit Aceton gereinigt und dann in ein Bad getaucht, das 5 g/L der Verbindung (A110) gemäß Beispiel 10 in 5%iger HCl (w/V) enthielt. Der Probenkörper wurde für 10 Minuten ohne Rühren in dem Bad gelassen und danach mit Leitungswasser und deionisiertem Wasser gewaschen und in einem Luftstrom getrocknet. Nach dieser Behandlung erschien der Probenkörper bei optischer Prüfung weißlich und ein Polymernetzwerk konnte mit Hilfe von SEM nachgewiesen werden.A copper specimen (Rocholl, 15×15 cm) was first cleaned with acetone and then immersed in a bath containing 5 g/L of the compound (A1 10 ) according to Example 10 in 5% HCl (w/v). The specimen was left in the bath without agitation for 10 minutes and then washed with tap water and deionized water and dried in a stream of air. After this treatment, the specimen appeared whitish on visual inspection and a polymer network could be detected by SEM.
Mehrere 10 x 2,5 cm große Probenkörper aus einer Aluminium-Kupfer-Legierung (Al2024-T3; 93,5% AI, 4,5% Cu, 1,5% Mg, 0,5% Mn) der Firma Rocholl wurden einer Standardvorbehandlung unterzogen, wie sie für in der Luftfahrt verwendete Al-Legierungen üblich ist: nicht-ätzende, alkalische Entfettung, alkalisches Ätzen und saure Deoxidation. Die so vorbereiteten Probenkörper wurden jeweils in Beschichtungsbäder mit unterschiedlichen Konzentrationen der Verbindung (A110) gemäß Beispiel 10 in 0,04 M Schwefelsäure gegebenen. Der pH-Wert wurde mit 30%igem Ammoniak auf 4 eingestellt. Zu einigen der Bäder wurde weiterhin NaF und/oder CuSO4 gegeben. Nach 10 Minuten ohne Rühren wurden die Probenkörper jeweils aus dem Bad entfernt und mit Leitungswasser und deionisiertem Wasser gewaschen und im Luftstrom getrocknet. Auf der Oberfläche gebildetes Polymer wurde in allen Fällen mit Hilfe von SEM/EDX und PM-RAIRS nachgewiesen. Die jeweiligen Bedingungen sind Tabelle 1 zusammengefasst.
In allen Fällen wurde eine zufriedenstellende Ausbildung von Polymer auf der Oberfläche beobachtet. Die höchste Polymerabscheidung auf der Oberfläche wurde beobachtet, wenn das Beschichtungsbad 2 g/L der Verbindung (A110), 500 mg/L NaF und 200 mg/L CuSO4 enthielt, wobei erste Abscheidungen von Kupfer auf der Oberfläche beobachtet wurden. Keine Abscheidung von Kupfer bei guter Ausbildung eines Polymernetzwerks auf der Oberfläche des Prüfkörpers wurde bei Verwendung eines Beschichtungsbads mit 0,25 g/L der Verbindung (A110) und 500 mg/L NaF festgestellt.In all cases satisfactory formation of polymer on the surface was observed. The highest polymer deposition on the surface was observed when the plating bath contained 2 g/L of the compound (A1 10 ), 500 mg/L NaF and 200 mg/L CuSO 4 , with the first deposits of copper being observed on the surface. No deposition of copper with good formation of a polymer network on the surface of the test specimen was found when using a coating bath with 0.25 g/L of the compound (A1 10 ) and 500 mg/L of NaF.
Mehrere 10 x 2,5 cm große Probenkörper aus einer Aluminium-Kupfer-Legierung (Al2024-T3; 93,5% Al, 4,5% Cu, 1,5% Mg, 0,5% Mn) der Firma Rocholl wurden einer Standardvorbehandlung unterzogen, wie sie für in der Luftfahrt verwendete Al-Legierungen üblich ist: nicht-ätzende, alkalische Entfettung, alkalisches Ätzen und saure Deoxidation. Die so vorbereiteten Probenkörper wurden jeweils in Beschichtungsbäder mit unterschiedlichen Konzentrationen der Verbindung (A110) gemäß Beispiel 10 in 0,04 M Schwefelsäure gegebenen, zu denen zusätzlich eine Menge an Hexafluorozirkonsäure (132 ppm berechnet als Zr) additiviert wurde. Der pH-Wert wurde mit 30%igem Ammoniak auf 4 eingestellt. Nach 10 Minuten ohne Rühren wurden die Probenkörper jeweils aus dem Bad entfernt und mit Leitungswasser und deionisiertem Wasser gewaschen und im Luftstrom getrocknet. Auf der Oberfläche gebildetes Polymer und Zr wurde in allen Fällen mit Hilfe von SEM/EDX und PM-RAIRS nachgewiesen. Die jeweiligen Bedingungen sind Tabelle 2 zusammengefasst.
Die Beschichtung wurde mittels XRF analysiert und es konnte ein Anstieg von bis zu 46% für die Fälle festgestellt werden, in denen das Beschichtungsbad die Verbindung (A110) enthielt. Potentiometrische Polarisationsuntersuchungen zeigten außerdem eine kathodische Verschiebung des Potentials im Vergleich zu den Probenkörpern, die nur mit Zr behandelt wurden.The coating was analyzed by XRF and an increase of up to 46% was observed for cases where the coating bath contained compound (A1 10 ). Potentiometric polarization studies also showed a cathodic potential shift compared to the specimens treated with Zr only.
