CN103459666B - 三价铬化学转化膜用整理剂及黑色三价铬化学转化膜的整理方法 - Google Patents
三价铬化学转化膜用整理剂及黑色三价铬化学转化膜的整理方法 Download PDFInfo
- Publication number
- CN103459666B CN103459666B CN201280016325.8A CN201280016325A CN103459666B CN 103459666 B CN103459666 B CN 103459666B CN 201280016325 A CN201280016325 A CN 201280016325A CN 103459666 B CN103459666 B CN 103459666B
- Authority
- CN
- China
- Prior art keywords
- trivalent chromium
- chemical conversion
- conversion film
- chromium chemical
- finishing agent
- 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.)
- Active
Links
- 239000011651 chromium Substances 0.000 title claims abstract description 131
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 125
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 125
- 239000000126 substance Substances 0.000 title claims abstract description 88
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims description 11
- 239000000203 mixture Substances 0.000 title claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 75
- 238000007739 conversion coating Methods 0.000 claims abstract description 33
- 239000002738 chelating agent Substances 0.000 claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 15
- -1 polyethylene Polymers 0.000 claims abstract description 15
- 229920003169 water-soluble polymer Polymers 0.000 claims abstract description 15
- 229940085991 phosphate ion Drugs 0.000 claims abstract description 13
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 8
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 8
- 229920003086 cellulose ether Polymers 0.000 claims abstract description 6
- 229920001515 polyalkylene glycol Polymers 0.000 claims abstract description 6
- 239000011701 zinc Substances 0.000 claims description 31
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 27
- 229910052725 zinc Inorganic materials 0.000 claims description 27
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 21
- 239000000758 substrate Substances 0.000 claims description 14
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 14
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 13
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 13
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims description 10
- 239000011574 phosphorus Substances 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 229910000151 chromium(III) phosphate Inorganic materials 0.000 claims description 8
- IKZBVTPSNGOVRJ-UHFFFAOYSA-K chromium(iii) phosphate Chemical compound [Cr+3].[O-]P([O-])([O-])=O IKZBVTPSNGOVRJ-UHFFFAOYSA-K 0.000 claims description 8
- RYYXDZDBXNUPOG-UHFFFAOYSA-N 4,5,6,7-tetrahydro-1,3-benzothiazole-2,6-diamine;dihydrochloride Chemical compound Cl.Cl.C1C(N)CCC2=C1SC(N)=N2 RYYXDZDBXNUPOG-UHFFFAOYSA-N 0.000 claims description 7
- 239000004202 carbamide Substances 0.000 claims description 7
- 229910021645 metal ion Inorganic materials 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 239000004094 surface-active agent Substances 0.000 claims description 7
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 235000011090 malic acid Nutrition 0.000 claims description 2
- 239000001630 malic acid Substances 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 150000003628 tricarboxylic acids Chemical class 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 claims 1
- 230000002401 inhibitory effect Effects 0.000 claims 1
- 150000002763 monocarboxylic acids Chemical class 0.000 claims 1
- 238000005260 corrosion Methods 0.000 abstract description 27
- 230000007797 corrosion Effects 0.000 abstract description 27
- 238000009413 insulation Methods 0.000 abstract description 8
