TWI673391B - 鋅或鋅合金基材用之3價鉻化學轉換處理液及化學轉換被膜 - Google Patents
鋅或鋅合金基材用之3價鉻化學轉換處理液及化學轉換被膜 Download PDFInfo
- Publication number
- TWI673391B TWI673391B TW104143764A TW104143764A TWI673391B TW I673391 B TWI673391 B TW I673391B TW 104143764 A TW104143764 A TW 104143764A TW 104143764 A TW104143764 A TW 104143764A TW I673391 B TWI673391 B TW I673391B
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- TW
- Taiwan
- Prior art keywords
- chemical conversion
- zinc
- conversion treatment
- zirconium
- treatment liquid
- Prior art date
Links
- 239000000126 substance Substances 0.000 title claims abstract description 76
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 62
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 34
- 239000011701 zinc Substances 0.000 title claims abstract description 34
- 229910001297 Zn alloy Inorganic materials 0.000 title claims abstract description 33
- 239000000758 substrate Substances 0.000 title claims abstract description 26
- 239000011651 chromium Substances 0.000 title claims description 31
- 229910052804 chromium Inorganic materials 0.000 title claims description 13
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims description 12
- 238000007739 conversion coating Methods 0.000 title claims description 12
- 238000012545 processing Methods 0.000 title description 2
- 239000007788 liquid Substances 0.000 claims abstract description 38
- 150000003839 salts Chemical class 0.000 claims abstract description 25
- 229910001430 chromium ion Inorganic materials 0.000 claims abstract description 18
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 12
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims abstract description 12
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 8
- 150000002500 ions Chemical class 0.000 claims abstract description 5
- 239000002253 acid Substances 0.000 claims description 17
- 229910052726 zirconium Inorganic materials 0.000 claims description 15