Mehrere 10 x 2,5 cm große Probenkörper aus einer Aluminium-Kupfer-Legierung (Al2024-T3; 93,5% Al, 4,5% Cu, 1,5% Mg, 0,5% Mn) der Firma Rocholl wurden einer Standardvorbehandlung unterzogen, wie sie für in der Luftfahrt verwendete Al-Legierungen üblich ist: nicht-ätzende, alkalische Entfettung, alkalisches Ätzen und saure Deoxidation. Die so vorbereiteten Probenkörper wurden zunächst in Beschichtungsbäder mit unterschiedlichen Konzentrationen der Verbindung (A110) gemäß Beispiel 10 in 0,04 M Schwefelsäure gegebenen. Der pH-Wert wurde mit 30%igem Ammoniak auf 4 eingestellt. Nach 10 Minuten ohne Rühren wurden die Probenkörper jeweils aus dem Bad entfernt und mit deionisiertem Wasser gewaschen. Dann wurden sie für 10 Minuten in ein Beschichtungsbad enthaltend 132 ppm an Hexafluorozirkonsäure (berechnet als Zr) getaucht. Nach Entfernen aus dem Bad wurde die Probenkörper mit Leitungswasser und deionisiertem Wasser gewaschen und im Luftstrom getrocknet. Auf der Oberfläche gebildetes Polymer und Zr wurden in allen Fällen mit Hilfe von SEM/EDX und PM-RAIRS nachgewiesen. Die jeweiligen Bedingungen sind Tabelle 3 zusammengefasst.
Claims (16)
wobei mindestens ein Rest R1 oder R2 aus einer aliphatischen Alkyl-Gruppe mit nicht mehr als 6 Kohlenstoff-Atomen ausgewählt ist;
wobei die Reste R3 und R4 in jeder n-ten Einheit (-HCR3-CHR4-O-) unabhängig voneinander ausgewählt sind aus Wasserstoff oder einer Methyl-Gruppe;
wobei die Reste R3 und R4 innerhalb einer n-ten Einheit (-HCR3-CHR4-O-) nicht beide aus einer Methyl-Gruppe ausgewählt sein können;
wobei n gleich Null oder eine natürliche Zahl kleiner 6, vorzugsweise kleiner als 4 ist;
wobei die wasserlösliche schwefelorganische Verbindung (A1) vorzugsweise folgender Strukturformel (II) entspricht:
wobei die Reste R5, R6 und R7 ausgewählt sind aus Wasserstoff, einer aliphatischen Alkyl-Gruppe mit nicht mehr als 6 Kohlenstoff-Atomen, dem Rest -FG oder dem Rest -CHR1-FG; wobei mindestens einer der Reste R5, R6 und R7, vorzugsweise alle Reste R5, R6 und R7, entweder einen Rest -FG oder einen Rest -CHR1-FG, vorzugsweise einen Rest -CHR1-FG darstellen.Composition (A) according to one or both of the preceding claims, characterized in that the water-soluble organosulfur compound (A1) has the following structural unit (I) as an adhesion-promoting functional group (FG):
wherein at least one R 1 or R 2 is selected from an aliphatic alkyl group having no more than 6 carbon atoms;
wherein the radicals R 3 and R 4 in every nth unit (-HCR 3 -CHR 4 -O-) are independently selected from hydrogen or a methyl group;
wherein the radicals R 3 and R 4 within an nth unit (-HCR 3 -CHR 4 -O-) cannot both be selected from a methyl group;
where n is zero or a natural number less than 6, preferably less than 4;
where the water-soluble organosulfur compound (A1) preferably corresponds to the following structural formula (II):
wherein the radicals R 5 , R 6 and R 7 are selected from hydrogen, an aliphatic alkyl group having not more than 6 carbon atoms, the radical -FG or the radical -CHR 1 -FG; where at least one of the radicals R 5 , R 6 and R 7 , preferably all radicals R 5 , R 6 and R 7 , represent either a radical -FG or a radical -CHR 1 -FG, preferably a radical -CHR 1 -FG.
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| GB2324084A (en) * | 1997-04-11 | 1998-10-14 | Atochem Elf Sa | Use of mono- or polythiols as corrosion inhibitors |
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| US20050186347A1 (en) | 2004-02-25 | 2005-08-25 | Hyung-Joon Kim | Method of protecting metals from corrosion using thiol compounds |
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| EP2986678A1 (en) | 2013-04-19 | 2016-02-24 | The Boeing Company | Systems, compositions, and methods for corrosion inhibition |
| US20160168724A1 (en) | 2014-12-15 | 2016-06-16 | The Boeing Company | Polyvinylbutyral coating containing thiol corrosion inhibitors |
| US20160289537A1 (en) | 2014-07-29 | 2016-10-06 | Halliburton Energy Services, Inc. | Sulfide-containing corrosion inhibitors |
| EP3310837A1 (en) | 2015-06-19 | 2018-04-25 | PRC-Desoto International, Inc. | Flexible non-chromate corrosion inhibitive primer |
-
2021
- 2021-06-28 EP EP21382567.2A patent/EP4112772A1/en not_active Withdrawn
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| GB2324084A (en) * | 1997-04-11 | 1998-10-14 | Atochem Elf Sa | Use of mono- or polythiols as corrosion inhibitors |
| JP2000109460A (en) * | 1998-10-01 | 2000-04-18 | Nippon Shokubai Co Ltd | New amino group-containing sulfide compound, its production and corrosion inhibitor for metal containing the same |
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| JP2014132107A (en) * | 2012-12-03 | 2014-07-17 | Mec Co Ltd | Etching fluid, replenishing fluid, and method for forming copper wiring |
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| EP3310837A1 (en) | 2015-06-19 | 2018-04-25 | PRC-Desoto International, Inc. | Flexible non-chromate corrosion inhibitive primer |
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