- 239000004698 Polyethylene Substances 0.000 abstract description 2
- 229920000573 polyethylene Polymers 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 description 15
- 239000002184 metal Substances 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000007747 plating Methods 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 229910001297 Zn alloy Inorganic materials 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 8
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000000576 coating method Methods 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000002736 nonionic surfactant Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 239000011787 zinc oxide Substances 0.000 description 5
- GUUULVAMQJLDSY-UHFFFAOYSA-N 4,5-dihydro-1,2-thiazole Chemical class C1CC=NS1 GUUULVAMQJLDSY-UHFFFAOYSA-N 0.000 description 4
- XGEGHDBEHXKFPX-UHFFFAOYSA-N N-methyl urea Chemical compound CNC(N)=O XGEGHDBEHXKFPX-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 230000000843 anti-fungal effect Effects 0.000 description 4
- 229940121375 antifungal agent Drugs 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 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
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- LUBJCRLGQSPQNN-UHFFFAOYSA-N 1-Phenylurea Chemical compound NC(=O)NC1=CC=CC=C1 LUBJCRLGQSPQNN-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 229910000640 Fe alloy Inorganic materials 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- 239000004640 Melamine resin Substances 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- KQJQICVXLJTWQD-UHFFFAOYSA-N N-Methylthiourea Chemical compound CNC(N)=S KQJQICVXLJTWQD-UHFFFAOYSA-N 0.000 description 2
- GMEHFXXZSWDEDB-UHFFFAOYSA-N N-ethylthiourea Chemical compound CCNC(N)=S GMEHFXXZSWDEDB-UHFFFAOYSA-N 0.000 description 2
- 229910000990 Ni alloy Inorganic materials 0.000 description 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- UCGFRIAOVLXVKL-UHFFFAOYSA-N benzylthiourea Chemical compound NC(=S)NCC1=CC=CC=C1 UCGFRIAOVLXVKL-UHFFFAOYSA-N 0.000 description 2
- 150000001844 chromium Chemical class 0.000 description 2
- 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 2
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 2
- 229910001429 cobalt ion Inorganic materials 0.000 description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 2
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910001453 nickel ion Inorganic materials 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000011667 zinc carbonate Substances 0.000 description 2
- 235000004416 zinc carbonate Nutrition 0.000 description 2
- 229910000010 zinc carbonate Inorganic materials 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 2
- JOFCKRRWICDWHD-UHFFFAOYSA-N 1-ethoxy-1-phenylthiourea Chemical compound CCON(C(N)=S)C1=CC=CC=C1 JOFCKRRWICDWHD-UHFFFAOYSA-N 0.000 description 1
- NYMPFTQOEPVAMT-UHFFFAOYSA-N 1-ethoxy-1-phenylurea Chemical compound CCON(C(N)=O)C1=CC=CC=C1 NYMPFTQOEPVAMT-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 229910021555 Chromium Chloride Inorganic materials 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
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- RYECOJGRJDOGPP-UHFFFAOYSA-N Ethylurea Chemical compound CCNC(N)=O RYECOJGRJDOGPP-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- VLCDUOXHFNUCKK-UHFFFAOYSA-N N,N'-Dimethylthiourea Chemical compound CNC(=S)NC VLCDUOXHFNUCKK-UHFFFAOYSA-N 0.000 description 1
- MGJKQDOBUOMPEZ-UHFFFAOYSA-N N,N'-dimethylurea Chemical compound CNC(=O)NC MGJKQDOBUOMPEZ-UHFFFAOYSA-N 0.000 description 1