- -1 zirconium ions Chemical class 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 150000003755 zirconium compounds Chemical class 0.000 claims description 12
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 7
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- 239000010941 cobalt Substances 0.000 claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 5
- 150000002739 metals Chemical class 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 150000003018 phosphorus compounds Chemical class 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims 1
- 125000003118 aryl group Chemical group 0.000 claims 1
- 125000001142 dicarboxylic acid group Chemical group 0.000 claims 1
- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical compound [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 0.000 abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 36
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 30
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 28
- 239000000243 solution Substances 0.000 description 28
- 238000012360 testing method Methods 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 18
- 238000007747 plating Methods 0.000 description 15
- 238000005260 corrosion Methods 0.000 description 12
- 230000007797 corrosion Effects 0.000 description 12
- 235000011121 sodium hydroxide Nutrition 0.000 description 12
- 235000006408 oxalic acid Nutrition 0.000 description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229910017604 nitric acid Inorganic materials 0.000 description 6
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 3
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 3
- 150000001845 chromium compounds Chemical class 0.000 description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 3
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 2
- WRAGBEWQGHCDDU-UHFFFAOYSA-M C([O-])([O-])=O.[NH4+].[Zr+] Chemical compound C([O-])([O-])=O.[NH4+].[Zr+] WRAGBEWQGHCDDU-UHFFFAOYSA-M 0.000 description 2