- FULZLIGZKMKICU-UHFFFAOYSA-N N-phenylthiourea Chemical compound NC(=S)NC1=CC=CC=C1 FULZLIGZKMKICU-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229920000604 Polyethylene Glycol 200 Polymers 0.000 description 1
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910005965 SO 2 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 241000519995 Stachys sylvatica Species 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- HSSJULAPNNGXFW-UHFFFAOYSA-N [Co].[Zn] Chemical compound [Co].[Zn] HSSJULAPNNGXFW-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 125000005036 alkoxyphenyl group Chemical group 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- RJNJWHFSKNJCTB-UHFFFAOYSA-N benzylurea Chemical compound NC(=O)NCC1=CC=CC=C1 RJNJWHFSKNJCTB-UHFFFAOYSA-N 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- CNWSQCLBDWYLAN-UHFFFAOYSA-N butylurea Chemical compound CCCCNC(N)=O CNWSQCLBDWYLAN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 description 1
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- QNDQILQPPKQROV-UHFFFAOYSA-N dizinc Chemical compound [Zn]=[Zn] QNDQILQPPKQROV-UHFFFAOYSA-N 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000113 methacrylic resin Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920002523 polyethylene Glycol 1000 Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
-
- 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
- C23C22/07—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 phosphates
- C23C22/08—Orthophosphates
- C23C22/12—Orthophosphates containing zinc cations
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/21—Urea; Derivatives thereof, e.g. biuret
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/39—Thiocarbamic acids; Derivatives thereof, e.g. dithiocarbamates
- C08K5/405—Thioureas; Derivatives thereof
-
- 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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/56—After-treatment
-
- 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
- C23C22/07—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 phosphates
- C23C22/08—Orthophosphates
- C23C22/12—Orthophosphates containing zinc cations
- C23C22/17—Orthophosphates containing zinc cations containing also organic acids
-
- 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
- C23C22/07—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 phosphates
- C23C22/08—Orthophosphates
- C23C22/18—Orthophosphates containing manganese cations
-
- 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
- C23C22/07—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 phosphates
- C23C22/08—Orthophosphates
- C23C22/20—Orthophosphates containing aluminium cations
-
- 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
- C23C22/46—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 oxalates
- C23C22/47—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 oxalates containing also phosphates
-
- 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
- C23C22/68—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 solutions with pH between 6 and 8
-
- 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
-
- 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
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/10—Use of solutions containing trivalent chromium but free of hexavalent chromium
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12771—Transition metal-base component
- Y10T428/12778—Alternative base metals from diverse categories
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Chemical Treatment Of Metals (AREA)
- Paints Or Removers (AREA)