- 229910000640 Fe alloy Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 2
- 150000001869 cobalt compounds Chemical class 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 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
- 239000010936 titanium Substances 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- XJUNLJFOHNHSAR-UHFFFAOYSA-J zirconium(4+);dicarbonate Chemical compound [Zr+4].[O-]C([O-])=O.[O-]C([O-])=O XJUNLJFOHNHSAR-UHFFFAOYSA-J 0.000 description 2
- ZGMMMTSCLMMPDI-UHFFFAOYSA-J 2,3-dihydroxybutanedioate;zirconium(4+) Chemical compound [Zr+4].[O-]C(=O)C(O)C(O)C([O-])=O.[O-]C(=O)C(O)C(O)C([O-])=O ZGMMMTSCLMMPDI-UHFFFAOYSA-J 0.000 description 1
- ZFQCFWRSIBGRFL-UHFFFAOYSA-B 2-hydroxypropane-1,2,3-tricarboxylate;zirconium(4+) Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O ZFQCFWRSIBGRFL-UHFFFAOYSA-B 0.000 description 1
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 description 1
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HSSJULAPNNGXFW-UHFFFAOYSA-N [Co].[Zn] Chemical compound [Co].[Zn] HSSJULAPNNGXFW-UHFFFAOYSA-N 0.000 description 1
- FYNPOIYWZJKWMW-UHFFFAOYSA-O [Zr].[N+](=O)([O-])[O-].[NH4+] Chemical compound [Zr].[N+](=O)([O-])[O-].[NH4+] FYNPOIYWZJKWMW-UHFFFAOYSA-O 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000013475 authorization Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 1
- 229940075614 colloidal silicon dioxide Drugs 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- WBFZBNKJVDQAMA-UHFFFAOYSA-D dipotassium;zirconium(4+);pentacarbonate Chemical compound [K+].[K+].[Zr+4].[Zr+4].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O WBFZBNKJVDQAMA-UHFFFAOYSA-D 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229940049920 malate Drugs 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N malic acid Chemical compound OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 1