Abstract
本发明的目的在于提供一种三价铬化学转化膜用水溶性整理剂，其能够得到绝缘性低、在牢固性方面没有问题、具有优异的光泽和高耐腐蚀性且擦伤和斑点少的三价铬化学转化膜、尤其是黑色三价铬化学转化膜。本发明提供的三价铬化学转化膜用整理剂的特征在于，其含有三价铬源、磷酸离子源、锌离子源、能够与三价铬形成络合物的螯合剂，以及从由聚乙烯醇及其衍生物、聚乙烯吡咯烷酮及其衍生物、聚烷撑二醇及其衍生物和纤维素醚及其衍生物组成的组中选择的非离子性水溶性高分子化合物。
Description
技术领域
本发明涉及一种三价铬化学转化膜用整理剂（仕上げ剤），尤其涉及一种用于形成擦伤、斑点少且光泽及耐腐蚀性优异的无六价铬的耐腐蚀性膜的整理剂、使用其的整理方法和具有无六价铬的耐腐蚀性膜的金属物品。
背景技术
近年来，作为金属表面的防腐蚀方法，大多使用镀锌或锌合金的方法，但是单独进行电镀时，耐腐蚀性不够充分，电镀后还广泛采用铬酸处理，即所谓的铬酸盐处理。在通过此时进行的铬酸处理形成铬酸盐膜时，六价铬被用作主要成分。但是，近年来，六价铬被指出会对人体、环境造成恶劣影响，限制六价铬使用的倾向越发显著。尤其是在产业界，强烈需要代替六价铬酸盐的技术。
在这种状况下，已提出形成无六价铬的三价铬化学转化膜的方法（例如，美国专利第5415702号，日本专利申请特开2003-166074号及特开2003-166075号）。通过该方法形成的三价铬化学转化膜虽然耐腐蚀性优异，但与现有的黑色六价铬酸盐相比，外观的光泽稍稍不足。因此，为了得到更优异的光泽，需要在三价铬化学转化膜表面再厚厚地外涂布树脂膜或硅酸盐膜。但是，实施这种外涂布的情况下，在绝缘性或牢固性方面有时会出现问题。此外，用含有三价铬源、磷酸离子源、锌离子源和能够与三价铬形成络合物的螯合剂的三价铬化学转化膜用整理剂（例如，日本专利申请特开2005-23372号）进行处理的情况下，虽然在绝缘性或牢固性方面没有问题，但该膜在例如整理处理中的干燥工序等时，有时会出现因物品之间的接触导致多处擦伤或因液体残留等导致产生绿斑、白斑等斑点的问题。此外，有时还会出现整理剂发霉的问题。
发明内容
本发明的目的在于提供一种三价铬化学转化膜用水溶性整理剂，其能够得到绝缘性低、在牢固性方面没有问题、具有优异的光泽和高耐腐蚀性且擦伤和斑点少的三价铬化学转化膜、尤其是黑色三价铬化学转化膜。
本发明的目的还在于提供一种用来得到上述三价铬化学转化膜的整理方法。
本发明的另一目的还在于提供一种具有无六价铬的耐腐蚀性膜的金属物品。
本发明是基于下述发现而完成的，即在使整理剂水溶液附着到具有三价铬化学转化膜的基体上时，在三价铬化学转化膜上形成整理层（仕上げ層），所述整理剂含有三价铬源、磷酸离子源、锌离子源、能够与三价铬形成络合物的螯合剂，以及从由聚乙烯醇及其衍生物、聚乙烯吡咯烷酮及其衍生物、聚烷撑二醇及其衍生物和纤维素醚及其衍生物组成的组中选择的非离子性水溶性高分子化合物，和/或从尿素、硫脲、二氧化硫脲和它们的衍生物中选择的防斑点剂，从而能够解决上述技术问题。
即，本发明提供一种三价铬化学转化膜用整理剂，其特征在于，其含有三价铬源、磷酸离子源、锌离子源、能够与三价铬形成络合物的螯合剂，以及从由聚乙烯醇及其衍生物、聚乙烯吡咯烷酮及其衍生物、聚烷撑二醇及其衍生物和纤维素醚及其衍生物组成的组中选择的非离子性水溶性高分子化合物。
本发明还提供一种三价铬化学转化膜用整理剂，其特征在于，其含有三价铬源、磷酸离子源、锌离子源、能够与三价铬形成络合物的螯合剂，以及从尿素、硫脲、二氧化硫脲及它们的衍生物中选择的防斑点剂。
本发明还提供一种三价铬化学转化膜用整理剂，其特征在于，其含有三价铬源、磷酸离子源、锌离子源、能够与三价铬形成络合物的螯合剂，以及所述非离子性水溶性高分子化合物及所述防斑点剂。
本发明还提供一种三价铬化学转化膜用整理剂，其含有三价铬络合物、磷酸离子、锌离子、非离子性水溶性高分子和/或防斑点剂以及水，呈水溶液的形态，非离子性水溶性高分子化合物是从由聚乙烯醇及其衍生物、聚乙烯吡咯烷酮及其衍生物、聚烷撑二醇及其衍生物和纤维素醚及其衍生物组成的组中选择的；防斑点剂是从尿素、硫脲、二氧化硫脲及它们的衍生物中选择的。
本发明还提供一种黑色三价铬化学转化膜的整理方法，其特征在于，对具有黑色三价铬化学转化膜的基体，使呈水溶液形态的所述三价铬化学转化膜用整理剂附着在该黑色三价铬化学转化膜上，然后进行干燥。
本发明还提供一种金属物品，其具有金属基体和无六价铬的耐腐蚀性膜，所述无六价铬的耐腐蚀性膜包括设置在所述金属基体上的黑色三价铬化学转化膜和设置在所述黑色三价铬化学转化膜上的整理层，其特征在于，整理层含有三价铬、锌和磷元素，在三价铬、锌和磷元素的总计为100重量份时，三价铬为10～40重量份，锌为20～75重量份，磷为3～40重量份。
为了得到三价铬化学转化膜的耐腐蚀性和具有光泽的外观，需要使三价铬化学转化膜的阻挡膜致密且厚。但是，在三价铬化学转化膜的情况下，仅通过化学处理反应难以形成与使用六价铬酸盐得到的厚度相当的阻挡膜。
但是，通过本发明，能够在锌、锌合金镀层上形成擦伤、斑点（尤其是因液体残留引起的绿斑）少、低绝缘性、且不损害牢固性而光泽、耐腐蚀性优异的无六价铬的耐腐蚀性膜，特别是黑色三价铬化学转化膜，因此，能够期待今后广泛用在电子仪器等各种领域中。
具体实施方式
作为本发明的三价铬膜用整理剂中使用的三价铬源，可例举氯化铬、硫酸铬、硝酸铬、磷酸铬、乙酸铬等三价铬盐等。此外，也可以是用还原剂将铬酸或重铬酸盐等六价铬还原成三价的三价铬。这些三价铬源可以使用一种，或两种以上组合使用。其浓度换算为铬浓度优选为0.1g/L～20g/L，更优选为0.3g/L～10g/L。
作为本发明的三价铬膜用整理剂中使用的磷酸离子源，可例举磷酸、亚磷酸等磷的含氧酸及它们的盐，尤其是碱金属盐（アルカリ塩）等。这些磷酸离子源可以使用一种，或两种以上组合使用。其浓度优选为0.3～70g/L，更优选为1～40g/L。
本发明中，作为三价铬源及磷酸离子源，可以使用磷酸铬。这里，若使用的磷酸铬具有Cr(HnPO4)(3/3-n)的结构式（式中，n为1～2），则可得到高温高湿下的耐久性，因此优选，尤其最优选n为1。
作为本发明的三价铬膜用整理剂中使用的锌离子源，可例举氧化锌、碳酸锌、硝酸锌、氯化锌、硫酸锌及各种有机羧酸的锌盐等，但优选氧化锌、碳酸锌。这些锌离子源可以使用一种，或两种以上组合使用。其浓度换算为锌浓度，优选为0.1g/L～30g/L，更优选为0.5g/L～20g/L。
作为本发明的三价铬膜用整理剂中使用的能够与三价铬形成络合物的螯合剂，可例举单羧酸、二羧酸或三羧酸等多元羧酸，羟基羧酸，氨基羧酸（例如甘氨酸）或它们的盐。其中，优选草酸、丙二酸、柠檬酸、酒石酸、苹果酸。这些螯合剂可以使用一种、或两种以上组合使用。其浓度优选为在水溶液中含有0.5～100g/L，更优选1～50g/L。
为了影响耐腐蚀性、整理后的外观（处理后的外观），螯合剂相对于三价铬的摩尔比优选0.2～2。进一步优选0.5～1。螯合剂相对于锌的摩尔比优选0.5以上，更优选0.7～1。
本发明的三价铬膜用整理剂中使用的非离子性水溶性高分子化合物是从聚乙烯醇及其衍生物、聚乙烯吡咯烷酮及其衍生物、聚烷撑二醇及其衍生物以及纤维素醚及其衍生物组成的组中选择的。
作为聚乙烯醇及其衍生物，可例举聚乙烯醇、磺酸改性聚乙烯醇等。例如，可例举日本合成化学的PVANL05、GM-13、GOHSERANL3266等，但并不限于此。
作为聚乙烯吡咯烷酮及其衍生物，可例举聚乙烯吡咯烷酮、乙酸乙烯酯-乙烯吡咯烷酮共聚物等。例如，可例举日本触媒的K-30、K-30W、K-90等，但并不限于此。
作为聚烷撑二醇及其衍生物，可例举聚乙二醇、聚丙二醇及它们的醚衍生物等。例如，可例举日油（株）的PEG-200、PEG-1000及PEG-4000，日油（株）的UNIOLD-700及D-2000，以及日油（株）的UNIOLTG-1000等，但并不限于此。
作为纤维素醚及其衍生物，可例举甲基纤维素、乙基纤维素、羟乙基纤维素、羟丙基纤维素、羟甲基丙基纤维素等。例如，可例举信越化学的MetoloseSM、SH、SH型等，但并不限于此。
这些非离子性水溶性高分子化合物可以使用一种，或两种以上组合使用。非离子性水溶性高分子化合物的浓度优选0.01g/L～50g/L，更优选0.1g/L～10g/L。但是，即使超过50g/L在性能上也没有问题，但无法期待获得更好的效果。