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- GQJPVGNFTLBCIQ-UHFFFAOYSA-L sodium;zirconium(4+);carbonate Chemical compound [Na+].[Zr+4].[O-]C([O-])=O GQJPVGNFTLBCIQ-UHFFFAOYSA-L 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- GZCWPZJOEIAXRU-UHFFFAOYSA-N tin zinc Chemical compound [Zn].[Sn] GZCWPZJOEIAXRU-UHFFFAOYSA-N 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- 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
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Abstract
本發明係提供一種鋅或鋅合金基材用之化學轉換處理液,其係含有2至200mmol/L之3價鉻離子、1至300mmol/L之鋯離子、以及氟離子及水溶性羧酸或其鹽之至少一種,並且不含有Co離子及6價鉻離子。
Description
本發明係關於一種新穎的化學轉換處理液及由其所得到之化學轉換被膜,該化學轉換處理液係用以對於鋅或鋅合金金屬表面賦予優異的耐腐蝕性。
化學轉換處理係自古以來為了對金屬表面賦予耐腐蝕性而使用之技術,現在亦使用於飛機、建築用材料、汽車零件等之表面處理。然而,以鉻酸鉻酸鹽化學轉換處理為代表之化學轉換被膜係含有有害的6價鉻作為其一部分。
6價鉻係因WEEE(Waste Electrical and Electronic Equipment,廢電子電機設備)指令和RoHS(Restriction of Hazardous Substances,危害性物質限制)指令、ELV(End of Life Vehicles,廢車輛)指令等而成為規範對象,使用3價鉻取代6價鉻之化學轉換處理液係經積極研究而工業化。
然而,為了提升耐腐蝕性,在鋅或鋅合金基材用之3價鉻化學處理轉換液中通常添加鈷化合物。
鈷係所謂稀有金屬之一,由於使用用途的擴大或者是受生產國限制等理由,並不能說是必然可安定供給之體制。又,氯化鈷、硫酸鈷、硝酸鈷、碳酸鈷亦相當於REACH(Registration,Evalation,Authorization and Restriction of Chemicals,關於化學品之註冊、評估、許可和限制之法案)規範中之SVHC(Substances of Very High Concern,高度關注物質),而有限制使用之傾向。
再者,亦有數個報告提到無鉻的化學轉換處理液係作為鋅或鋅合金基材用之對應環境之化學轉換處理液。例如,已知有一種處理劑,其係含有選自鋯、鈦之化合物,選自釩、鉬、鎢之化合物,並更含有磷無機化合物(日本特開2010-150626號公報);以及一種不含氟及鉻之化學轉換處理劑,其係含有選自水溶性鈦化合物、水溶性鋯化合物之化合物,以及具有官能基之有機化合物(國際公開第2011/002040號手冊)。
然而,如此之無鉻的化學轉換處理劑,在與以往之含有鈷的鋅或鋅合金用化學轉換處理劑相比時,由於其化學轉換被膜性能係在耐腐蝕性等方面為不佳,因而被期望改良。
本發明之課題係有鑑於上述現狀,而提供一種鋅或鋅合金基材用之化學轉換處理液,其係實質上不含
有鈷化合物,並且可形成耐腐蝕性優異且對環境亦有考量之化學轉換被膜。
本發明者等人係精心研究不含有6價鉻離子、鈷離子且可形成耐腐蝕性優異並且對環境亦有考量之化學轉換被膜的化學轉換處理液,結果發現同時含有鋯離子與3價鉻離子,並且更含有氟離子及水溶性羧酸或其鹽之至少一種的化學轉換處理液可解決上述課題,進而完成本發明。亦即,本發明係提供一種鋅或鋅合金基材用之化學轉換處理液,其係含有2至200mmol/L之3價鉻離子、1至300mmol/L之鋯離子、以及氟離子及水溶性羧酸或其鹽之至少一種,並且不含有Co離子及6價鉻離子。
又,本發明係提供一種鋅或鋅合金基材之化學轉換處理方法,其係包含:使上述化學轉換處理液與鋅或鋅合金基材接觸。
再者,本發明係提供一種化學轉換被膜,其係由上述化學轉換處理液所形成之含有3價鉻及鋯並且不含有6價鉻及鈷者。
依據本發明,可提供一種鋅或鋅合金基材用之化學轉換處理液,其係不含有6價鉻、鈷,並且可形成耐腐蝕性優異且對環境亦有考量之化學轉換被膜。
就本發明中使用之基體而言,係可列舉如
鐵、鎳、銅等各種金屬以及該等之合金、或經施予鋅取代處理之鋁等金屬或合金之板狀物、長方體、圓柱、圓筒、球狀物等各種形狀者。