添加这些非离子性水溶性高分子化合物尤其可赋予防擦伤，因此，在改善三价铬化学转化膜外观的基础上，耐腐蚀性也得以提高。通过本发明的三价铬化学转化膜用整理剂，能够形成低绝缘性且在不损害牢固性的前提下具有无擦伤的程度的光泽、耐腐蚀性优异的无六价铬的耐腐蚀性化学转化膜，尤其可形成黑色的三价铬化学转化膜。
本发明的三价铬膜用整理剂中使用的防斑点剂是从由尿素、硫脲、二氧化硫脲及其衍生物组成的组中选择的。
作为尿素、硫脲、二氧化硫脲及其衍生物可例举如下述通式所示的化合物等。
（化学式1）
式中，X为O、S或SO2H,R1～R4各自独立地为氢原子、链烃基、环烃基、芳烷基或芳基。
作为R1～R4的链烃基，优选为碳原子数1～8的链烃基，更优选碳原子数1～8的烷基，例如可例举甲基、乙基、直链或支链丙基、丁基、己基等。
作为环烃基，优选碳原子数3～8的环烃基，更优选碳原子数5～6的环烃基，例如可例举环戊基、环己基等。
作为芳烷基，优选苄基、苯乙基等。在它们的苯基上也可以用烷基等进行取代。
作为芳基，优选苯基、甲苯基、低级烷氧基苯基等。
R1～R4更优选各自独立地为氢原子或碳原子数1～3的烷基。
作为防斑点剂，可例举如尿素、N-甲基尿素、N-乙基尿素、N-丁基尿素、N,N’-二甲基尿素、苯基尿素、苄基尿素、乙氧基苯基尿素、硫脲、N-甲基硫脲、N-乙基硫脲、N,N’-二甲基硫脲、苯基硫脲、苄基硫脲、乙氧基苯基硫脲、二氧化硫脲、N-甲基硫脲二氧化物、N-乙基硫脲二氧化物等。
这些防斑点剂可以使用一种、或两种以上组合使用。防斑点剂的浓度优选为0.01g/L～30g/L，更优选为0.1g/L～15g/L。
添加这些防斑点剂尤其可防止斑点，特别是防止因液体残留引起的绿斑，在此基础上耐腐蚀性也提高。通过本发明的三价铬化学转化膜用整理剂，能够形成低绝缘性且在不损害牢固性的前提下具有无斑点的程度的光泽、耐腐蚀性优异的无六价铬的耐腐蚀性化学转化膜，尤其可形成黑色的三价铬化学转化膜。
进而，在本发明中，通过在所述非离子性水溶性高分子化合物的基础上添加并用所述防斑点剂，能够形成低绝缘性且在不损害牢固性的前提下具有无擦伤及斑点的程度的光泽、耐腐蚀性优异的无六价铬的耐腐蚀性化学转化膜，尤其可形成黑色的三价铬化学转化膜。在非离子性水溶性高分子化合物的基础上添加并用防斑点剂的情况下，各自的添加浓度分别为所述添加浓度的范围，此外，作为合计浓度优选为0.01g/L～50g/L，更优选为0.1g/L～15g/L。
本发明的三价铬膜用整理剂优选还含有防霉成分。通过在上述整理剂中含有防霉成分，可抑制细菌，能够长期使用而不发霉。作为防霉成分，优选异噻唑啉类化合物。作为异噻唑啉类化合物优选下述通式所示的异噻唑啉类化合物。
（化学式2）
式中，R表示碳原子数1～8的烷基，X表示氢原子、Cl原子或Br原子。
这些防霉成分可以使用一种，或两种以上组合使用。防霉成分的浓度优选为0.01g/L～50g/L，更优选为0.1g/L～5g/L。但是，即使超过50g/L在性能上也没有问题，但在经济方面不优选。
本发明的三价铬膜用整理剂还含有水，可以呈水溶液的形态。此时，水溶液的pH优选为2.5～8。更优选为3～7，最优选为4～6。为了将pH调整至该范围，优选使用碱金属的氢氧化物（水酸化アルカリ）、氨水或胺类等碱剂（アルカリ剤）。
为了进一步提高得到的膜的耐腐蚀性，在本发明的三价铬膜用整理剂中还可添加从由铝、硅、钼、锰及钴组成的组中选择的金属离子。这些金属离子可以使用一种，或两种以上组合使用。其浓度优选0.1g/L～30g/L，更优选0.5g/L～5g/L。
此外，在本发明的三价铬膜用整理剂中添加下述表面活性剂或水溶性树脂时，能够提高整理后的膜的外观均匀性并进一步提高光泽性，因此优选。
作为添加的表面活性剂，可例举醚类非离子表面活性剂、聚氧乙烯·聚氧丙烯嵌段聚合物、聚氧乙烯壬基苯基醚等。其浓度优选为0.01g/L～100g/L，更优选为1g/L～50g/L。
作为添加的水溶性树脂，可例举水溶性丙烯酸树脂、水溶性聚氨酯树脂、水溶性三聚氰胺树脂、乳液型蜡等。其浓度优选为0.01g/L～100g/L，更优选为1g/L～50g/L。此外，在添加水溶性树脂的情况下，优选使整理剂组合物的pH为7～8。
此外，为了促进本发明的三价铬膜用整理剂的脱液并防止干燥斑点，还可以添加有机硅塑料。其浓度优选为1～1000ppm，更优选为10～100ppm。
本发明的三价铬膜用整理剂优选不含有卤离子、硫酸离子及磺酸离子。由此可抑制在高温高湿下白色生成物的产生。
作为本发明中使用的基体，可例举铁、镍、铜等各种金属以及它们的合金，或实施了锌置换处理的铝等金属或合金的板状物、长方体、圆柱、圆筒、球状物等各种形状的基体。其中，优选由锌或锌合金制成的基体，或者表面形成了锌或锌合金镀膜的基体。这里，锌或锌合金镀膜可以通过常规方法容易地形成。
例如，可以使用硫酸浴、铵浴、钾浴等酸性浴以及碱性无氰浴、碱性氰化物浴等碱性浴中的任意一种来形成锌镀膜。这里，尤其优选使用碱性无氰镀液（日本迪普索尔（Dipsol）制，NZ-98浴、NZ-87浴等）。
此外，作为锌合金镀层，可例举锌-铁合金镀层、锌-镍合金镀层、锌-钴合金镀层等。锌或锌合金镀层的厚度可以是任意的，但优选1μm以上，更优选5～25μm。
本发明中，作为对象的具有三价铬化学转化膜（优选为黑色三价铬化学转化膜）的基体，可以通过将上述基体，尤其是具有锌或锌合金镀层的基体水洗后，进行三价铬化学转化处理，从而形成三价铬化学转化膜来制得。
三价铬化学转化膜可以使用美国专利第5,415,702号说明书、日本专利申请特开2003-166074号公报或特开2003-166075号公报等记载的各种三价铬化学转化处理液来进行，但优选使用国际公开第2003/076686号记载的黑色三价铬化学转化处理液，即，优选使用具有以下特点的含有钴和/或镍、以及锌、铬、螯合剂的黑色三价铬化学转化处理溶液：硝酸离子与三价铬的摩尔比（NO3 -/Cr3+）小于0.5；三价铬以与螯合剂形成水溶性络合物的形态存在；含有钴离子和/或镍离子；钴离子和/或镍离子不会与螯合剂形成难溶性金属盐从而形成沉淀，而是在该处理溶液中稳定存在；当使锌及锌合金镀层接触该处理溶液时，该处理溶液与锌反应。
例如，优选将具有锌或锌类合金镀层的基体在例如10～80℃、更优选40～60℃的液温下在三价铬化学转化处理溶液中浸渍5～600秒，进行三价铬化学转化处理，更优选浸渍30～120秒。
由此，可以以0.1～0.3μm左右的厚度将三价铬化学转化膜设置在锌或锌类合金镀层上。
本发明中，通过使具有三价铬化学转化膜、尤其是黑色三价铬化学转化膜的基体在水洗后或未经水洗即在该三价铬化学转化膜上与呈水溶液形态的本发明的整理剂组合物接触（优选浸渍在整理剂组合物中），使整理剂组合物附着，然后干燥、优选不经水洗即脱水干燥，能够在三价铬化学转化膜上形成整理层。
接触温度（优选为浸渍温度）优选10～80℃，更优选为45～55℃。
接触时间（优选为浸渍时间）优选为3～30秒，更优选为3～5秒。
干燥温度优选为50℃～200℃，更优选为80℃～120℃。
干燥时间优选为5分钟～60分钟，更优选为10分钟～20分钟。
通过该整理处理，能够在三价铬化学转化膜上设置整理层，该整理层含有三价铬、锌及磷元素，例如在三价铬、锌及磷元素的总计为100重量份时，三价铬为10～40重量份，锌为20～75重量份，磷为3～40重量份。三价铬/锌/磷的最佳重量比为（20～25）/（60～50）/（20～25）。这里，优选整理层中的三价铬、锌及磷元素的总计为30～75重量%。
此外，整理层的厚度可以为任意的，但优选0.05～0.3μm左右。
此外，根据赋予润滑性等目的的不同，在本发明的三价铬化学转化膜上还可以进一步实施外涂层处理。外涂层除可以为硅酸盐、磷酸盐等无机膜以外，聚乙烯、聚氯乙烯、聚苯乙烯、聚丙烯、甲基丙烯酸树脂、聚碳酸酯、聚酰胺、聚缩醛、含氟树脂、尿素树脂、苯酚树脂、不饱和聚酯树脂、聚氨酯、醇酸树脂、环氧树脂、三聚氰胺树脂等有机膜或硅油、蜡、防锈油等也是有效的。
本发明中，提供一种金属物品，其具有金属基体和无六价铬的耐腐蚀性膜，所述无六价铬的耐腐蚀性膜包括设置在所述金属基体上的黑色三价铬化学转化膜和设置在所述黑色三价铬化学转化膜上的整理层。
该金属物品能够适合用作螺丝或螺栓等金属部件，或汽车用部件等金属制品。
下面通过实施例对本发明进行详细说明。
实施例
（实施例1）
使用日本迪普索尔制的NZ-87浴在M8螺栓上实施了厚度为8μm的锌酸盐镀锌，然后将其用黑色三价铬化学转化处理剂——日本迪普索尔（株）制的ZTB-447S123C3型（ZTB-447S1：50mL/L，ZTB-447S2：20mL/L及ZTB-447S3：7mL/L）处理（30℃下进行40秒），之后，在50℃下在表1所示的整理剂中浸渍5秒，离心脱水后，在120℃下干燥。
表1
表中，Cr3+使用磷酸铬。Zn2+使用氧化锌。异噻唑啉使用Chemicrea公司制的ZONEN-C。Si4+使用硅胶。Co2+使用碳酸钴（No.5、6、7和8）或硝酸钴（No.9）。Al3+使用磷酸铝。添加的金属离子的浓度为1g/L。pH用苛性钠（No.1、3、5、6、7和10）或氨水（No.2、4、8和9）进行调整。表面活性剂使用20g/L的醚类非离子表面活性剂“SEDORANFF200”（三洋化成株式会社制），有机硅塑料使用10ppm的东丽道康宁（株）制的L-720，丙烯酸树脂使用30g/L的日本触媒公司制AQUALICL系列DL。余量为水。
（实施例2）
在M8螺栓上实施了厚度为8μm的镀铁合金（Fe：0.5重量%），然后将其用黑色三价铬化学转化处理剂（日本迪普索尔（株）制的ZTB-447A（200mL/L）和ZTB-447K（8mL/L））处理（在50℃下进行60秒）后，在50℃下在表2所示的整理剂中浸渍5秒，离心脱水后，在120℃下干燥。
表2
表中，Cr3+使用磷酸铬。Zn2+使用氧化锌。异噻唑啉使用Chemicrea公司制的ZONEN-C。Co2+使用硝酸钴。添加的金属离子的浓度为1g/L。pH用苛性钠（No.1、2和4）或氨水（No.3）进行调整。表面活性剂使用20g/L的醚类非离子表面活性剂“SEDORANFF200”（三洋化成株式会社制）。余量为水。
（实施例3）
在M8螺栓上实施了厚度为8μm的镀锌镍合金（Ni：15重量%），然后将其用黑色三价铬化学转化处理剂——日本迪普索尔（株）制的IZB-256（IZB-256AY：150mL/L和IZB-256BY：50mL/L）处理（在25℃下进行45秒）后，在50℃下在表3所示的整理剂中浸渍5秒，离心脱水后，在120℃下干燥。
表3
表中，Cr3+使用磷酸铬。Zn2+使用氧化锌。异噻唑啉使用Chemicrea公司制的ZONEN-C。Co2+使用硝酸钴。添加的金属离子的浓度为1g/L。pH用苛性钠（No.1、2和4）或氨水（No.3）进行调整。表面活性剂使用20g/L的醚类非离子表面活性剂“SEDORANFF200”（三洋化成株式会社制）。余量为水。
比较例1
作为比较例，在M8螺栓上实施了与实施例1相同的厚度为8μm的镀锌，然后将其进行黑色六价铬酸盐处理（25℃下进行60秒）。
黑色六价铬酸盐使用日本迪普索尔（株）制的ZB-535A（200mL/L）和ZB-黑50B（10mL/L）。
（比较例2）
作为比较例，在M8螺栓上实施了8μm的镀锌，然后对其进行黑色三价铬酸盐处理后，用从实施例1的No.1～No.4的整理剂中除去了聚乙烯醇、防斑点剂及防霉成分后的、表4所述的整理剂进行整理处理。黑色三价铬化学转化处理使用日本迪普索尔（株）制的ZTB-447A（200mL/L）和ZTB-447K（8mL/L）（处理条件为50℃下进行60秒）。
表4
表中，Cr3+使用磷酸铬。Zn2+使用氧化锌。Co2+使用碳酸钴。金属离子的浓度为1g/L。pH用苛性钠（No.1、2和4）或氨水（No.3）进行调整。表面活性剂使用20g/L的醚类非离子表面活性剂“SEDORANFF200”（三洋化成株式会社制）。余量为水。
将实施例1～3，以及比较例1和2中得到的化学转化处理膜处理后的外观、盐雾实验的结果以及室温放置一个月后的整理剂的发霉情况总结表示在表5中。
如表5所示，含有聚乙烯醇的实施例1的No.1及3～10的膜，与不含有聚乙烯醇的比较例2的No.1、3和4的膜相比，可得到伤痕少的光泽外观，耐腐蚀性也良好。实施例2及3的No.1～4也可得到伤痕及残液斑点少的光泽外观，耐腐蚀性也优异。
在室温放置一个月的整理剂的发霉情况如下：不含有防霉成分的比较例2的No.1～No.4全部都发霉，但含有防霉成分的实施例1的No.3～10、实施例2和3的No.2～4全部都没有发现发霉。
表5
（耐腐蚀性试验方法）
根据JISZ2371进行盐雾试验，以到产生白锈时为止的时间进行评价。
（发霉试验、评价方法）
将整理剂在室温下自然放置一个月，目测判断发霉情况（发霉、未发霉）。
（处理后的外观评价方法）
（擦伤试验、评价方法）
将70根进行了与实施例1～3及比较例1和2相同处理的M10×60mm的法兰螺栓从1m高空落下3次，目测判断擦伤情况（有擦伤、无擦伤）。
（斑点试验、评价方法）
在头部有凹陷的螺栓上实施至三价铬黑色化学转化处理后，在头部滴加整理液，形成液体残留，直接在80℃下干燥10分钟，目测判断斑点产生的情况（有斑点、无斑点）。
（光泽试验、评价方法）
以目测判断处理品的外观颜色和光泽，例如将有光泽的黑色判断为光泽黑。
Claims (13)
1.一种三价铬化学转化膜用整理剂，其特征在于，其含有三价铬源、磷酸离子源、锌离子源、能够与三价铬形成络合物的螯合剂，以及从由聚乙烯醇及其衍生物、聚乙烯吡咯烷酮及其衍生物、聚烷撑二醇及其衍生物和纤维素醚及其衍生物组成的组中选择的非离子性水溶性高分子化合物，并进一步含有从尿素、硫脲、二氧化硫脲及它们的衍生物中选择的防斑点剂，
所述三价铬源的浓度换算为铬浓度为0.1g/L～20g/L，所述磷酸离子源的浓度为0.3～70g/L，所述锌离子源的浓度换算为锌浓度为0.1g/L～30g/L，所述螯合剂的浓度为0.5～100g/L，所述非离子性水溶性高分子化合物的浓度为0.01g/L～50g/L，所述防斑点剂浓度为0.01g/L～30g/L，所述非离子性水溶性高分子化合物与所述防斑点剂的合计浓度为0.01g/L～50g/L。
2.如权利要求1所述的三价铬化学转化膜用整理剂，其特征在于，所述聚乙烯醇及其衍生物为聚乙烯醇或磺酸改性聚乙烯醇。
3.如权利要求1所述的三价铬化学转化膜用整理剂，其特征在于，还含有防霉成分。
4.如权利要求1所述的整理剂组合物，其特征在于，所述磷酸离子源为磷的含氧酸或其盐。
5.如权利要求1所述的三价铬化学转化膜用整理剂，其特征在于，所述三价铬源与所述磷酸离子源为磷酸铬。
6.如权利要求1所述的三价铬化学转化膜用整理剂，其特征在于，所述螯合剂为从由单羧酸、二羧酸、三羧酸及它们的盐组成的组中选择的。
7.如权利要求6所述的三价铬化学转化膜用整理剂，其特征在于，所述螯合剂为从由草酸、丙二酸、柠檬酸、酒石酸及苹果酸组成的组中选择的。
8.如权利要求3所述的三价铬化学转化膜用整理剂，其特征在于，防霉抑制成分为异噻唑啉类化合物。
9.如权利要求1所述的三价铬化学转化膜用整理剂，其特征在于，还含有从由铝、硅、钼、锰及钴组成的组中选择的金属离子。
10.如权利要求1所述的三价铬化学转化膜用整理剂，其特征在于，还含有表面活性剂。
11.如权利要求1-10中任意一项所述的三价铬化学转化膜用整理剂，其特征在于，不含有卤离子、硫酸离子及磺酸离子。
12.一种黑色三价铬化学转化膜的整理方法，其特征在于，对具有黑色三价铬化学转化膜的基体，使呈水溶液形态的权利要求1所述的三价铬化学转化膜用整理剂附着在该黑色三价铬化学转化膜上，然后进行干燥。
13.如权利要求12所述的方法，其特征在于，在10～80℃下使整理剂附着在黑色三价铬化学转化膜上。
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011081758 | 2011-04-01 | ||
| JP2011-081758 | 2011-04-01 | ||
| PCT/JP2012/058561 WO2012137680A1 (ja) | 2011-04-01 | 2012-03-30 | ３価クロム化成皮膜用仕上げ剤及び黒色３価クロム化成皮膜の仕上げ方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103459666A CN103459666A (zh) | 2013-12-18 |
| CN103459666B true CN103459666B (zh) | 2015-11-25 |
Family
ID=46969081