上述基體係藉由常法而施予鋅及鋅合金鍍覆。若欲在基體上使鋅鍍覆析出,係可為硫酸浴、氟硼化浴、氯化鉀浴、氯化鈉浴、氯化銨組合浴等酸性/中性浴,氰浴、鋅酸鹽浴、焦磷酸浴等鹼性浴之任一者;若要特別列舉則較佳為鋅酸鹽浴。又,鋅合金鍍覆係可為氯化銨浴、有機螯合物浴等鹼性浴之任一者。
又,就鋅合金鍍覆而言,可列舉如鋅-鐵合金鍍覆、鋅-鎳合金鍍覆、鋅-鈷合金鍍覆、錫-鋅合金鍍覆等。較佳為鋅-鐵合金鍍覆。在基體上析出之鋅或鋅合金鍍覆的厚度係可為任意,通常為1μm以上,較佳係為5至25μm。
在本發明中,如上述般在基體上使鋅或鋅合金鍍覆析出後,係根據必要而適宜地進行前處理,例如水洗、或水洗後再進行硝酸活性處理之後,使用本發明之鋅或鋅合金基材用之化學轉換處理液,例如以浸漬處理等方法進行化學轉換處理。
本發明之鋅或鋅合金基材用之化學轉換處理液係含有2至200mmol/L之3價鉻離子、1至300mmol/L之鋯離子、以及氟離子及水溶性羧酸或其鹽之至少一種,並且不含有Co離子及6價鉻離子。
提供3價鉻離子之3價鉻化合物的種類係無特別限
制,較佳為水溶性者。3價鉻化合物係可列舉例如:Cr(NO3)3‧9H2O、Cr(CH3COO)3、Cr2(SO4)3‧18H2O、CrK(SO4)2‧12H2O等。該等3價鉻化合物係可單獨使用,亦可將2種以上組合使用。3價鉻離子之含量係2至200mmol/L,較佳為5至100mmol/L,更佳為10至80mmol/L。將3價鉻離子的含量設為如此之範圍時,可得到優異的耐腐蝕性。
提供鋯離子之鋯化合物的種類係無特別限制,較佳為水溶性者。鋯化合物係可列舉例如:作為無機鋯化合物或其鹽之硝酸鋯、硝酸氧鋯、硝酸鋯銨、氯化鋯、硫酸鋯、碳酸鋯、碳酸鋯銨、碳酸鋯鉀、碳酸鋯鈉、碳酸鋯鋰等;作為有機鋯化合物之乙酸鋯、乳酸鋯、酒石酸鋯、蘋果酸鋯、檸檬酸鋯等。作為鋯化合物,較佳為氟鋯酸(H2ZrF6)及其鹽,例如氟鋯酸(H2ZrF6)的鈉鹽、鉀鹽、鋰鹽及銨鹽[(NH4)2ZrF6]等。該等鋯化合物可單獨使用,亦可將2種以上組合使用。鋯離子的含量係1至300mmol/L,較佳為5至150mmol/L,更佳為10至100mmol/L。將鋯離子的含量設為如此之範圍時,可得到優異的耐腐蝕性。
3價鉻離子與鋯離子之莫耳比(3價鉻離子/鋯離子)較佳為2.5以下,更佳為0.1至2.5,又更佳為0.2至2.1,最佳為0.3至2.0。將3價鉻離子與鋯離子的莫耳比設為如此之範圍時,可得到優異的耐腐蝕性。
本發明之鋅或鋅合金基材用之化學轉換處理液係更含有氟離子及水溶性羧酸或其鹽之至少一種。
提供氟離子之含氟化合物的種類係無特別限制。含氟
化合物係可列舉例如:氫氟酸、氟硼酸、氟化銨、六氟鋯酸或其鹽等,較佳為六氟鋯酸。該等含氟化合物係可單獨使用,亦可將2種以上組合使用。氟離子之含量較佳為5至500mmol/L,更佳為60至300mmol/L。氟離子係成為鋯離子之相對離子,將氟離子的含量設為如此之範圍時,可使鋯離子安定化。
水溶性羧酸的種類係無特別限制。水溶性羧酸係可列舉例如:能以R1-(COOH)2[R1=C0~C8]所示之草酸、丙二酸、琥珀酸、戊二酸、己二酸、辛二酸等二羧酸,較佳為R1各為C0及C1之草酸及丙二酸。水溶性羧酸之鹽係可列舉例如:鉀、鈉等鹼金屬之鹽;鈣、鎂等鹼土金屬之鹽;銨鹽等。該等水溶性羧酸或其鹽係可單獨使用,亦可將2種以上組合使用。水溶性羧酸或其鹽之含量較佳為0.1g/L至10g/L,更佳為0.5g/L至8g/L,又更佳為1g/L至5g/L。將水溶性羧酸或其鹽之含量設為如此之範圍時,可藉由與鉻離子形成錯合物而使Cr3+安定化。
本發明之鋅或鋅合金基材用之化學轉換處理液較佳為含有氟鋯酸作為水溶性鋯化合物及含氟化合物。
本發明之鋅或鋅合金基材用之化學轉換處理液可更包含選自由下述i)、ii)及iii)所成群組中之一種以上:i)含有選自由Al、Ti、Mo、V、Ce及W所成群組中之金屬的水溶性金屬鹽;ii)Si化合物;以及iii)磷化合物。
水溶性金屬鹽係可舉例如K2TiF6等。該等水溶性金屬鹽係可單獨使用,亦可將2種以上組合使用。水溶性金屬
鹽之含量較佳為0.1g/L至1.5g/L,更佳為0.2g/L至1.0g/L。
Si化合物係可舉例如SiO2(膠體二氧化矽)等。該等Si化合物係可單獨使用,亦可將2種以上組合使用。Si化合物之含量較佳為0.1g/L至10g/L,更佳為0.5g/L至5.0g/L,又更佳為1.0g/L至3.0g/L。
磷化合物係可舉例如NaH2PO2(次磷酸鈉)等。該等磷化合物係可單獨使用,亦可將2種以上組合使用。磷化合物之含量較佳為0.01g/L至1.0g/L,更佳為0.1g/L至0.5g/L。
本發明之鋅或鋅合金基材用之化學轉換處理液之pH較佳為1至6的範圍,更佳為1.5至4的範圍。
本發明之鋅或鋅合金基材用之化學轉換處理液中之上述成分的剩餘成分為水。
使用本發明之鋅或鋅合金基材用之化學轉換處理液而在鋅或鋅合金鍍覆上形成3價鉻化學轉換被膜之方法,一般而言係將經鋅或鋅合金鍍覆之基體浸漬在前述化學轉換處理液中。浸漬時之化學轉換處理液的溫度較佳為20至60℃,更佳為30至40℃。浸漬時間較佳為5至600秒,較佳為30至300秒。再者,為了將鋅或鋅合金鍍覆表面予以活化,可在3價鉻化學轉換處理前,予以浸漬於稀硝酸溶液(5%硝酸等)或稀硫酸溶液、稀鹽酸溶液、稀氫氟酸溶液等。上述以外的條件或處理操作係可遵照以往之6價鉻酸鹽處理方法而進行。
使用本發明之鋅或鋅合金基材用之化學轉換處理液而
在鋅或鋅合金鍍覆上形成之3價鉻化學轉換被膜,係含有3價鉻及鋯,且不含有6價鉻及鈷。3價鉻化學轉換被膜中之鋯的比例(Zr/(Cr+Zr))較佳為60至90重量%。
接著,依據實施例及比較例說明本發明,惟本發明係不限定於該等者。
試驗片係使用0.5公釐×50公釐×70公釐之SPCC鋼板,並在其表面施以鋅酸鹽鋅鍍覆。鋅鍍覆之膜厚為9至10微米。
將經施行鋅鍍覆之試驗片浸漬於常溫的5%硝酸水溶液中10秒,接著以流動的自來水充分洗滌而使表面清淨化。另外,亦可根據試驗片表面狀態而添加鹼浸泡或熱水洗滌等。
化學轉換處理的實施方法係記載於下述實施例及比較例。
經實行化學轉換處理的試驗片,係以自來水及離子交換水充分地洗淨後,在保持於80℃的電乾燥爐中靜置10分鐘使其乾燥。
化學轉換被膜的外觀係以色調與均勻性之觀點進行評價。
良好=色調為淡藍色至淡黃色而沒有不均勻狀,為具有光澤之均勻外觀;可=色調為淡藍色至淡黃色而有些許不均勻,為均勻性低之外觀;
不可=色調係超出淡藍色至淡黃色之範圍、及/或為不具有均勻性且光澤亦低之外觀。
經化學轉換處理之試驗片係遵照JIS Z-2371進行鹽水噴霧試驗(以下稱為SST),以在72小時、120小時、240小時產生之白銹面積評價耐腐蝕性。試驗結果分成4階段,以「○=沒有產生白銹、△=白銹未達5%、▲=白銹5%以上、×=產生紅銹」而進行評價。
1.金屬濃度之評價
(實施例1)
調製如下述之化學轉換處理液,使用燒鹼溶液調整為pH=2.0之後,針對前述之試驗片以30℃、40秒進行浸漬處理。
(A)40%硝酸鉻:12g/L(Cr為20mmol/L)
(B)氟鋯酸:5.2g/L(Zr為10mmol/L)
(C)草酸:1.4g/L(15mmol/L)
丙二酸:1.6g/L(15mmol/L)
剩餘成分為水。
(實施例2)
調製如下述之化學轉換處理液,使用燒鹼溶液調整為pH=2.0之後,針對前述之試驗片以30℃、40秒進行浸漬處理。
(A)40%硝酸鉻:12g/L(Cr為20mmol/L)
(B)氟鋯酸:10.4g/L(Zr為20mmol/L)
(C)草酸:1.4g/L(15mmol/L)
丙二酸:1.6g/L(15mmol/L)
剩餘成分為水。
(實施例3)
調製如下述之化學轉換處理液,使用燒鹼溶液調整為pH=2.0之後,針對前述之試驗片以30℃、40秒進行浸漬處理。
(A)40%硝酸鉻:12g/L(Cr為20mmol/L)
(B)氟鋯酸:15.6g/L(Zr為30mmol/L)
(C)草酸:1.4g/L(15mmol/L)
丙二酸:1.6g/L(15mmol/L)
剩餘成分為水。
(實施例4)
調製如下述之化學轉換處理液,使用燒鹼溶液調整為pH=2.0之後,針對前述之試驗片以30℃、40秒進行浸漬處理。
(A)40%硝酸鉻:12g/L(Cr為20mmol/L)
(B)氟鋯酸:26g/L(Zr為50mmol/L)
(C)草酸:1.4g/L(15mmol/L)
丙二酸:1.6g/L(15mmol/L)
剩餘成分為水。
(實施例5)
調製如下述之化學轉換處理液,使用62%硝酸調整為pH=4.0之後,針對前述之試驗片以30℃、40秒進行浸漬處理。
(A)40%硝酸鉻:3g/L(Cr為5mmol/L)
(B)氟鋯酸:5.2g/L(Zr為10mmol/L)
剩餘成分為水。
(實施例6)
調製如下述之化學轉換處理液,使用62%硝酸調整為pH=2.0之後,針對前述之試驗片以30℃、40秒進行浸漬處理。
(A)40%硝酸鉻:12g/L(Cr為20mmol/L)
(B)碳酸鋯銨溶液(ZrO220%:6.2g/L(Zr為10mmol/L)
(C)50%乳酸:3.6g/L(乳酸為20mmol/L)
剩餘成分為水。
(比較例1)
調製如下述之化學轉換處理液,使用燒鹼溶液調整為pH=2.0之後,針對前述之試驗片以30℃、40秒進行浸漬處理。
(A)40%硝酸鉻:48g/L(Cr為80mmol/L)