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201280016325.8A Active CN103459666B (zh) | 2011-04-01 | 2012-03-30 | 三价铬化学转化膜用整理剂及黑色三价铬化学转化膜的整理方法 |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US9567453B2 (zh) |
| EP (1) | EP2695970B1 (zh) |
| JP (1) | JP6024053B2 (zh) |
| KR (1) | KR101589355B1 (zh) |
| CN (1) | CN103459666B (zh) |
| IN (1) | IN2013MN01714A (zh) |
| MX (1) | MX358841B (zh) |
| MY (1) | MY168161A (zh) |
| PH (1) | PH12013502030A1 (zh) |
| TW (1) | TWI555880B (zh) |
| WO (1) | WO2012137680A1 (zh) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5877423B2 (ja) * | 2012-05-10 | 2016-03-08 | ディップソール株式会社 | 亜鉛系めっき金属部材表面の硝酸活性処理溶液の再生方法及びそれを用いた再生処理装置 |
| EP2711444A1 (en) * | 2012-09-20 | 2014-03-26 | Coventya SAS | Alkaline aqueous solution for improving corrosion resistance of a Cr(III) conversion coating and method for producing such coating and its use |
| JP6074042B2 (ja) * | 2013-08-28 | 2017-02-01 | ディップソール株式会社 | ３価クロム化成皮膜又はクロムフリー化成皮膜のトップコート剤用摩擦調整剤及びそれを含むトップコート剤 |
| DE202013010956U1 (de) * | 2013-09-13 | 2014-12-17 | Ewh Industrieanlagen Gmbh & Co. Kg | Behandlungslösung für ein Verfahren zum Erzeugen einer korrosionsschützenden Überzugsschicht und Konzentrat einer solchen Behandlungslösung |
| JP6532003B2 (ja) * | 2015-01-16 | 2019-06-19 | 日本表面化学株式会社 | 三価クロム黒色化成皮膜処理液、三価クロム含有水溶性仕上げ処理液及び金属基材の処理方法 |
| JP2017110246A (ja) * | 2015-12-15 | 2017-06-22 | 古河電気工業株式会社 | 銅管 |
| CN106424701B (zh) * | 2016-08-31 | 2019-06-04 | 中国东方电气集团有限公司 | 一种改性金属粉的制备方法 |
| KR101786392B1 (ko) | 2016-10-10 | 2017-10-17 | 주식회사 포스코 | 3가 크롬 및 무기화합물을 함유한 표면처리 용액조성물, 이를 이용하여 표면 처리된 아연계 도금강판 및 그 제조방법 |
| EP3569734A1 (en) | 2018-05-18 | 2019-11-20 | Henkel AG & Co. KGaA | Passivation composition based on trivalent chromium |
| EP3771748A1 (de) | 2019-07-30 | 2021-02-03 | Dr.Ing. Max Schlötter GmbH & Co. KG | Chrom(vi)- und kobalt-freie schwarzpassivierung für zink-nickel-oberflächen |
| CN112030170A (zh) * | 2020-07-27 | 2020-12-04 | 西安金诺表面精饰有限公司 | 一种镀镍件黄膜处理方法 |
| EP3964609A1 (en) | 2020-08-28 | 2022-03-09 | Coventya SAS | Electroplated product and method for preparing such products with a high temperature treatment |
| CN112226795B (zh) * | 2020-10-09 | 2024-05-03 | 宁波晶美科技有限公司 | 一种汽车门把手的制造方法 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100335575C (zh) * | 2003-07-22 | 2007-09-05 | 株式会社放电精密加工研究所 | 金属用的无铬水稀释性防锈漆 |
Family Cites Families (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1532230A (en) * | 1975-11-24 | 1978-11-15 | Imasa Ltd | Treatment of chromated metal surfaces with sulphur-compounds |
| US5009962A (en) * | 1989-01-04 | 1991-04-23 | Nippon Paint Co., Ltd. | Surface treatment chemical and bath for forming hydrophilic coatings and method of surface-treating aluminum members |
| US5350791A (en) * | 1992-07-02 | 1994-09-27 | Henkel Corporation | Hydrophilicizing treatment for metal objects |
| US5415702A (en) | 1993-09-02 | 1995-05-16 | Mcgean-Rohco, Inc. | Black chromium-containing conversion coatings on zinc-nickel and zinc-iron alloys |
| JP2001009362A (ja) * | 1999-06-29 | 2001-01-16 | Nippon Light Metal Co Ltd | 親水性表面処理組成物及び親水性表面処理皮膜 |
| US6736908B2 (en) * | 1999-12-27 | 2004-05-18 | Henkel Kommanditgesellschaft Auf Aktien | Composition and process for treating metal surfaces and resulting article |
| JP3332373B1 (ja) | 2001-11-30 | 2002-10-07 | ディップソール株式会社 | 亜鉛及び亜鉛合金めっき上に六価クロムフリー防錆皮膜を形成するための処理溶液、六価クロムフリー防錆皮膜及びその形成方法。 |
| JP3332374B1 (ja) | 2001-11-30 | 2002-10-07 | ディップソール株式会社 | 亜鉛及び亜鉛合金めっき上に六価クロムフリー防錆皮膜を形成するための処理溶液、六価クロムフリー防錆皮膜及びその形成方法。 |
| JP3774415B2 (ja) | 2002-03-14 | 2006-05-17 | ディップソール株式会社 | 亜鉛及び亜鉛合金めっき上に黒色の六価クロムフリー化成皮膜を形成するための処理溶液及び亜鉛及び亜鉛合金めっき上に黒色の六価クロムフリー化成皮膜を形成する方法。 |