(B)硝酸鈷:Co為1.0g/L
(C)草酸:1.4g/L(15mmol/L)
丙二酸:1.6g/L(15mmol/L)
剩餘成分為水。
(比較例2)
調製如下述之化學轉換處理液,使用燒鹼溶液調整為pH=2.0之後,針對前述之試驗片以30℃、40秒進行浸漬處理。
(A)40%硝酸鉻:24g/L(Cr為40mmol/L)
(B)硝酸鈷:Co為1.0g/L
(C)草酸:1.4g/L(15mmol/L)
丙二酸:1.6g/L(15mmol/L)
剩餘成分為水。
實施例1至6以及比較例1及2之各處理液的組成係整理於表1,評價結果係示於表2,被膜中的3價鉻及鋯之含量係示於表3。
由表2的結果可知,在實施例1至6中,可得到具有與含有鈷之比較例1及2同等之性能的被膜。
2.二羧酸的評價
(實施例7)
調製如下述之化學轉換處理液,使用燒鹼溶液調整為pH=2.0之後,針對前述之試驗片以30℃、40秒進行浸漬處理。
(A)40%硝酸鉻:12g/L(Cr為20mmol/L)
(B)氟鋯酸:10.4g/L(Zr為20mmol/L)
(C)草酸:1.8g/L(20mmol/L)
剩餘成分為水。
(實施例8)
調製如下述之化學轉換處理液,使用燒鹼溶液調整為pH=2.0之後,針對前述之試驗片以30℃、40秒進行浸漬處理。
(A)40%硝酸鉻:12g/L(Cr為20mmol/L)
(B)氟鋯酸:10.4g/L(Zr為20mmol/L)
(C)丙二酸:2.0g/L(20mmol/L)
剩餘成分為水。
(實施例9)
調製如下述之化學轉換處理液,使用燒鹼溶液調整為pH=2.0之後,針對前述之試驗片以30℃、40秒進行浸漬處理。
(A)40%硝酸鉻:12g/L(Cr為20mmol/L)
(B)氟鋯酸:10.4g/L(Zr為20mmol/L)
(C)琥珀酸:2.4g/L(20mmol/L)
剩餘成分為水。
(實施例10)
調製如下述之化學轉換處理液,使用燒鹼溶液調整為pH=2.0之後,針對前述之試驗片以30℃、40秒進行浸漬處理。
(A)40%硝酸鉻:12g/L(Cr為20mmol/L)
(B)氟鋯酸:10.4g/L(Zr為20mmol/L)
(C)戊二酸:2.4g/L(20mmol/L)
剩餘成分為水。
(實施例11)
調製如下述之化學轉換處理液,使用燒鹼溶液調整為pH=2.0之後,針對前述之試驗片以30℃、40秒進行浸漬處理。
(A)40%硝酸鉻:12g/L(Cr為20mmol/L)
(B)氟鋯酸:10.4g/L(Zr為20mmol/L)
(C)己二酸:3.0g/L(20mmol/L)
剩餘成分為水。
(實施例12)
調製如下述之化學轉換處理液,使用燒鹼溶液調整為pH=2.0之後,針對前述之試驗片以30℃、40秒進行浸漬處理。
(A)40%硝酸鉻:12g/L(Cr為20mmol/L)
(B)氟鋯酸:10.4g/L(Zr為20mmol/L)
(C)辛二酸:3.5g/L(20mmol/L)
剩餘成分為水。
實施例7至12之各處理液的組成係整理於表4,評價結果係示於表5。
如上述所顯示,使用屬於C0-(COOH)2之草酸、與屬於C1-(COOH)2之丙二酸時的耐腐蝕性為特別良好。
Claims (8)
- 一種鋅或鋅合金基材用之化學轉換處理液,其係含有2至200mmol/L之3價鉻離子、1至300mmol/L之鋯離子、以及氟離子及水溶性羧酸或其鹽之至少一種,並且不含有芳香族磺酸、Co離子及6價鉻離子。
- 如申請專利範圍第1項所述之化學轉換處理液,其中,3價鉻離子與鋯離子之莫耳比(3價鉻離子/鋯離子)為2.5以下。
- 如申請專利範圍第1項所述之化學轉換處理液,其中,提供鋯離子之鋯化合物為無機鋯化合物或其鹽、或者是有機鋯化合物。
- 如申請專利範圍第1項所述之化學轉換處理液,其中,提供鋯離子之鋯化合物為氟鋯酸或其鹽。
- 如申請專利範圍第1項所述之化學轉換處理液,其中,水溶性羧酸或其鹽為二羧酸或其鹽。
- 如申請專利範圍第1至5項中任一項所述之化學轉換處理液,其更包含選自由下述i)、ii)及iii)所成群組中之一種以上:i)含有選自Al、Ti、Mo、V、Ce及W所成群組中之金屬的水溶性金屬鹽;ii)Si化合物;以及iii)磷化合物。
- 一種鋅或鋅合金基材之化學轉換處理方法,其係包含:使申請專利範圍第1至6項中任一項所述之化學轉換處理液與鋅或鋅合金基材接觸。
- 一種化學轉換被膜,其係由申請專利範圍第1至6項中任一項所述之化學轉換處理液所形成之含有3價鉻及鋯並且不含有6價鉻及鈷之化學轉換被膜。
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