| JP2004093784A (ja) * | 2002-08-30 | 2004-03-25 | Toppan Forms Co Ltd | 抗菌剤含有電子写真方式用トナー |
| JP4625244B2 (ja) | 2003-07-02 | 2011-02-02 | ディップソール株式会社 | ３価クロメート皮膜用仕上げ剤組成物及び３価クロメート皮膜の仕上方法 |
| JP2007268387A (ja) * | 2006-03-30 | 2007-10-18 | Kobe Steel Ltd | 熱交換器用表面処理フィン材 |
| ES2444406T3 (es) * | 2007-06-14 | 2014-02-24 | Atotech Deutschland Gmbh | Tratamiento anti-corrosión para capas de conversión |
| US8591670B2 (en) * | 2008-05-07 | 2013-11-26 | Bulk Chemicals, Inc. | Process and composition for treating metal surfaces using trivalent chromium compounds |
| CN102046843A (zh) * | 2008-05-27 | 2011-05-04 | 油研工业股份有限公司 | 表面剂及具有由表面剂形成的外涂层的部件 |
| EP2281923A1 (de) * | 2009-07-03 | 2011-02-09 | ATOTECH Deutschland GmbH | Korrosionsschutzbehandlung für Oberflächen aus Zink und Zinklegierungen |
-
2012
- 2012-03-23 TW TW101110061A patent/TWI555880B/zh active
- 2012-03-30 MX MX2013010913A patent/MX358841B/es active IP Right Grant
- 2012-03-30 KR KR1020137024048A patent/KR101589355B1/ko active IP Right Grant
- 2012-03-30 EP EP12767336.6A patent/EP2695970B1/en active Active
- 2012-03-30 WO PCT/JP2012/058561 patent/WO2012137680A1/ja active Application Filing
- 2012-03-30 MY MYPI2013003464A patent/MY168161A/en unknown
- 2012-03-30 JP JP2013508839A patent/JP6024053B2/ja active Active
- 2012-03-30 IN IN1714MUN2013 patent/IN2013MN01714A/en unknown
- 2012-03-30 CN CN201280016325.8A patent/CN103459666B/zh active Active
- 2012-03-30 US US14/008,362 patent/US9567453B2/en active Active
-
2013
- 2013-09-30 PH PH1/2013/502030A patent/PH12013502030A1/en unknown
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100335575C (zh) * | 2003-07-22 | 2007-09-05 | 株式会社放电精密加工研究所 | 金属用的无铬水稀释性防锈漆 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103459666A (zh) | 2013-12-18 |
| JP6024053B2 (ja) | 2016-11-09 |
| MX2013010913A (es) | 2013-10-07 |
| TW201250057A (en) | 2012-12-16 |
| MY168161A (en) | 2018-10-11 |
| US20140017514A1 (en) | 2014-01-16 |
| PH12013502030B1 (en) | 2013-12-16 |
| PH12013502030A1 (en) | 2013-12-16 |
| IN2013MN01714A (zh) | 2015-06-12 |
| MX358841B (es) | 2018-09-05 |
| US9567453B2 (en) | 2017-02-14 |
| KR20130124380A (ko) | 2013-11-13 |
| TWI555880B (zh) | 2016-11-01 |
| EP2695970A1 (en) | 2014-02-12 |
| JPWO2012137680A1 (ja) | 2014-07-28 |
| EP2695970B1 (en) | 2020-03-04 |
| WO2012137680A1 (ja) | 2012-10-11 |
| KR101589355B1 (ko) | 2016-02-12 |
| EP2695970A4 (en) | 2014-12-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103459666B (zh) | 三价铬化学转化膜用整理剂及黑色三价铬化学转化膜的整理方法 | |
| KR101212335B1 (ko) | 아연 또는 아연 합금 도금에 내식성 피막을 형성시키기 위한 표면 처리 수용액 및 처리 방법 | |
| ES2912177T3 (es) | Hojalata con tratamiento de superficie libre de cromo, método de producción y agente de tratamiento de superficie para la misma | |
| JPS6352114B2 (zh) | ||
| JP4625244B2 (ja) | ３価クロメート皮膜用仕上げ剤組成物及び３価クロメート皮膜の仕上方法 | |
| CN101545125A (zh) | 一种光亮耐蚀锌铁合金电镀工艺 | |
| AU2012254470A1 (en) | Chemical conversion treatment agent for surface treatment of metal substrate, and surface treatment method of metal substrate using same | |
| US9206321B2 (en) | Trivalent chromium-conversion processing solution containing aluminum-modified colloidal silica | |
| WO1991011542A2 (en) | Surface treatment method and composition for zinc coated steel sheet | |
| TWI545232B (zh) | 鋅－鐵合金層材料 | |
| US5318640A (en) | Surface treatment method and composition for zinc coated steel sheet | |
| US9435047B2 (en) | Process for corrosion protection of iron containing materials | |
| JP4226063B1 (ja) | 溶融亜鉛めっき処理品の生産方法 | |
| JP2717406B2 (ja) | 亜鉛合金メッキの黒色化方法 | |
| KR20050068072A (ko) | 박막수지피복 하지용 실란올 용액 처리 강판 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |