EP2759621A1 - Reactive-type chemical conversion treatment composition and production method of member with chemical conversion coated surface - Google Patents
Reactive-type chemical conversion treatment composition and production method of member with chemical conversion coated surface Download PDFInfo
- Publication number
- EP2759621A1 EP2759621A1 EP14152315.9A EP14152315A EP2759621A1 EP 2759621 A1 EP2759621 A1 EP 2759621A1 EP 14152315 A EP14152315 A EP 14152315A EP 2759621 A1 EP2759621 A1 EP 2759621A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- chemical conversion
- water
- mol
- soluble
- containing substance
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000126 substance Substances 0.000 title claims abstract description 316
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 161
- 239000000203 mixture Substances 0.000 title claims abstract description 69
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- -1 carboxylic acid compound Chemical class 0.000 claims abstract description 87
- 239000011651 chromium Substances 0.000 claims abstract description 62
- 238000007739 conversion coating Methods 0.000 claims abstract description 60
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 45
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 43
- 230000002378 acidificating effect Effects 0.000 claims abstract description 39
- 239000010936 titanium Substances 0.000 claims abstract description 38
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 25
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 17
- 239000010941 cobalt Substances 0.000 claims abstract description 17
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 17
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Natural products OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 82
- 229910052751 metal Inorganic materials 0.000 claims description 78
- 239000002184 metal Substances 0.000 claims description 78
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Natural products OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 66
- 239000000463 material Substances 0.000 claims description 50
- 239000011701 zinc Substances 0.000 claims description 49
- 229910052725 zinc Inorganic materials 0.000 claims description 48
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 46
- 235000006408 oxalic acid Nutrition 0.000 claims description 35
- 150000001875 compounds Chemical class 0.000 claims description 22
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 16
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- 239000007788 liquid Substances 0.000 abstract description 126
- 238000005260 corrosion Methods 0.000 abstract description 20
- 230000007797 corrosion Effects 0.000 abstract description 20
- 230000007613 environmental effect Effects 0.000 abstract description 6
- 238000012360 testing method Methods 0.000 description 48
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 25
- 235000015165 citric acid Nutrition 0.000 description 24
- 239000000654 additive Substances 0.000 description 21
- 230000000996 additive effect Effects 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 18
- 238000007747 plating Methods 0.000 description 18
- 150000003839 salts Chemical class 0.000 description 18
- 238000001035 drying Methods 0.000 description 11
- 150000002736 metal compounds Chemical class 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 230000007935 neutral effect Effects 0.000 description 7
- 239000007921 spray Substances 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 6
- 150000003609 titanium compounds Chemical class 0.000 description 6
- 239000002699 waste material Substances 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 230000002542 deteriorative effect Effects 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 150000007522 mineralic acids Chemical class 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 230000000007 visual effect Effects 0.000 description 5
- 150000003752 zinc compounds Chemical class 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 150000001845 chromium compounds Chemical class 0.000 description 4
- 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 4
- 238000004090 dissolution Methods 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000006748 scratching Methods 0.000 description 4
- 230000002393 scratching effect Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 3
- 229910001297 Zn alloy Inorganic materials 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000009713 electroplating Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000004310 lactic acid Substances 0.000 description 3
- 235000014655 lactic acid Nutrition 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- NMGYKLMMQCTUGI-UHFFFAOYSA-J diazanium;titanium(4+);hexafluoride Chemical compound [NH4+].[NH4+].[F-].[F-].[F-].[F-].[F-].[F-].[Ti+4] NMGYKLMMQCTUGI-UHFFFAOYSA-J 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000001630 malic acid Substances 0.000 description 2
- 235000011090 malic acid Nutrition 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- QVLTXCYWHPZMCA-UHFFFAOYSA-N po4-po4 Chemical compound OP(O)(O)=O.OP(O)(O)=O QVLTXCYWHPZMCA-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 231100000615 substance of very high concern Toxicity 0.000 description 2
- 235000010215 titanium dioxide Nutrition 0.000 description 2
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 description 2
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 2
- KQTIIICEAUMSDG-UHFFFAOYSA-N tricarballylic acid Chemical compound OC(=O)CC(C(O)=O)CC(O)=O KQTIIICEAUMSDG-UHFFFAOYSA-N 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 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
- 239000011787 zinc oxide Substances 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- 239000001124 (E)-prop-1-ene-1,2,3-tricarboxylic acid Substances 0.000 description 1
- 229910019985 (NH4)2TiF6 Inorganic materials 0.000 description 1
- RYSXWUYLAWPLES-MTOQALJVSA-N (Z)-4-hydroxypent-3-en-2-one titanium Chemical compound [Ti].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O RYSXWUYLAWPLES-MTOQALJVSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- HNUKTDKISXPDPA-UHFFFAOYSA-N 2-oxopropyl Chemical compound [CH2]C(C)=O HNUKTDKISXPDPA-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- IBPROSHOIXGDCD-UHFFFAOYSA-N C=C.C=C.[Na].[Na].[Na].[Na].[Na].[Na].[Na] Chemical group C=C.C=C.[Na].[Na].[Na].[Na].[Na].[Na].[Na] IBPROSHOIXGDCD-UHFFFAOYSA-N 0.000 description 1
- BKCSLWVTTCJBRE-UHFFFAOYSA-N CC(C)=O.CC(C)=O.CC(C)O[Ti]OC(C)C Chemical compound CC(C)=O.CC(C)=O.CC(C)O[Ti]OC(C)C BKCSLWVTTCJBRE-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- ODBLHEXUDAPZAU-ZAFYKAAXSA-N D-threo-isocitric acid Chemical compound OC(=O)[C@H](O)[C@@H](C(O)=O)CC(O)=O ODBLHEXUDAPZAU-ZAFYKAAXSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- 229910003708 H2TiF6 Inorganic materials 0.000 description 1
- ODBLHEXUDAPZAU-FONMRSAGSA-N Isocitric acid Natural products OC(=O)[C@@H](O)[C@H](C(O)=O)CC(O)=O ODBLHEXUDAPZAU-FONMRSAGSA-N 0.000 description 1
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- TTZMPOZCBFTTPR-UHFFFAOYSA-N O=P1OCO1 Chemical compound O=P1OCO1 TTZMPOZCBFTTPR-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 229910010298 TiOSO4 Inorganic materials 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 229940091181 aconitic acid Drugs 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 235000004279 alanine Nutrition 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003788 bath preparation Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 description 1
- 229940005991 chloric acid Drugs 0.000 description 1
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 1
- 229940077239 chlorous acid Drugs 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 150000001844 chromium Chemical class 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
- 229910000151 chromium(III) phosphate Inorganic materials 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
- IKZBVTPSNGOVRJ-UHFFFAOYSA-K chromium(iii) phosphate Chemical compound [Cr+3].[O-]P([O-])([O-])=O IKZBVTPSNGOVRJ-UHFFFAOYSA-K 0.000 description 1
- GTZCVFVGUGFEME-IWQZZHSRSA-N cis-aconitic acid Chemical compound OC(=O)C\C(C(O)=O)=C\C(O)=O GTZCVFVGUGFEME-IWQZZHSRSA-N 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
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 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
- 238000004040 coloring Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 238000013461 design 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
- 150000002009 diols Chemical class 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 description 1
- AMGXTMFXWTXVHS-UHFFFAOYSA-J dodecanoate titanium(4+) Chemical compound [Ti+4].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O AMGXTMFXWTXVHS-UHFFFAOYSA-J 0.000 description 1
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- YOYLLRBMGQRFTN-SMCOLXIQSA-N norbuprenorphine Chemical compound C([C@@H](NCC1)[C@]23CC[C@]4([C@H](C3)C(C)(O)C(C)(C)C)OC)C3=CC=C(O)C5=C3[C@@]21[C@H]4O5 YOYLLRBMGQRFTN-SMCOLXIQSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 150000002913 oxalic acids Chemical class 0.000 description 1
- KADRTWZQWGIUGO-UHFFFAOYSA-L oxotitanium(2+);sulfate Chemical compound [Ti+2]=O.[O-]S([O-])(=O)=O KADRTWZQWGIUGO-UHFFFAOYSA-L 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- QPTMDBQLCWRDCK-UHFFFAOYSA-I pentasodium;[2-[bis[[hydroxy(oxido)phosphoryl]methyl]amino]ethyl-(phosphonatomethyl)amino]methyl-hydroxyphosphinate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].OP([O-])(=O)CN(CP(O)([O-])=O)CCN(CP(O)([O-])=O)CP([O-])([O-])=O QPTMDBQLCWRDCK-UHFFFAOYSA-I 0.000 description 1
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000001508 potassium citrate Substances 0.000 description 1
- 229960002635 potassium citrate Drugs 0.000 description 1
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 description 1
- 235000011082 potassium citrates Nutrition 0.000 description 1
- FQLQNUZHYYPPBT-UHFFFAOYSA-N potassium;azane Chemical compound N.[K+] FQLQNUZHYYPPBT-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 229960001790 sodium citrate Drugs 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 description 1
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 description 1
- 229940039790 sodium oxalate Drugs 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- KWXLCDNSEHTOCB-UHFFFAOYSA-J tetrasodium;1,1-diphosphonatoethanol Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P(=O)([O-])C(O)(C)P([O-])([O-])=O KWXLCDNSEHTOCB-UHFFFAOYSA-J 0.000 description 1
- ODBLHEXUDAPZAU-UHFFFAOYSA-N threo-D-isocitric acid Natural products OC(=O)C(O)C(C(O)=O)CC(O)=O ODBLHEXUDAPZAU-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- XROWMBWRMNHXMF-UHFFFAOYSA-J titanium tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[Ti+4] XROWMBWRMNHXMF-UHFFFAOYSA-J 0.000 description 1
- SOBXOQKKUVQETK-UHFFFAOYSA-H titanium(3+);trisulfate Chemical compound [Ti+3].[Ti+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O SOBXOQKKUVQETK-UHFFFAOYSA-H 0.000 description 1
- HDUMBHAAKGUHAR-UHFFFAOYSA-J titanium(4+);disulfate Chemical compound [Ti+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O HDUMBHAAKGUHAR-UHFFFAOYSA-J 0.000 description 1
- NLPMQGKZYAYAFE-UHFFFAOYSA-K titanium(iii) fluoride Chemical compound F[Ti](F)F NLPMQGKZYAYAFE-UHFFFAOYSA-K 0.000 description 1
- GTZCVFVGUGFEME-UHFFFAOYSA-N trans-aconitic acid Natural products OC(=O)CC(C(O)=O)=CC(O)=O GTZCVFVGUGFEME-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 150000003627 tricarboxylic acid derivatives Chemical class 0.000 description 1
- SOBHUZYZLFQYFK-UHFFFAOYSA-K trisodium;hydroxy-[[phosphonatomethyl(phosphonomethyl)amino]methyl]phosphinate Chemical compound [Na+].[Na+].[Na+].OP(O)(=O)CN(CP(O)([O-])=O)CP([O-])([O-])=O SOBHUZYZLFQYFK-UHFFFAOYSA-K 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 150000003682 vanadium compounds Chemical class 0.000 description 1
- MCPTUMJSKDUTAQ-UHFFFAOYSA-N vanadium;hydrate Chemical compound O.[V] MCPTUMJSKDUTAQ-UHFFFAOYSA-N 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 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
- C23C22/46—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
-
- 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
- C23C22/48—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 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/53—Treatment of zinc or alloys based thereon
-
- 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
Definitions
- the present invention relates to a chemical conversion treatment composition which is substantially free from a water-soluble cobalt-containing substance and which is capable of forming a chemical conversion coating that has enhanced corrosion resistance with consideration for environmental conservation, and a production method of a member having a surface coated with the chemical conversion treatment composition.
- chromate coatings which are effective as chemical conversion coatings for anticorrosion of members having metal surfaces, such as zinc-plated members, have been formed through the use of a chemical conversion treatment liquid that contains trivalent chromium rather than the use of a composition for chemical conversion treatment using a chromate salt that contains hexavalent chromium (a composition for chemical conversion treatment is referred to as "chemical conversion treatment liquid", here and hereinafter).
- the chemical conversion coating obtained using a conventional hexavalent chromium-containing chemical conversion treatment liquid contains soluble hexavalent chromium in the coating. Therefore, such a coating is a subject of regulations according to the above directives.
- Cobalt as the metal for a water-soluble cobalt-containing substance is a kind of so-called rare metal, and involves a possibility that it will be difficult to stably be obtained at low cost.
- some of stably available ones among compounds that contain cobalt (cobalt chloride, cobalt carbonate, cobalt nitrate and cobalt sulfate) belong to SVHC (Substances of Very High Concern), so that many companies appear to restrict the use of such substances.
- a trivalent chromium-containing chemical conversion treatment liquid may be required to be substantially free from a water-soluble cobalt-containing substance.
- a metal-based component contained in the coating excessively dissolves out therefrom during the use, unless the possibility that the metal-based component negatively affects the environment is denied. Therefore, even though a chemical conversion coating has enhanced corrosion resistance, but if the enhanced corrosion resistance results from excessive dissolution of the metal-based component from the chemical conversion coating, then it may not be appropriate for the chemical conversion treatment liquid to contain a water-soluble metal-containing substance that gives the metal-based component, with consideration for the environment.
- an object of the present invention is to provide a chemical conversion treatment liquid which contains trivalent chromium, and which is substantially free from a water-soluble cobalt-containing substance and which is capable of forming a chemical conversion coating that has enhanced corrosion resistance with consideration for environmental conservation.
- Another object of the invention is to provide a production method of a member having a surface coated with the chemical conversion treatment liquid.
- a chemical conversion coating can be formed which has enhanced corrosion resistance and reduced dissolving amount of metal.
- a chemical conversion treatment liquid capable of forming a chemical conversion coating that has enhanced corrosion resistance with consideration for environmental conservation, without using any water-soluble cobalt-containing substance which has conventionally been in heavy usage for forming a chemical conversion coating that has enhanced corrosion resistance.
- a production method of a member having a surface coated with the chemical conversion treatment liquid is also provided.
- composition of an acidic composition for reactive chemical conversion treatment according to one embodiment of the present invention (also referred herein to as "chemical conversion treatment liquid).
- the chemical conversion treatment liquid according to one embodiment of the present invention contains at least one type of a water-soluble trivalent chromium-containing substance.
- the water-soluble trivalent chromium-containing substance may be selected from the group consisting of trivalent chromium (Cr 3+ ) and a water-soluble substance that contains trivalent chromium.
- water-soluble trivalent chromium compound capable of generating the water-soluble trivalent chromium-containing substance in water
- water-soluble trivalent chromium compound a water-soluble compound capable of generating the water-soluble trivalent chromium-containing substance in water
- the water-soluble trivalent chromium compound examples include trivalent chromium salt, such as chromium chloride, chromium sulfate, chromium nitrate, chromium phosphate and chromium acetate, and a compound obtained by reducing a hexavalent chromium compound, such as chromic acid and bichromate, to trivalent using a reductant.
- the water-soluble trivalent chromium compound may consist only of one type of compound, or may comprise plural types. It should be appreciated that the chemical conversion treatment liquid according to the present embodiment is substantially free from hexavalent chromium because any hexavalent chromium compound is not added actively as a raw material to the chemical conversion treatment liquid according to the present embodiment.
- Preferred content of the water-soluble trivalent chromium-containing substance in the chemical conversion treatment liquid according to the present embodiment is about 0.01 mol/L or more in terms of chromium with consideration for improving formability of the chemical conversion coating, more preferred content thereof is about 0.02 mol/L or more, or most preferred content thereof is about 0.04 mol/L or more.
- the upper limit of the content may preferably be, but not limited to, about 0.15 mol/L, more preferable be about 0.12 mol/L, or most preferably be about 0.1 mol/L in terms of chromium because unduly large content may possibly lead to problems, such as from the viewpoints of economic efficiency and waste liquid treatment.
- the chemical conversion treatment liquid according to the present embodiment contains at least one type of a water-soluble titanium-containing substance.
- the water-soluble titanium-containing substance may be selected from the group consisting of titanium ion (Ti 3+ , Ti 4+ ) and a water-soluble substance that contains titanium ion.
- water-soluble titanium compound capable of generating the water-soluble titanium-containing substance in water
- water-soluble titanium compound a substance to be compounded for containing the water-soluble titanium-containing substance in the chemical conversion treatment liquid, i.e., a raw material substance for the water-soluble titanium-containing substance.
- water-soluble titanium compound examples include carbonate, oxide, hydroxide, nitrate, sulfate, phosphate, fluoride, fluoro acid (salt), organic acid salt and organic complex compound of Ti.
- These may be in any form of anhydride or hydrate. It is
- Preferred content of the water-soluble titanium-containing substance in the chemical conversion treatment liquid according to the present embodiment is about 0.0001 mol/L or more in terms of titanium with consideration for improving formability of the chemical conversion coating, more preferred content thereof is about 0.0005 mol/L or more, or most preferred content thereof is about 0.001 mol/L or more.
- the upper limit of the content may preferably be, but not limited to, about 1 mol/L in terms of titanium, more preferably be about 0.5 mol/L or more, or most preferably be about 0.1 mol/L or more because unduly large content may increase the possibility of deteriorating the stability of the chemical conversion treatment liquid and also increase the possibility of problems, such as from the viewpoints of economic efficiency and waste liquid treatment.
- the chemical conversion treatment liquid according to the present embodiment contains a carboxylic acid compound.
- the "carboxylic acid compound” as used herein means a compound that comprises one or more types selected from the group consisting of a carboxylic acid, which is an organic acid having a carboxylic group, and ions, salts, derivatives and coordination compounds thereof, and is in a state of being dissolved in the chemical conversion treatment liquid as an aqueous composition.
- Examples of a carboxylic acid that gives the carboxylic acid compound according to the present invention include: monocarboxylic acid, such as formic acid, acetic acid and propionic acid; dicarboxylic acid, such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, phthalic acid and terephthalic acid; tricarboxylic acid, such as tricarballylic acid and aconitic acid; hydroxy carboxylic acid, such as glycolic acid, lactic acid, malic acid, tartaric acid, citric acid, isocitric acid and ascorbic acid; and aminocarboxylic acid, such as glycine and alanine.
- monocarboxylic acid such as formic acid, acetic acid and propionic acid
- dicarboxylic acid such as oxalic acid, malonic acid, succinic acid,
- the carboxylic acid compound according to the present embodiment may contain one or more types selected from the group consisting of a citric acid compound and an oxalic acid compound.
- the "citric acid compound” as used herein means a compound that comprises one or more types selected from the group consisting of a citric acid, and ions, salts, derivatives and coordination compounds thereof, and is in a state of being dissolved in the chemical conversion treatment liquid as an aqueous composition.
- oxalic acid compound as used herein means a compound that comprises one or more types selected from the group consisting of an oxalic acid, and ions, salts, derivatives and coordination compounds thereof, and is in a state of being dissolved in the chemical conversion treatment liquid as an aqueous composition.
- the carboxylic acid compound contained in the chemical conversion treatment liquid according to the present embodiment may contain either one or both of a citric acid compound and an oxalic acid compound.
- the carboxylic acid compound contained in the chemical conversion treatment liquid according to the present embodiment may contain at least one acid from a citric acid compound and an oxalic acid compound, or may preferably consist essentially of either one of them.
- the carboxylic acid compound contained in the chemical conversion treatment liquid according to the present embodiment may contain oxalic acid compound, or may preferably consist essentially of oxalic acid compound.
- the carboxylic acid compound contained in the chemical conversion treatment liquid according to the present embodiment may contain at least one from a citric acid compound and an oxalic acid compound, or may preferably consist essentially of either one of them.
- carboxylic acid source a water-soluble compound capable of generating the carboxylic acid compound in water
- carboxylic acid source a substance to be compounded for containing the carboxylic acid compound in the chemical conversion treatment liquid, i.e., a raw material substance for the carboxylic acid compound.
- carboxylic acid source include: carboxylic acid derivatives, such as carboxylic ester; carboxylic acid; and carboxylic salt (metal salt).
- carboxylic acid source may be carboxylic salt. Examples of such carboxylic salt include sodium oxalate, sodium citrate, potassium oxalate, and potassium citrate.
- Preferred content of the carboxylic acid compound in the chemical conversion treatment liquid according to the present embodiment is about 0.001 mol/L or more in terms of carboxylic acid with consideration for improving formability of the chemical conversion coating, more preferred content thereof is about 0.004 mol/L or more, or most preferred content thereof is about 0.008 mol/L or more.
- the upper limit of the content may preferably be, but not limited to, about 0.4 mol/L in terms of carboxylic acid, more preferably about 0.2 mol/L, or most preferably about 0.1 mol/L because unduly large content may increase the possibility of deteriorating the stability of the chemical conversion treatment liquid and also increase the possibility of problems, such as from the viewpoints of economic efficiency and waste liquid treatment.
- a ratio (first ratio) of the content of citric acid compound in terms of citric acid (unit: mol/L) of the chemical conversion treatment liquid according to the present embodiment (unit: mol/L) to the content of water-soluble trivalent chromium-containing substance in terms of chromium (unit: mol/L) may preferably be about 0.05 or more and about 0.8 or less, more preferably about 0.1 or more and about 0.6 or less, and most preferably about 0.2 or more and about 0.4 or less, from the viewpoint of easily forming a chemical conversion coating that has enhanced corrosion resistance.
- a ratio (second ratio) of the content of oxalic acid compound in terms of oxalic acid (unit: mol/L) to the content of the water-soluble trivalent chromium-containing substance in terms of chromium (unit: mol/L) may preferably be about 0.05 or more and about 2 or less, easily forming a chemical conversion coating that has enhanced corrosion resistance from the viewpoint of easily forming a chemical conversion coating that has enhanced corrosion resistance, may more preferably be about 0.1 or more and about 1.7 or less, or may most preferably be about 0.6 or more and about 1.7 or less.
- the chemical conversion treatment liquid according to the present embodiment may contain an organic acid compound other than the above carboxylic acid compound.
- an organic acid associated with such an organic acid compound include sulfonic acid.
- the content of such organic acid compounds in the chemical conversion treatment liquid according to the present embodiment may preferably be, but not limited to, within a range where the above carboxylic acid compound can function appropriately.
- the chemical conversion treatment liquid according to the present embodiment may contain an organic phosphonic acid compound.
- organic phosphonic acid examples include 1-hydroxyethylidene-1,1-diphosphonic acid, 2-phosphonobutane1,2,4-tricarboxylic acid, amino(trimethylene phosphonic acid), ethylenediamine tetra(methylene phosphonic acid), and diethylene triamine penta(methylene phosphonic acid).
- salts of the organic phosphonic acids include tetrasodium 1-hydroxyethylidene-1,1-diphosphonate, trisodium 1-hydroxyethylidene-1,1-diphosphonate, pentasodium ethylenediamine tetra(methylene phosphonate), and heptasodium diethylene triamine penta(methylene phosphonate). These salts may often be such that sodium ions are dissociated in the chemical conversion treatment liquid.
- the chemical conversion treatment liquid according to the present embodiment contains the organic phosphonic acid compound
- preferred content of the organic phosphonic acid compound is about 0.001 mol/L or more in terms of phosphorus in view of making it easy to form the chemical conversion coating having an excellent property
- more preferred content thereof is about 0.005 mol/L or more
- most preferred content thereof is about 0.01 mol/L or more.
- the upper limit of the content may preferably be, but not limited to, about 1 mol/L in terms of phosphorous, or may more preferably be about 0.1 mol/L because unduly large content may increase the possibility of deteriorating the appearance of obtained chemical conversion coating and also increase the possibility of problems, such as from the viewpoints of economic efficiency and waste liquid treatment. It may be possibly preferred that the chemical conversion treatment liquid according to the present embodiment is substantially free from the organic phosphonic acid compound.
- the chemical conversion treatment liquid according to the present embodiment may further contain at least one type of a water-soluble zinc-containing substance.
- the water-soluble zinc-containing substance may be selected from the group consisting of zinc ions (Zn 2+ ) and a water-soluble substance that contains zinc ions. If, when the chemical conversion treatment liquid according to the present embodiment contains the organic phosphonic acid compound, the water-soluble zinc-containing substance is further contained, then it may be able to enhance the quality stability of the chemical conversion coating formed using the chemical conversion treatment liquid.
- water-soluble zinc compound capable of generating the water-soluble zinc-containing substance in water
- water-soluble zinc compound a substance to be compounded for containing the water-soluble zinc-containing substance in the chemical conversion treatment liquid, i.e., a raw material substance for the water-soluble zinc-containing substance.
- water-soluble zinc compound examples include compounds, such as zinc chloride, zinc carbonate, zinc oxide, zinc borate, zinc acetate, zinc sulfate, and zinc nitrate.
- the water-soluble zinc compound may consist only of one type of compound, or may comprise plural types.
- the chemical conversion treatment liquid according to the present embodiment contains the water-soluble zinc-containing substance
- preferred content of the water-soluble zinc-containing substance is 0.005 mol/L or more in terms of zinc in view of making it easy to form the chemical conversion coating, more preferred content thereof is about 0.01 mol/L or more, or most preferable content thereof is about 0.015 mol/L or more.
- the upper limit of the content may preferably be, but not limited to, about 0.1 mol/L in terms of zinc, may more preferably be about 0.075 mol/L, or may most preferably be about 0.05 mol/L because unduly large content may increase the possibility of deteriorating the stability of the chemical conversion treatment liquid and also increase the possibility of problems, such as from the viewpoints of economic efficiency and waste liquid treatment.
- the chemical conversion treatment liquid according to the present embodiment may contain, in addition to the above substances, one or more types selected from the group consisting of a water-soluble metal-containing substance associated with a metal other than the above metals (Cr, Zn and Ti), an inorganic acid and anions thereof, an inorganic colloid, a silane coupling agent, and an organic phosphorous compound.
- the chemical conversion treatment liquid may further contain: polyphenol, such as pyrogallol and benzenediol; corrosion inhibitor; surfactant, such as diol, triol and amine; plastic dispersant; coloring material, such as dye, pigment, metal pigment generating agent and other pigment generating agents; desiccant; and dispersant.
- the chemical conversion treatment liquid according to the present embodiment is substantially free from a water-soluble substance including fluorine in view of decreasing environmental impact. Moreover, the chemical conversion treatment using the chemical conversion treatment liquid according to the present embodiment is reactive-type, so that substantially no film-forming organic component is contained therein.
- Examples of a metal element that is contained in the water-soluble metal-containing substance associated with a metal other than the above metals include Ni, Na, K, Ag, Fe, Ca, Mg, Sc, Mn, Cu, Sn, Mo, Al, and W, which may be present in a form of oxygen acid ion, such as tungstate ion, or in a form of coordination compound.
- a water-soluble metal-containing substance may be contained thereby to provide additional advantageous effects.
- the appearance of obtained chemical conversion coating may be improved, and/or the dependency of the coating properties, such as corrosion resistance and dissolving amount of metal, on the base material may be reduced (specific example of the dependency may be such that the coating properties are likely to vary if the type of bath used to form a zinc-based plating is different).
- the content of the water-soluble additive metal compound may not be particularly limited. It may be set in consideration of a role of the metal element contained in each water-soluble additive metal compound.
- the content may be about 0.0001 mol/L or more in terms of aluminum, may preferably be about 0.0005 mol/L or more, or may most preferably be about 0.001 mol/L or more.
- the upper limit of the content may preferably be, but not limited to, about 1 mol/L in terms of aluminum, may more preferably be about 0.5 mol/L, or may most preferably be about 0.1 mol/L because unduly large content may increase the possibility of deteriorating the stability of the chemical conversion treatment liquid and also increase the possibility of problems, such as from the viewpoints of economic efficiency and waste liquid treatment.
- the chemical conversion treatment liquid according to the present embodiment is substantially free from a water-soluble cobalt-containing substance which involves concerns about affecting the environment. Moreover, the chemical conversion treatment liquid according to the present embodiment is substantially free from a water-soluble vanadium-containing substance because the dissolving amount of V may be unduly large from a chemical conversion coating that contains V, in which case concern is that the dissolved V affects the environment.
- the inorganic acid examples include hydrohalic acid other than hydrofluoric acid such as hydrochloric acid and hydrobromic acid; chloric acid, perchloric acid, chlorous acid, hypochlorous acid, sulfuric acid, sulfurous acid, nitric acid, nitrous acid, phosphoric acid (orthophosphoric acid), polyphosphoric acid, metaphosphoric acid, pyrophosphoric acid, ultraphosphoric acid, hypophosphorous acid, and superphosphoric acid, among which, one or more of the inorganic acid selected from the group consisting of hydrohalic acid other than hydrofluoric acid, sulfuric acid, nitric acid, and phosphoric acid (orthophosphoric acid) may preferably be contained as anions.
- hydrohalic acid other than hydrofluoric acid such as hydrochloric acid and hydrobromic acid
- the concentration of these inorganic acids and/or inorganic acid ions in the chemical conversion treatment liquid is not particularly limited.
- the ratio of the total molar concentration of inorganic acids and inorganic acid ions to the total molar concentration in terms of metal of the water-soluble metal-containing substance may ordinarily be about 0.1 or more and about 10 or less, and preferably about 0.5 or more and about 3 or less.
- examples of the inorganic colloid include silica sol, alumina sol, titanium sol and zirconia sol, and examples of the silane coupling agent include vinyltriethoxysilane and ⁇ -methacryloxypropyltrimethoxysilane.
- the solvent of the chemical conversion treatment liquid according to the present embodiment contains water as the main component.
- An organic solvent such as alcohol, ether and ketone, which has a high solubility in water may be mixed with water as solvent except water.
- the ratio thereof may preferably be about 10 vol% or less to the whole solvent in view of the stability in the whole chemical conversion treatment liquid.
- the chemical conversion treatment liquid according to the present embodiment is caused to be acidic, and the pH is therefore less than 7.
- the preferable value of pH within the acidic range is not particularly limited.
- the pH may appropriately be set considering that unduly low pH increases the possibility that the formation of the chemical conversion coating will be non-uniform while unduly high pH increases the possibility that the stability of the chemical conversion treatment liquid will deteriorate.
- the pH may preferably be about 1 or more and about 5 or less, and more preferably about 1.5 or more and about 3 or less.
- concentrated liquid for chemical conversion treatment a liquid composition having a composition in which major components of the above chemical conversion treatment liquid are concentrated about 5 to about 20 times (referred hereinafter to as "concentrated liquid for chemical conversion treatment")
- concentration liquid for chemical conversion treatment a liquid composition having a composition in which major components of the above chemical conversion treatment liquid are concentrated about 5 to about 20 times
- bother of preparing individually the content of each component can be saved and storage thereof may be easy, thus being preferable.
- this concentrated liquid for chemical conversion treatment is prepared, upper limits may be provided for the contents of the above respective components with consideration for the solubility of each component.
- the material quality of a base material to be subjected to the chemical conversion treatment according to the present embodiment is not particularly limited so long as the base material has a metal surface on which the chemical conversion coating can be formed using the chemical conversion treatment liquid according to the present embodiment.
- Preferable material is a metal-based material, and in particular a steel plate formed thereon with zinc-based plating is most preferable.
- Method of plating may be electroplating or may also be hot-dip plating, and when hot-dip plating is employed, an alloying process by heat may be performed after the plating.
- the composition of the above zinc-based plating may be pure zinc or may also be zinc alloy.
- zinc alloy plating examples of metal to be alloyed include iron, nickel, and aluminum.
- Method of plating may be electroplating or may also be hot-dip plating.
- electroplating any of cyanide bath, chloride bath, sulfuric acid bath and zincate bath may be used, and a baking treatment may be performed after preparing the plated film.
- hot-dip plating an alloying process may be performed after the plating.
- the production method according to the present embodiment comprises: a contacting step that causes the chemical conversion treatment liquid according to the present embodiment to contact with a base material having a metal-based surface thereby forming a chemical conversion coating on the metal-based surface of the base material; and a washing step that washes the base material having been subjected to the contacting step to obtain a member having a surface provided thereon with the chemical conversion coating.
- method of causing the chemical conversion treatment liquid according to the present embodiment to contact with the base material having a metal-based surface is not particularly limited.
- the simplest method is immersing, but spraying may be employed, or application may also be possible using a roll, etc.
- the contacting condition (contacting temperature, contacting time) is not particularly limited, and may be set in consideration of the composition of the chemical conversion treatment liquid, the composition of a material that constitutes the base material surface, and the productivity, etc.
- the temperature of the chemical conversion treatment liquid ranges from room temperature (about 23 °C) to about 40°C
- the contacting time may typically be within a range of about 10 seconds to about 5 minutes.
- the chemical conversion treatment liquid according to the present embodiment is a reactive chemical conversion treatment liquid, and hence, even if the time duration is set to be unduly long, the thickness of the chemical conversion coating will not increase in general as time goes on.
- a base material to be subjected to the contacting step may be washed (e.g., degreasing and rinsing) using a known method, followed by an activation treatment designed such that the base material is contacted (at room temperature (about 23 °C) for about 10 seconds) with an acid aqueous solution (e.g., nitric acid aqueous solution of several ml/L).
- an acid aqueous solution e.g., nitric acid aqueous solution of several ml/L.
- the base material having been subjected to the contacting step is washed using water, for example.
- the washing step is a step to be performed due to the reason that the chemical conversion treatment liquid according to the present embodiment is a reactive chemical conversion treatment liquid.
- Such a step washes away the chemical conversion treatment liquid that remains on the surface of the base material having been subjected to the contacting step, and a member is thus obtained which comprises the base material and the chemical conversion coating formed on the surface of the base material.
- a drying step is conducted ordinarily for the purpose of removing the water adhering to the chemical conversion coating and the base material.
- the drying condition drying temperature, drying time
- the drying condition is not particularly limited.
- the drying condition may appropriately be set in consideration of heat resistance of the base material, productivity, and the like.
- Various cases for drying may be possible, such as a case where the member is stationarily placed for about 10 minutes in an oven maintained at a temperature of about 100°C or less, a case where a centrifuge separator is used for drying, and a case where the member is stationarily placed in ordinary environment.
- the drying may cause a change in the composition, such as a change of a part or whole of the hydroxide into oxide.
- the production method according to the present embodiment may comprise a finishing step that, after the above member has been treated using the chemical conversion treatment liquid according to the present embodiment to form the chemical conversion coating, performs treatment using a finishing agent for enhancing the corrosion resistance and scratch resistance to form a finishing coating.
- the relationship between the finishing step and the drying step is freely selected such that, after the washing step, the drying step may be performed after the finishing step has been completed, or the finishing step may be performed after the drying step has been completed.
- the metal-based surface of the base material being the surface to be treated may include a surface of the zinc-based plated film formed using a chloride bath, a surface of the plated film obtainable by forming a zinc-based plated film using a zincate bath and subjecting this to baking treatment, and a surface of the zinc-based plated film formed using a zincate bath without baking treatment.
- the carboxylic acid compound may include at least one from citric acid compound and oxalic acid compound, or may preferably consist essentially of citric acid compound or oxalic acid compound.
- the carboxylic acid compound may preferably include oxalic acid compound, or may more preferably consist essentially of oxalic acid compound.
- the use of the chemical conversion coating of the present embodiment includes contacting the acidic composition according to the present embodiment to a base material having metal-based surface to form the chemical conversion coating on the metal-based surface of the base material.
- the relation between the metal-based surface of the base material being the treatment surface and the carboxylic acid composition are the same in the production method of the member having the chemical conversion coating on its surface, therefore descriptions on the relation will be omitted.
- Chemical conversion treatment liquids were prepared to have a basic composition shown in Table 1 and respective detailed compositions shown in Table 2.
- the chemical conversion treatment liquid 1-25 was such that the compounding amount in terms of titanium of the water-soluble titanium compound was 0.001 mol/L, and the compounding amount in terms of aluminum of the water-soluble aluminum compound was 0.001 mol/L.
- [Table 1] Compounding component Content at bath preparation Chromium nitrate 42 mmol/L in terms of Cr Zinc chloride 15 mmol/L in terms of Zn Source of carboxylic acid, etc. 8 mmol/L in terms of carboxylic acid Organic phosphonic acid compound 0.01 mol/L in terms of P Water-soluble additive metal compound 0.001 mol/L in terms of metal
- the "source of carboxylic acid, etc.” collectively means a carboxylic acid source and a water-soluble compound that is able to generate an organic acid compound in water.
- the "water-soluble additive metal compound” means those other than the water-soluble trivalent chromium compound and the water-soluble zinc compound among water-soluble metal compounds to involve water-soluble metal-containing substance in the chemical conversion treatment liquid.
- the organic phosphonic acid compound was "DEQUEST 2010" available from Thermphos Japan Ltd. [Table 2] Chemical conversion treatment liquid Source of carboxylic acid, etc.
- additive metal in Table 2 means a metal that is associated with the water-soluble additive metal compound in Table 1.
- the type of water-soluble metal compound associated with each metal was as follows:
- Zinc plating treatment was performed under the condition below for base materials comprising steel M10 bolts, and each base material was thus obtained to have a zinc plated film on the surface:
- Rinsing was performed for the base materials after the zinc plating treatment by immersing the base materials in pure water of 23°C for 10 seconds while swinging them.
- Activation treatment was then performed for the base materials after the zinc plating treatment and rinsing, by immersing the base materials in diluted nitric acid aqueous solution (3 ml/L) of 23°C for 10 seconds while swinging them.
- Rinsing was performed again for the base materials put out from the diluted nitric acid aqueous solution by immersing the base materials in pure water of 23°C for 10 seconds while swinging them.
- Chemical conversion treatment was performed for each base material after the activation treatment and rinsing, by immersing the base material in either one of the above chemical conversion treatment liquids 1-1 to 1-25, maintained at 30°C, for 45 seconds while swinging the base material. Rinsing was then performed for the base material put out from the chemical conversion treatment liquid by immersing the base material in pure water of 23°C for 10 seconds while swinging the base material.
- the base material after the chemical conversion treatment and rinsing was dried by being stationarily placed for 10 minutes in an oven maintained at 80°C. A member having its surface formed thereon with the chemical conversion coating was thus obtained as each of test members 1-1 to 1-25.
- the neutral salt spray test in conformity with JIS Z2371: 2000 (ISO 9227: 1990) was conducted for 96 hours, followed by visual observation of the surface of each test member after the test to measure a white rust generating area, and the white rust area ratio (unit: %) was obtained by measuring the ratio of the white generating area to the area of the main surface of the test member.
- test member surface area: 25 cm 2
- test member was immersed in 100 ml of pure water for 24 hours.
- the test member was then put out therefrom, and the metal amount dissolved into water was measured using an ICP (SPS 5520 available from SII NanoTechnology Inc.) to obtain the dissolving amount (unit: ⁇ g/cm 2 ).
- the surface formed of the chemical conversion coating of each test member was visually observed, and the color tone was evaluated.
- Chemical conversion treatment liquids 2-1 to 2-13 were obtained with the compositions listed in Table 1 by excluding water-soluble additive metal compound and changing the content of citric acids as the source of carboxylic acid, etc. to have the ratio values listed in Table 3.
- This ratio also refers hereinafter to "CA1/Cr ratio", which is a ratio of the content of citric acid compound in terms of citric acid (unit: mol/L) to the content of water-soluble trivalent chromium-containing substance in terms of chromium (unit: mol/L).
- Chemical conversion treatment liquids 2-14 to 2-27 were obtained with the compositions listed in Table 1 by excluding water-soluble additive metal compound and changing the content of oxalic acids as the source of carboxylic acid, etc. to have the ratio values listed in Table 3.
- CA2/Cr ratio is a ratio of the content of oxalic acid compound in terms of oxalic acid (unit: mol/L) to the content of water-soluble trivalent chromium-containing substance in terms of chromium (unit: mol/L).
- Test members 2-1 to 2-27 corresponding to the chemical conversion treatment liquids 2-1 to 2-27 were obtained in the same manner in Example 1.
- test members 2-1 to 2-27 For the obtained test members 2-1 to 2-27, the neutral salt spray test in conformity with JIS Z2371: 2000 (ISO 9227: 1990) was conducted, followed by visual observation of the surface of each test member after the test of 48 hours, 72 hours, and 96 hours, to obtain the white rust area ratio (unit: %) at each timing.
- the white rust area ratio was confirmed to vary by changing the CA1/Cr ratio or CA2/Cr ratio as shown in Table 2.
- test members 3-1 to 3-15 were prepared by using the chemical conversion treatment liquids prepared in Example 1 and performing the same operations as those in Example 1.
- Test member Chemical conversion treatment liquid Source of carboxylic acid, etc.
- Additive metal White rust area ratio (%) Dissolving amount ( ⁇ g/cm 2 ) 72h 120h 168h 216h chromium
- Additive metal 3-1 1-1 Citric acid None 2 5 15 30 0.05 - 3-2 1-2 Co 0 1 3 5 0.04 0.02 3-3 1-4 Ti 0 1 2 5 0.03 0.08 3-4 1-5 V 0 1 1 3 0.03 0.34 3-5 1-6 Al 10 25 30 40 0.02 ⁇ 0.01 3-6 1-7
- An Auto-gilder was used, into which 1 kg of steel M10 bolts as dummies and each 1 kg of the test members 3-1 to 3-15 were put to be rotated for 2 minutes, thereby scratching each test member, and a state was obtained where metal dissolution was likely to occur.
- the neutral salt spray test in conformity with JIS Z2371: 2000 (ISO 9227: 1990) was conducted, followed by visual observation of the surface of each test member after the test of 72 hours, 120 hours, 168 hours, and 216 hours, to obtain the white rust area ratio (unit: %) at each timing.
- test member surface area: 25 cm 2
- test member was immersed in 100 ml of pure water for 24 hours.
- the test member was then put out therefrom, and the metal amount dissolved into water was measured using an ICP (SK-150 available from Shinkyoritsu Kako Co., Ltd.) to obtain the dissolving amount (unit: ⁇ g/cm 2 ).
- the test members 3-3, 3-8 and 3-13 obtained using the chemical conversion treatment liquids 1-4, 1-10 and 1-22 each containing the water-soluble titanium-containing substance had excellent corrosion resistance and metal dissolving amount comparable with or more than those of the test members (3-2, 3-7 and 3-12) obtained using the chemical conversion treatment liquids (1-2, 1-8 and 1-20) each containing the water-soluble cobalt-containing substance.
- the result upon the chemical conversion treatment liquids each containing the water-soluble metal-containing substance other than the water-soluble titanium-containing substance, the result was such that at least one of the corrosion resistance and metal dissolving amount of each obtained chemical conversion coating was far poorer than those of the test members obtained using the chemical conversion treatment liquids each containing the water-soluble cobalt-containing substance.
- Chemical conversion treatment liquid 4 was prepared by excluding the zinc oxide as the water-soluble zinc compound and the organic phosphonic acid compound from the chemical conversion treatment liquid 1-4 prepared in Example 1.
- Example 2 Two types of test members were produced by using these chemical conversion treatment liquid 4 and chemical conversion treatment liquid 1-4 and performing the same operations as those in Example 1.
- the same neutral salt spray test as that for Example 1 and the same neutral salt spray test after scratching as that for Example 3 were conducted, and each white rust area ratio (unit: %) was measured after the test of 72 hours and 120 hours.
- measurement of the dissolving amount of metal was performed like in Example 1.
- Table 5 Chemical conversion treatment liquid White rust area ratio (%) Dissolving amount ( ⁇ g/cm 2 ) Without scratching With scratching 72h 120h 72h 120h Chromium Additive metal 4 0 3 1 5 0.07 0.08 1-4 0 1 1 4 0.03 0.08
- Chemical conversion treatment liquids 5-1 to 5-8 were obtained with the compositions listed in Table 1 by adding 0.001 mol/L of water-soluble titanium compound in terms of titanium as the water-soluble additive metal compound and changing the content of citric acid or oxalic acid to have respective CA1/Cr ratio or CA2/Cr ratio values listed in Table 6.
- Test members 5-1 to 5-8 corresponding to the chemical conversion treatment liquids 5-1 to 5-8 were obtained in the same manner in Example 1.
- Example 1 The surface of each of obtained test members 5-1 to 5-8 was visually observed, then the gloss and the uniformity in appearance were evaluated in accordance with the criteria in Example 1 (A to D).
- the neutral salt spray test in conformity with JIS Z2371: 2000 (ISO 9227: 1990) was conducted, followed by visual observation of the surface of each test member after the test of 48 hours, 72 hours, and 96 hours, to obtain the white rust area ratio (unit: %) at each timing.
- Chemical conversion treatment liquids 6-1 to 6-10 were obtained with the compositions listed in Table 1 except using, as water-soluble additive metal compound, two kinds of water-soluble additive metals from water-soluble titanium compound, water-soluble aluminum compound, water-soluble vanadium compound, and water-soluble nickel compound as listed in Table 7.
- the content of the water-soluble additive metal was 0.001 mol/L in terms of metal in each compound and the content of citric acid or oxalic acid was adjusted to have respective CA1/Cr ratio or CA2/Cr ratio values listed in Table 7.
- Test members 6-1 to 6-10 corresponding to the chemical conversion treatment liquids 6-1 to 6-10 were obtained in the same manner in Example 1.
- Example 1 The surface of each of obtained test members 6-1 to 6-10 was visually observed, then the gloss and the uniformity in appearance were evaluated in accordance with the criteria in Example 1 (A to D).
- the neutral salt spray test in conformity with JIS Z2371: 2000 (ISO 9227: 1990) was conducted, followed by visual observation of the surface of each test member after the test of 48 hours, 72 hours, and 96 hours, to obtain the white rust area ratio (unit: %) at each timing.
- Table 7 Chemical conversion treatment liquid Source of Carboxylic acid, etc.
Abstract
Description
- The present invention relates to a chemical conversion treatment composition which is substantially free from a water-soluble cobalt-containing substance and which is capable of forming a chemical conversion coating that has enhanced corrosion resistance with consideration for environmental conservation, and a production method of a member having a surface coated with the chemical conversion treatment composition.
- In recent years, according to directives with consideration for environment, such as RoHS (Restriction of the Use of Certain Hazardous Substances in Electrical and Electronic Equipment) directive and ELV (End of Life Vehicles) directive, it has been required to regulate the use of harmful substances (such as lead, mercury, cadmium, and hexavalent chromium).
- To this end, chromate coatings, which are effective as chemical conversion coatings for anticorrosion of members having metal surfaces, such as zinc-plated members, have been formed through the use of a chemical conversion treatment liquid that contains trivalent chromium rather than the use of a composition for chemical conversion treatment using a chromate salt that contains hexavalent chromium (a composition for chemical conversion treatment is referred to as "chemical conversion treatment liquid", here and hereinafter). The chemical conversion coating obtained using a conventional hexavalent chromium-containing chemical conversion treatment liquid contains soluble hexavalent chromium in the coating. Therefore, such a coating is a subject of regulations according to the above directives.
- To enhance the corrosion resistance, there has been a case where a water-soluble cobalt-containing substance is contained in a chemical conversion treatment liquid that contains trivalent chromium (e.g., Patent Literature 1).
- [Patent Literature 1]
JP2010-196174A - Cobalt as the metal for a water-soluble cobalt-containing substance is a kind of so-called rare metal, and involves a possibility that it will be difficult to stably be obtained at low cost. In addition, some of stably available ones among compounds that contain cobalt (cobalt chloride, cobalt carbonate, cobalt nitrate and cobalt sulfate) belong to SVHC (Substances of Very High Concern), so that many companies appear to restrict the use of such substances. In this regard, a trivalent chromium-containing chemical conversion treatment liquid may be required to be substantially free from a water-soluble cobalt-containing substance.
- In addition, with regard to a chemical conversion coating formed using a chemical conversion treatment liquid, it may not be preferable that a metal-based component contained in the coating excessively dissolves out therefrom during the use, unless the possibility that the metal-based component negatively affects the environment is denied. Therefore, even though a chemical conversion coating has enhanced corrosion resistance, but if the enhanced corrosion resistance results from excessive dissolution of the metal-based component from the chemical conversion coating, then it may not be appropriate for the chemical conversion treatment liquid to contain a water-soluble metal-containing substance that gives the metal-based component, with consideration for the environment.
- In view of such circumstances, an object of the present invention is to provide a chemical conversion treatment liquid which contains trivalent chromium, and which is substantially free from a water-soluble cobalt-containing substance and which is capable of forming a chemical conversion coating that has enhanced corrosion resistance with consideration for environmental conservation. Another object of the invention is to provide a production method of a member having a surface coated with the chemical conversion treatment liquid.
- As a result of studies for solving the above problems, the present inventors have found the followings. That is, in a chemical conversion treatment liquid that contains trivalent chromium, by containing a water-soluble titanium-containing substance as substitute for the water-soluble cobalt-containing substance and also containing a carboxylic acid compound, a chemical conversion coating can be formed which has enhanced corrosion resistance and reduced dissolving amount of metal.
- The present invention that has been accomplished on the basis of the above founding is as follows:
- (1) A reactive-type chemical conversion treating acidic composition comprising a water-soluble trivalent chromium-containing substance, a water-soluble titanium-containing substance, and a carboxylic acid compound, the acidic composition being free from a water-soluble cobalt-containing substance.
- (2) The reactive-type chemical conversion treating acidic composition according to the above (1), wherein the content of the water-soluble trivalent chromium-containing substance in the composition is 0.01 mol/L or more and 0.15 mol/L or less in terms of chromium, the content of the water-soluble titanium-containing substance in the composition is 0.0001 mol/L or more and 1 mol/L or less in terms of titanium, and the content of the carboxylic acid compound in the composition is 0.001 mol/L or more and 0.2 mol/L or less in terms of carboxylic acid.
- (3) The reactive-type chemical conversion treating acidic composition according to the above (1) or (2), further comprising at least one acid compound from the group consisting of citric acid compound and oxalic acid compound .
- (4) The reactive-type chemical conversion treating acidic composition according to any one of the above (1) to (3), wherein first ratio, which is ratio of the content of citric acid compound in terms of citric acid (unit: mol/L) to the content of water-soluble trivalent chromium-containing substance in terms of chromium (unit: mol/L), is 0.05 or more and 0.8 or less.
- (5) The reactive-type chemical conversion treating acidic composition according to the above (4) wherein the first ratio is 0.1 or more and 0.6 or less.
- (6) The reactive-type chemical conversion treating acidic composition according to any one of the above (1) to (5), wherein second ratio, which is ratio of the content of oxalic acid compound in terms of oxalic acid (unit: mol/L) to the content of water-soluble trivalent chromium-containing substance in terms of chromium (unit: mol/L), is 0.05 or more and 2 or less.
- (7) The reactive-type chemical conversion treating acidic composition according to the above (6) wherein the second ratio is 0.1 or more and 1.7 or less.
- (8) The reactive-type chemical conversion treating acidic composition according to the above (1) to (7), wherein the composition is free from water-soluble vanadium-containing substance, water-soluble fluorine-containing substance, or film-forming organic component.
- (9) The reactive-type chemical conversion treating acidic composition according to the above (1) to (8), further comprising organic phosphoric acid compound of 0.001 mol/L or more and 1 mol/L or less in terms of phosphorus.
- (10) The reactive-type chemical conversion treating acidic composition according to the above (9), further comprising water-soluble zinc-containing substance of 0.005 mol/L or more and 0.1 mol/L or less in terms of zinc.
- (11) The reactive-type chemical conversion treating acidic composition according to any one of the above (1) to (10), further comprising water-soluble aluminum-containing substance of 0.0001 mol/L or more and 0.1 mol/L or less in terms of aluminum.
- (12) A production method of a member having a surface provided thereon with a chemical conversion coating, the production method comprising: a contacting step that causes the acidic composition according to any one of the above (1) to (11) to contact with a base material having a metal-based surface thereby forming a chemical conversion coating on the metal-based surface of the base material; and a washing step that washes the base material having been subjected to the contacting step to obtain a member having a surface provided thereon with the chemical conversion coating.
- (13) The production method of a member according to the above (12), wherein the metal-based surface is either one surface selected from the group consisting of a surface of the zinc-based plated film formed using a chloride bath, a surface of the plated film obtainable by forming a zinc-based plated film using a zincate bath and subjecting this to baking treatment, and a surface of the zinc-based plated film formed using a zincate bath without baking treatment.
- (14) The production method of a member according to the above (13), wherein the metal-based surface is the surface of the plated film obtainable by forming a zinc-based plated film using a zincate bath and subjecting this to baking treatment, and the carboxylic acid compound includes oxalic acid compound.
- (15) A use of a reactive-type chemical conversion treating acidic composition comprising contacting the acidic composition according to any one of the above (1) to (11) to a base material having metal-based surface to form the chemical conversion coating on the metal-based surface of the base material.
- (16) The use of a reactive-type chemical conversion treating acidic composition according to the above (15), wherein the metal-based surface is either one surface selected from the group consisting of a surface of the zinc-based plated film formed using a chloride bath, a surface of the plated film obtainable by forming a zinc-based plated film using a zincate bath and subjecting this to baking treatment, and a surface of the zinc-based plated film formed using a zincate bath without baking treatment.
- (17) The use of a reactive-type chemical conversion treating acidic composition according to the above (16), wherein the metal-based surface is the surface of the plated film obtainable by forming a zinc-based plated film using a zincate bath and subjecting this to baking treatment, and the carboxylic acid compound includes oxalic acid compound.
- According to the present invention, there is provided a chemical conversion treatment liquid capable of forming a chemical conversion coating that has enhanced corrosion resistance with consideration for environmental conservation, without using any water-soluble cobalt-containing substance which has conventionally been in heavy usage for forming a chemical conversion coating that has enhanced corrosion resistance. A production method of a member having a surface coated with the chemical conversion treatment liquid is also provided.
- Embodiments of the present invention will hereinafter be described in detail.
- Descriptions will now be directed to the composition of an acidic composition for reactive chemical conversion treatment according to one embodiment of the present invention (also referred herein to as "chemical conversion treatment liquid).
- The chemical conversion treatment liquid according to one embodiment of the present invention contains at least one type of a water-soluble trivalent chromium-containing substance. The water-soluble trivalent chromium-containing substance may be selected from the group consisting of trivalent chromium (Cr3+) and a water-soluble substance that contains trivalent chromium.
- It is preferred to use a water-soluble compound capable of generating the water-soluble trivalent chromium-containing substance in water (referred hereinafter to as "water-soluble trivalent chromium compound") as a substance to be compounded for containing the water-soluble trivalent chromium-containing substance in the chemical conversion treatment liquid, i.e., a raw material substance for the water-soluble trivalent chromium-containing substance.
- Examples of the water-soluble trivalent chromium compound include trivalent chromium salt, such as chromium chloride, chromium sulfate, chromium nitrate, chromium phosphate and chromium acetate, and a compound obtained by reducing a hexavalent chromium compound, such as chromic acid and bichromate, to trivalent using a reductant. The water-soluble trivalent chromium compound may consist only of one type of compound, or may comprise plural types. It should be appreciated that the chemical conversion treatment liquid according to the present embodiment is substantially free from hexavalent chromium because any hexavalent chromium compound is not added actively as a raw material to the chemical conversion treatment liquid according to the present embodiment.
- Preferred content of the water-soluble trivalent chromium-containing substance in the chemical conversion treatment liquid according to the present embodiment is about 0.01 mol/L or more in terms of chromium with consideration for improving formability of the chemical conversion coating, more preferred content thereof is about 0.02 mol/L or more, or most preferred content thereof is about 0.04 mol/L or more. The upper limit of the content may preferably be, but not limited to, about 0.15 mol/L, more preferable be about 0.12 mol/L, or most preferably be about 0.1 mol/L in terms of chromium because unduly large content may possibly lead to problems, such as from the viewpoints of economic efficiency and waste liquid treatment.
- The chemical conversion treatment liquid according to the present embodiment contains at least one type of a water-soluble titanium-containing substance. The water-soluble titanium-containing substance may be selected from the group consisting of titanium ion (Ti3+, Ti4+) and a water-soluble substance that contains titanium ion.
- It is preferred to use a water-soluble compound capable of generating the water-soluble titanium-containing substance in water (referred hereinafter to as "water-soluble titanium compound") as a substance to be compounded for containing the water-soluble titanium-containing substance in the chemical conversion treatment liquid, i.e., a raw material substance for the water-soluble titanium-containing substance.
- Examples of the water-soluble titanium compound which can be used include carbonate, oxide, hydroxide, nitrate, sulfate, phosphate, fluoride, fluoro acid (salt), organic acid salt and organic complex compound of Ti. Specific examples include titanium (IV) oxide (titania), titanium nitrate, titanium (III) sulfate, titanium (IV) sulfate, titanyl sulfate TiOSO4, titanium (III) fluoride, titanium (IV) fluoride, hexafluorotitanic acid H2TiF6, ammonium hexafluorotitanate [(NH4)2TiF6], titanium laurate, diisopropoxy titanium bisacetone (C5H7O2)2Ti[OCH(CH3)2]2, and titanium acetylacetonate Ti(OC(=CH2)CH2COCH3)3. These may be in any form of anhydride or hydrate. It is preferred that the water-soluble titanium compound is free from fluorine because the chemical conversion treatment liquid according to the present embodiment may preferably be a chemical conversion treatment liquid with less environmental burden.
- Preferred content of the water-soluble titanium-containing substance in the chemical conversion treatment liquid according to the present embodiment is about 0.0001 mol/L or more in terms of titanium with consideration for improving formability of the chemical conversion coating, more preferred content thereof is about 0.0005 mol/L or more, or most preferred content thereof is about 0.001 mol/L or more. The upper limit of the content may preferably be, but not limited to, about 1 mol/L in terms of titanium, more preferably be about 0.5 mol/L or more, or most preferably be about 0.1 mol/L or more because unduly large content may increase the possibility of deteriorating the stability of the chemical conversion treatment liquid and also increase the possibility of problems, such as from the viewpoints of economic efficiency and waste liquid treatment.
- The chemical conversion treatment liquid according to the present embodiment contains a carboxylic acid compound. The "carboxylic acid compound" as used herein means a compound that comprises one or more types selected from the group consisting of a carboxylic acid, which is an organic acid having a carboxylic group, and ions, salts, derivatives and coordination compounds thereof, and is in a state of being dissolved in the chemical conversion treatment liquid as an aqueous composition.
- Examples of a carboxylic acid that gives the carboxylic acid compound according to the present invention include: monocarboxylic acid, such as formic acid, acetic acid and propionic acid; dicarboxylic acid, such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, phthalic acid and terephthalic acid; tricarboxylic acid, such as tricarballylic acid and aconitic acid; hydroxy carboxylic acid, such as glycolic acid, lactic acid, malic acid, tartaric acid, citric acid, isocitric acid and ascorbic acid; and aminocarboxylic acid, such as glycine and alanine.
- The carboxylic acid compound according to the present embodiment may contain one or more types selected from the group consisting of a citric acid compound and an oxalic acid compound. The "citric acid compound" as used herein means a compound that comprises one or more types selected from the group consisting of a citric acid, and ions, salts, derivatives and coordination compounds thereof, and is in a state of being dissolved in the chemical conversion treatment liquid as an aqueous composition. The "oxalic acid compound" as used herein means a compound that comprises one or more types selected from the group consisting of an oxalic acid, and ions, salts, derivatives and coordination compounds thereof, and is in a state of being dissolved in the chemical conversion treatment liquid as an aqueous composition.
- The carboxylic acid compound contained in the chemical conversion treatment liquid according to the present embodiment may contain either one or both of a citric acid compound and an oxalic acid compound. When the surface to be treated is provided by a zinc-based plated film (which collectively means herein a zinc plated film and zinc alloy plated film) formed using a chloride bath, the carboxylic acid compound contained in the chemical conversion treatment liquid according to the present embodiment may contain at least one acid from a citric acid compound and an oxalic acid compound, or may preferably consist essentially of either one of them. When the surface to be treated is provided by a film obtained by forming a zinc-based plated film using a zincate bath and subjecting this to baking treatment, the carboxylic acid compound contained in the chemical conversion treatment liquid according to the present embodiment may contain oxalic acid compound, or may preferably consist essentially of oxalic acid compound. When the surface to be treated is provided by a film that is a zinc-based plated film formed using a zincate bath but without baking treatment, the carboxylic acid compound contained in the chemical conversion treatment liquid according to the present embodiment may contain at least one from a citric acid compound and an oxalic acid compound, or may preferably consist essentially of either one of them.
- It is preferred to use a water-soluble compound capable of generating the carboxylic acid compound in water (referred hereinafter to as "carboxylic acid source") as a substance to be compounded for containing the carboxylic acid compound in the chemical conversion treatment liquid, i.e., a raw material substance for the carboxylic acid compound. Specific examples of the carboxylic acid source include: carboxylic acid derivatives, such as carboxylic ester; carboxylic acid; and carboxylic salt (metal salt). In view of high solubility and improvement of easy interaction between the generated carboxylic acid compound and other components contained in the chemical conversion treatment liquid, the carboxylic acid source may be carboxylic salt. Examples of such carboxylic salt include sodium oxalate, sodium citrate, potassium oxalate, and potassium citrate.
- Preferred content of the carboxylic acid compound in the chemical conversion treatment liquid according to the present embodiment is about 0.001 mol/L or more in terms of carboxylic acid with consideration for improving formability of the chemical conversion coating, more preferred content thereof is about 0.004 mol/L or more, or most preferred content thereof is about 0.008 mol/L or more. The upper limit of the content may preferably be, but not limited to, about 0.4 mol/L in terms of carboxylic acid, more preferably about 0.2 mol/L, or most preferably about 0.1 mol/L because unduly large content may increase the possibility of deteriorating the stability of the chemical conversion treatment liquid and also increase the possibility of problems, such as from the viewpoints of economic efficiency and waste liquid treatment.
- A ratio (first ratio) of the content of citric acid compound in terms of citric acid (unit: mol/L) of the chemical conversion treatment liquid according to the present embodiment (unit: mol/L) to the content of water-soluble trivalent chromium-containing substance in terms of chromium (unit: mol/L) may preferably be about 0.05 or more and about 0.8 or less, more preferably about 0.1 or more and about 0.6 or less, and most preferably about 0.2 or more and about 0.4 or less, from the viewpoint of easily forming a chemical conversion coating that has enhanced corrosion resistance. A ratio (second ratio) of the content of oxalic acid compound in terms of oxalic acid (unit: mol/L) to the content of the water-soluble trivalent chromium-containing substance in terms of chromium (unit: mol/L) may preferably be about 0.05 or more and about 2 or less, easily forming a chemical conversion coating that has enhanced corrosion resistance from the viewpoint of easily forming a chemical conversion coating that has enhanced corrosion resistance, may more preferably be about 0.1 or more and about 1.7 or less, or may most preferably be about 0.6 or more and about 1.7 or less.
- The chemical conversion treatment liquid according to the present embodiment may contain an organic acid compound other than the above carboxylic acid compound. Examples of an organic acid associated with such an organic acid compound include sulfonic acid. The content of such organic acid compounds in the chemical conversion treatment liquid according to the present embodiment may preferably be, but not limited to, within a range where the above carboxylic acid compound can function appropriately.
- The chemical conversion treatment liquid according to the present embodiment may contain an organic phosphonic acid compound. The "organic phosphonic acid compound" as used herein means a compound that comprises one or more types selected from the group consisting of an organic phosphonic acid, and ions and salts thereof, while the "organic phosphonic acid" as used herein means one of which the rational formula is R-P(=O)(OH)2 (where R is an organic group) and in which an organic group is bonded to the phosphonic group. Containing an organic phosphonic acid compound can reduce the dissolving amount of metal, in particular the dissolving amount of chromium, from a chemical conversion film that is formed using the chemical conversion treatment liquid.
- Examples of the organic phosphonic acid include 1-hydroxyethylidene-1,1-diphosphonic acid, 2-phosphonobutane1,2,4-tricarboxylic acid, amino(trimethylene phosphonic acid), ethylenediamine tetra(methylene phosphonic acid), and diethylene triamine penta(methylene phosphonic acid).
- Examples of salts of the organic phosphonic acids include tetrasodium 1-hydroxyethylidene-1,1-diphosphonate, trisodium 1-hydroxyethylidene-1,1-diphosphonate, pentasodium ethylenediamine tetra(methylene phosphonate), and heptasodium diethylene triamine penta(methylene phosphonate). These salts may often be such that sodium ions are dissociated in the chemical conversion treatment liquid.
- When the chemical conversion treatment liquid according to the present embodiment contains the organic phosphonic acid compound, preferred content of the organic phosphonic acid compound is about 0.001 mol/L or more in terms of phosphorus in view of making it easy to form the chemical conversion coating having an excellent property, more preferred content thereof is about 0.005 mol/L or more, or most preferred content thereof is about 0.01 mol/L or more. The upper limit of the content may preferably be, but not limited to, about 1 mol/L in terms of phosphorous, or may more preferably be about 0.1 mol/L because unduly large content may increase the possibility of deteriorating the appearance of obtained chemical conversion coating and also increase the possibility of problems, such as from the viewpoints of economic efficiency and waste liquid treatment. It may be possibly preferred that the chemical conversion treatment liquid according to the present embodiment is substantially free from the organic phosphonic acid compound.
- When the chemical conversion treatment liquid according to the present embodiment contains the organic phosphonic acid compound as described above, the chemical conversion treatment liquid according to the present embodiment may further contain at least one type of a water-soluble zinc-containing substance. The water-soluble zinc-containing substance may be selected from the group consisting of zinc ions (Zn2+) and a water-soluble substance that contains zinc ions. If, when the chemical conversion treatment liquid according to the present embodiment contains the organic phosphonic acid compound, the water-soluble zinc-containing substance is further contained, then it may be able to enhance the quality stability of the chemical conversion coating formed using the chemical conversion treatment liquid.
- It is preferred to use a water-soluble compound capable of generating the water-soluble zinc-containing substance in water (referred hereinafter to as "water-soluble zinc compound") as a substance to be compounded for containing the water-soluble zinc-containing substance in the chemical conversion treatment liquid, i.e., a raw material substance for the water-soluble zinc-containing substance.
- Examples of the water-soluble zinc compound include compounds, such as zinc chloride, zinc carbonate, zinc oxide, zinc borate, zinc acetate, zinc sulfate, and zinc nitrate. The water-soluble zinc compound may consist only of one type of compound, or may comprise plural types.
- When the chemical conversion treatment liquid according to the present embodiment contains the water-soluble zinc-containing substance, preferred content of the water-soluble zinc-containing substance is 0.005 mol/L or more in terms of zinc in view of making it easy to form the chemical conversion coating, more preferred content thereof is about 0.01 mol/L or more, or most preferable content thereof is about 0.015 mol/L or more. The upper limit of the content may preferably be, but not limited to, about 0.1 mol/L in terms of zinc, may more preferably be about 0.075 mol/L, or may most preferably be about 0.05 mol/L because unduly large content may increase the possibility of deteriorating the stability of the chemical conversion treatment liquid and also increase the possibility of problems, such as from the viewpoints of economic efficiency and waste liquid treatment.
- The chemical conversion treatment liquid according to the present embodiment may contain, in addition to the above substances, one or more types selected from the group consisting of a water-soluble metal-containing substance associated with a metal other than the above metals (Cr, Zn and Ti), an inorganic acid and anions thereof, an inorganic colloid, a silane coupling agent, and an organic phosphorous compound. The chemical conversion treatment liquid may further contain: polyphenol, such as pyrogallol and benzenediol; corrosion inhibitor; surfactant, such as diol, triol and amine; plastic dispersant; coloring material, such as dye, pigment, metal pigment generating agent and other pigment generating agents; desiccant; and dispersant.
- It should be appreciated that the chemical conversion treatment liquid according to the present embodiment is substantially free from a water-soluble substance including fluorine in view of decreasing environmental impact. Moreover, the chemical conversion treatment using the chemical conversion treatment liquid according to the present embodiment is reactive-type, so that substantially no film-forming organic component is contained therein.
- Examples of a metal element that is contained in the water-soluble metal-containing substance associated with a metal other than the above metals (Cr, Zn and Ti) include Ni, Na, K, Ag, Fe, Ca, Mg, Sc, Mn, Cu, Sn, Mo, Al, and W, which may be present in a form of oxygen acid ion, such as tungstate ion, or in a form of coordination compound. Such a water-soluble metal-containing substance may be contained thereby to provide additional advantageous effects. For example, if the water-soluble aluminum-containing substance is contained, then the appearance of obtained chemical conversion coating may be improved, and/or the dependency of the coating properties, such as corrosion resistance and dissolving amount of metal, on the base material may be reduced (specific example of the dependency may be such that the coating properties are likely to vary if the type of bath used to form a zinc-based plating is different).
- The content of the water-soluble additive metal compound may not be particularly limited. It may be set in consideration of a role of the metal element contained in each water-soluble additive metal compound. For water-soluble aluminum-containing substance, for example, the content may be about 0.0001 mol/L or more in terms of aluminum, may preferably be about 0.0005 mol/L or more, or may most preferably be about 0.001 mol/L or more. The upper limit of the content may preferably be, but not limited to, about 1 mol/L in terms of aluminum, may more preferably be about 0.5 mol/L, or may most preferably be about 0.1 mol/L because unduly large content may increase the possibility of deteriorating the stability of the chemical conversion treatment liquid and also increase the possibility of problems, such as from the viewpoints of economic efficiency and waste liquid treatment.
- It should be appreciated that the chemical conversion treatment liquid according to the present embodiment is substantially free from a water-soluble cobalt-containing substance which involves concerns about affecting the environment. Moreover, the chemical conversion treatment liquid according to the present embodiment is substantially free from a water-soluble vanadium-containing substance because the dissolving amount of V may be unduly large from a chemical conversion coating that contains V, in which case concern is that the dissolved V affects the environment.
- Examples of the inorganic acid include hydrohalic acid other than hydrofluoric acid such as hydrochloric acid and hydrobromic acid; chloric acid, perchloric acid, chlorous acid, hypochlorous acid, sulfuric acid, sulfurous acid, nitric acid, nitrous acid, phosphoric acid (orthophosphoric acid), polyphosphoric acid, metaphosphoric acid, pyrophosphoric acid, ultraphosphoric acid, hypophosphorous acid, and superphosphoric acid, among which, one or more of the inorganic acid selected from the group consisting of hydrohalic acid other than hydrofluoric acid, sulfuric acid, nitric acid, and phosphoric acid (orthophosphoric acid) may preferably be contained as anions.
- The concentration of these inorganic acids and/or inorganic acid ions in the chemical conversion treatment liquid is not particularly limited. The ratio of the total molar concentration of inorganic acids and inorganic acid ions to the total molar concentration in terms of metal of the water-soluble metal-containing substance may ordinarily be about 0.1 or more and about 10 or less, and preferably about 0.5 or more and about 3 or less.
- Examples of the inorganic colloid include silica sol, alumina sol, titanium sol and zirconia sol, and examples of the silane coupling agent include vinyltriethoxysilane and γ-methacryloxypropyltrimethoxysilane.
- The solvent of the chemical conversion treatment liquid according to the present embodiment contains water as the main component. An organic solvent, such as alcohol, ether and ketone, which has a high solubility in water may be mixed with water as solvent except water. In this case, the ratio thereof may preferably be about 10 vol% or less to the whole solvent in view of the stability in the whole chemical conversion treatment liquid.
- From the viewpoint of progressing the chemical conversion treatment, the chemical conversion treatment liquid according to the present embodiment is caused to be acidic, and the pH is therefore less than 7. The preferable value of pH within the acidic range is not particularly limited. The pH may appropriately be set considering that unduly low pH increases the possibility that the formation of the chemical conversion coating will be non-uniform while unduly high pH increases the possibility that the stability of the chemical conversion treatment liquid will deteriorate. In view of improving the quality of the chemical conversion coating and the stability of the chemical conversion treatment liquid, the pH may preferably be about 1 or more and about 5 or less, and more preferably about 1.5 or more and about 3 or less.
- If a liquid composition having a composition in which major components of the above chemical conversion treatment liquid are concentrated about 5 to about 20 times (referred hereinafter to as "concentrated liquid for chemical conversion treatment") is prepared, then bother of preparing individually the content of each component can be saved and storage thereof may be easy, thus being preferable. When this concentrated liquid for chemical conversion treatment is prepared, upper limits may be provided for the contents of the above respective components with consideration for the solubility of each component.
- The material quality of a base material to be subjected to the chemical conversion treatment according to the present embodiment is not particularly limited so long as the base material has a metal surface on which the chemical conversion coating can be formed using the chemical conversion treatment liquid according to the present embodiment. Preferable material is a metal-based material, and in particular a steel plate formed thereon with zinc-based plating is most preferable. Method of plating may be electroplating or may also be hot-dip plating, and when hot-dip plating is employed, an alloying process by heat may be performed after the plating.
- The composition of the above zinc-based plating may be pure zinc or may also be zinc alloy. When zinc alloy plating is employed, examples of metal to be alloyed include iron, nickel, and aluminum. Method of plating may be electroplating or may also be hot-dip plating. When electroplating is employed, any of cyanide bath, chloride bath, sulfuric acid bath and zincate bath may be used, and a baking treatment may be performed after preparing the plated film. When hot-dip plating is employed, an alloying process may be performed after the plating.
- Descriptions will now be directed to a production method for a member having a surface provided thereon with a chemical conversion coating, using the chemical conversion treatment liquid according to the present embodiment.
- The production method according to the present embodiment comprises: a contacting step that causes the chemical conversion treatment liquid according to the present embodiment to contact with a base material having a metal-based surface thereby forming a chemical conversion coating on the metal-based surface of the base material; and a washing step that washes the base material having been subjected to the contacting step to obtain a member having a surface provided thereon with the chemical conversion coating.
- In the contacting step, method of causing the chemical conversion treatment liquid according to the present embodiment to contact with the base material having a metal-based surface is not particularly limited. The simplest method is immersing, but spraying may be employed, or application may also be possible using a roll, etc. The contacting condition (contacting temperature, contacting time) is not particularly limited, and may be set in consideration of the composition of the chemical conversion treatment liquid, the composition of a material that constitutes the base material surface, and the productivity, etc. When the temperature of the chemical conversion treatment liquid ranges from room temperature (about 23 °C) to about 40°C, the contacting time may typically be within a range of about 10 seconds to about 5 minutes. Note that the chemical conversion treatment liquid according to the present embodiment is a reactive chemical conversion treatment liquid, and hence, even if the time duration is set to be unduly long, the thickness of the chemical conversion coating will not increase in general as time goes on.
- A base material to be subjected to the contacting step may be washed (e.g., degreasing and rinsing) using a known method, followed by an activation treatment designed such that the base material is contacted (at room temperature (about 23 °C) for about 10 seconds) with an acid aqueous solution (e.g., nitric acid aqueous solution of several ml/L).
- The base material having been subjected to the contacting step is washed using water, for example. This feature is different from that for a so-called application-type chemical conversion treatment liquid, and the washing step is a step to be performed due to the reason that the chemical conversion treatment liquid according to the present embodiment is a reactive chemical conversion treatment liquid. Such a step washes away the chemical conversion treatment liquid that remains on the surface of the base material having been subjected to the contacting step, and a member is thus obtained which comprises the base material and the chemical conversion coating formed on the surface of the base material. For the member after the washing, a drying step is conducted ordinarily for the purpose of removing the water adhering to the chemical conversion coating and the base material. The drying condition (drying temperature, drying time) is not particularly limited. The drying condition may appropriately be set in consideration of heat resistance of the base material, productivity, and the like. Various cases for drying may be possible, such as a case where the member is stationarily placed for about 10 minutes in an oven maintained at a temperature of about 100°C or less, a case where a centrifuge separator is used for drying, and a case where the member is stationarily placed in ordinary environment. Depending on the type of chemical conversion coating, the drying may cause a change in the composition, such as a change of a part or whole of the hydroxide into oxide.
- The production method according to the present embodiment may comprise a finishing step that, after the above member has been treated using the chemical conversion treatment liquid according to the present embodiment to form the chemical conversion coating, performs treatment using a finishing agent for enhancing the corrosion resistance and scratch resistance to form a finishing coating. The relationship between the finishing step and the drying step is freely selected such that, after the washing step, the drying step may be performed after the finishing step has been completed, or the finishing step may be performed after the drying step has been completed.
- Specific examples of the metal-based surface of the base material being the surface to be treated may include a surface of the zinc-based plated film formed using a chloride bath, a surface of the plated film obtainable by forming a zinc-based plated film using a zincate bath and subjecting this to baking treatment, and a surface of the zinc-based plated film formed using a zincate bath without baking treatment. When the surface to be treated is the surface of the zinc-based plated film formed using a chloride bath, or the surface of the zinc-based plated film formed using a zincate bath without baking treatment, the carboxylic acid compound may include at least one from citric acid compound and oxalic acid compound, or may preferably consist essentially of citric acid compound or oxalic acid compound. When the metal-based surface is the surface of the zinc-based plated film formed using a chloride bath with the baking treatment, the carboxylic acid compound may preferably include oxalic acid compound, or may more preferably consist essentially of oxalic acid compound.
- Descriptions will be directed to the usage of chemical conversion treatment liquid of the present embodiment.
- The use of the chemical conversion coating of the present embodiment includes contacting the acidic composition according to the present embodiment to a base material having metal-based surface to form the chemical conversion coating on the metal-based surface of the base material. The relation between the metal-based surface of the base material being the treatment surface and the carboxylic acid composition are the same in the production method of the member having the chemical conversion coating on its surface, therefore descriptions on the relation will be omitted.
- It is to be noted that the embodiments as heretofore explained are described to facilitate understanding of the present invention and are not described to limit the present invention. Therefore, it is intended that the elements disclosed in the above embodiments include all design changes and equivalents to fall within the technical scope of the present invention.
- Advantageous effects of the present invention will hereinafter be described with reference to Examples, but the present invention is not limited thereto.
- Chemical conversion treatment liquids were prepared to have a basic composition shown in Table 1 and respective detailed compositions shown in Table 2. The chemical conversion treatment liquid 1-25 was such that the compounding amount in terms of titanium of the water-soluble titanium compound was 0.001 mol/L, and the compounding amount in terms of aluminum of the water-soluble aluminum compound was 0.001 mol/L.
[Table 1] Compounding component Content at bath preparation Chromium nitrate 42 mmol/L in terms of Cr Zinc chloride 15 mmol/L in terms of Zn Source of carboxylic acid, etc. 8 mmol/L in terms of carboxylic acid Organic phosphonic acid compound 0.01 mol/L in terms of P Water-soluble additive metal compound 0.001 mol/L in terms of metal - In Table 1, the "source of carboxylic acid, etc." collectively means a carboxylic acid source and a water-soluble compound that is able to generate an organic acid compound in water. The "water-soluble additive metal compound" means those other than the water-soluble trivalent chromium compound and the water-soluble zinc compound among water-soluble metal compounds to involve water-soluble metal-containing substance in the chemical conversion treatment liquid. The organic phosphonic acid compound was "DEQUEST 2010" available from Thermphos Japan Ltd.
[Table 2] Chemical conversion treatment liquid Source of carboxylic acid, etc. Additive metal White rust area ratio (%) after SST 96h Dissolving amount (µg/cm2) Appearance Chromium Additive metal Color tone Gloss and uniformity 1-1 Citric acid None 5 0.06 0 Blue to white A 1-2 Co 4 0.1 0.072 Blue to yellow A 1-3 Ni 15 0 0.02 Blue to yellow A 1-4 Ti 1 0.03 0.08 Blue to yellow B 1-5 V 2 0.07 0.52 Yellow C 1-6 Al 25 0 0.071 White to yellow C 1-7 Oxalic acid None 6 0.09 0 Blue A 1-8 Co 0 0.1 0.09 Blue to white A 1-9 Ni 8 0 0 Blue A 1-10 Ti 1 0.02 0.105 Yellow C 1-11 V 2 0 0.8 Yellow C 1-12 Al 5 0 0.11 Blue B 1-13 Malic acid None 60 0 0 Blue to white A 1-14 Co 4 0.05 0.05 Blue to white A 1-15 Ni 13 0 0 Blue to white A 1-16 Ti 5 0 0.1 White to yellow C 1-17 V 3 0 0.9 Yellow C 1-18 Al 15 0 0.18 Blue to white B 1-19 Lactic acid None 50 0 0.06 White to yellow B 1-20 Co 10 0.02 0 White to yellow B 1-21 Ni 60 0 0 Yellow C 1-22 Ti 3 0.07 0 White to red D 1-23 V 4 0 0.8 Yellow C 1-24 Al 12 0 0.07 Blue to white B 1-25 Oxalic acid Ti/Al 1 0.03 0.09/0.01 Blue to white B - The "additive metal" in Table 2 means a metal that is associated with the water-soluble additive metal compound in Table 1. The type of water-soluble metal compound associated with each metal was as follows:
- Co: cobalt nitrate;
- Ni: nickel chloride;
- Ti: titanyl sulfate;
- V: sodium vanadate; and
- Al: aluminum nitrate.
- Zinc plating treatment was performed under the condition below for base materials comprising steel M10 bolts, and each base material was thus obtained to have a zinc plated film on the surface:
- zinc plating composition: chloride bath (ammonium-potassium mixed bath);
- plating temperature: 30°C;
- plating time: 1,800 seconds; and
- electrolytic condition: 1.5 A/dm2.
- Rinsing was performed for the base materials after the zinc plating treatment by immersing the base materials in pure water of 23°C for 10 seconds while swinging them. Activation treatment was then performed for the base materials after the zinc plating treatment and rinsing, by immersing the base materials in diluted nitric acid aqueous solution (3 ml/L) of 23°C for 10 seconds while swinging them. Rinsing was performed again for the base materials put out from the diluted nitric acid aqueous solution by immersing the base materials in pure water of 23°C for 10 seconds while swinging them.
- Chemical conversion treatment was performed for each base material after the activation treatment and rinsing, by immersing the base material in either one of the above chemical conversion treatment liquids 1-1 to 1-25, maintained at 30°C, for 45 seconds while swinging the base material. Rinsing was then performed for the base material put out from the chemical conversion treatment liquid by immersing the base material in pure water of 23°C for 10 seconds while swinging the base material. The base material after the chemical conversion treatment and rinsing was dried by being stationarily placed for 10 minutes in an oven maintained at 80°C. A member having its surface formed thereon with the chemical conversion coating was thus obtained as each of test members 1-1 to 1-25.
- For the obtained test members 1-1 to 1-25, the neutral salt spray test in conformity with JIS Z2371: 2000 (ISO 9227: 1990) was conducted for 96 hours, followed by visual observation of the surface of each test member after the test to measure a white rust generating area, and the white rust area ratio (unit: %) was obtained by measuring the ratio of the white generating area to the area of the main surface of the test member.
- One test member (surface area: 25 cm2) was immersed in 100 ml of pure water for 24 hours. The test member was then put out therefrom, and the metal amount dissolved into water was measured using an ICP (SPS 5520 available from SII NanoTechnology Inc.) to obtain the dissolving amount (unit: µg/cm2).
- The surface formed of the chemical conversion coating of each test member was visually observed, and the color tone was evaluated.
- The surface of each test member was visually observed, and the gloss and the uniformity in appearance were evaluated in accordance with the criteria below:
- A (excellent): gloss present, no tarnish found, and uniform appearance over the entire surface;
- B (good): little tarnish found and/or gloss slightly weak;
- C (acceptable): tarnish present, gloss weak, and/or appearance uniformity slightly low; and
- D (defective): tarnish strong, no gloss, and/or appearance non-uniform.
- Evaluation results are listed in Table 2. As shown in Table 2, upon the chemical conversion treatment liquids each containing a water-soluble titanium-containing substance and a carboxylic acid compound (chemical conversion treatment liquids 1-4, 1-10, 1-16 and 1-22), the chemical conversion coatings formed using such chemical conversion treatment liquids (the present chemical conversion coatings) had excellent corrosion resistance comparable with or higher than those of the chemical conversion coatings formed using the chemical conversion treatment liquids each containing the water soluble cobalt-containing substance (Co-containing chemical conversion coatings). In addition, the dissolving amount of metal each from the present chemical conversion coatings was comparable with those from the Co-containing chemical conversion coatings, thus presenting low possibility of affecting the environment in view of the metal dissolution from the chemical conversion coating.
- In contrast, upon the chemical conversion treatment liquids each containing the water-soluble metal-containing substance associated with Ni or Al, the obtained chemical conversion coatings had far poorer corrosion resistance than those of the Co-containing chemical conversion coatings. Upon the chemical conversion treatment liquids each containing the water-soluble metal-containing substance associated with V, the dissolving amount of metal was unduly large, thus presenting high possibility of affecting the environment in view of the metal dissolution from the chemical conversion coating.
- Chemical conversion treatment liquids 2-1 to 2-13 were obtained with the compositions listed in Table 1 by excluding water-soluble additive metal compound and changing the content of citric acids as the source of carboxylic acid, etc. to have the ratio values listed in Table 3. This ratio also refers hereinafter to "CA1/Cr ratio", which is a ratio of the content of citric acid compound in terms of citric acid (unit: mol/L) to the content of water-soluble trivalent chromium-containing substance in terms of chromium (unit: mol/L). Chemical conversion treatment liquids 2-14 to 2-27 were obtained with the compositions listed in Table 1 by excluding water-soluble additive metal compound and changing the content of oxalic acids as the source of carboxylic acid, etc. to have the ratio values listed in Table 3. This ratio also refers hereinafter to "CA2/Cr ratio", which is a ratio of the content of oxalic acid compound in terms of oxalic acid (unit: mol/L) to the content of water-soluble trivalent chromium-containing substance in terms of chromium (unit: mol/L).
[Table 3] Chemical conversion treatment liquid Source of Carboxylic acid, etc. CA1/Cr ratio Appearance (gloss, uniformity) White rust area ratio (%) 48h 72h 96h 2-1 Citric Acid 0 C 12 25 50 2-2 0.1 A 1 15 25 2-3 0.2 A 3 5 5 2-4 0.4 A 0 2 7 2-5 0.6 B 5 7 10 2-6 0.8 B 3 15 17 2-7 1 C 1 15 25 2-8 1.2 C 3 25 35 2-9 1.5 C 45 55 60 2-10 1.7 C 30 60 80 2-11 2 C 40 60 80 2-12 2.3 D 50 80 90 2-13 2.5 D 50 80 90 Chemical conversion treatment liquid Source of Carboxylic acid, etc. CA2/Cr ratio Appearance (gloss, uniformity) White rust area ratio (%) 48h 72h 96h 2-1 Oxalic Acid 0 C 12 25 50 2-14 0.1 A 1 7 12 2-15 0.2 A 0 4 8 2-16 0.4 A 0 4 10 2-17 0.6 A 0 1 3 2-18 0.8 A 0 2 5 2-19 1 A 0 0 1 2-20 1.2 A 0 0 1 2-21 1.3 A 0 1 3 2-22 1.4 A 0 1 2 2-23 1.5 A 0 0 2 2-24 1.7 A 0 2 3 2-25 2 A 0 2 6 2-26 2.3 A 0 4 10 2-27 2.5 A 0 3 10 - Test members 2-1 to 2-27 corresponding to the chemical conversion treatment liquids 2-1 to 2-27 were obtained in the same manner in Example 1.
- For the obtained test members 2-1 to 2-27, the neutral salt spray test in conformity with JIS Z2371: 2000 (ISO 9227: 1990) was conducted, followed by visual observation of the surface of each test member after the test of 48 hours, 72 hours, and 96 hours, to obtain the white rust area ratio (unit: %) at each timing.
- As a result, the white rust area ratio was confirmed to vary by changing the CA1/Cr ratio or CA2/Cr ratio as shown in Table 2.
- As shown in Table 4, test members 3-1 to 3-15 were prepared by using the chemical conversion treatment liquids prepared in Example 1 and performing the same operations as those in Example 1.
[Table 4] Test member Chemical conversion treatment liquid Source of carboxylic acid, etc. Additive metal White rust area ratio (%) Dissolving amount (µg/cm2) 72h 120h 168h 216h chromium Additive metal 3-1 1-1 Citric acid None 2 5 15 30 0.05 - 3-2 1-2 Co 0 1 3 5 0.04 0.02 3-3 1-4 Ti 0 1 2 5 0.03 0.08 3-4 1-5 V 0 1 1 3 0.03 0.34 3-5 1-6 Al 10 25 30 40 0.02 <0.01 3-6 1-7 Oxalic acid None 2 3 8 11 0.02 - 3-7 1-8 Co 1 2 3 4 0.04 0.02 3-8 1-10 Ti 1 2 4 9 0.02 0.08 3-9 1-11 V 0.5 1 2 2 0.03 0.28 3-10 1-12 Al 10 18 30 45 0.01 <0.01 3-11 1-19 Lactic acid None 5 15 20 18 0.02 - 3-12 1-20 Co 5 10 12 15 0.02 <0.01 3-13 1-22 Ti 2 3 7 10 0.05 0.08 3-14 1-23 V 1 2 3 6 0.03 0.21 3-15 1-24 Al 10 15 25 35 0.01 <0.01 - An Auto-gilder was used, into which 1 kg of steel M10 bolts as dummies and each 1 kg of the test members 3-1 to 3-15 were put to be rotated for 2 minutes, thereby scratching each test member, and a state was obtained where metal dissolution was likely to occur.
- For these test members, the neutral salt spray test in conformity with JIS Z2371: 2000 (ISO 9227: 1990) was conducted, followed by visual observation of the surface of each test member after the test of 72 hours, 120 hours, 168 hours, and 216 hours, to obtain the white rust area ratio (unit: %) at each timing.
- One test member (surface area: 25 cm2) was immersed in 100 ml of pure water for 24 hours. The test member was then put out therefrom, and the metal amount dissolved into water was measured using an ICP (SK-150 available from Shinkyoritsu Kako Co., Ltd.) to obtain the dissolving amount (unit: µg/cm2).
- As a result, the test members 3-3, 3-8 and 3-13 obtained using the chemical conversion treatment liquids 1-4, 1-10 and 1-22 each containing the water-soluble titanium-containing substance had excellent corrosion resistance and metal dissolving amount comparable with or more than those of the test members (3-2, 3-7 and 3-12) obtained using the chemical conversion treatment liquids (1-2, 1-8 and 1-20) each containing the water-soluble cobalt-containing substance. In contrast, upon the chemical conversion treatment liquids each containing the water-soluble metal-containing substance other than the water-soluble titanium-containing substance, the result was such that at least one of the corrosion resistance and metal dissolving amount of each obtained chemical conversion coating was far poorer than those of the test members obtained using the chemical conversion treatment liquids each containing the water-soluble cobalt-containing substance.
- Chemical conversion treatment liquid 4 was prepared by excluding the zinc oxide as the water-soluble zinc compound and the organic phosphonic acid compound from the chemical conversion treatment liquid 1-4 prepared in Example 1.
- Two types of test members were produced by using these chemical conversion treatment liquid 4 and chemical conversion treatment liquid 1-4 and performing the same operations as those in Example 1. For these test members, the same neutral salt spray test as that for Example 1 and the same neutral salt spray test after scratching as that for Example 3 were conducted, and each white rust area ratio (unit: %) was measured after the test of 72 hours and 120 hours. In addition, for these test members, measurement of the dissolving amount of metal was performed like in Example 1. These results are listed in Table 5.
[Table 5] Chemical conversion treatment liquid White rust area ratio (%) Dissolving amount (µg/cm2) Without scratching With scratching 72h 120h 72h 120h Chromium Additive metal 4 0 3 1 5 0.07 0.08 1-4 0 1 1 4 0.03 0.08 - Chemical conversion treatment liquids 5-1 to 5-8 were obtained with the compositions listed in Table 1 by adding 0.001 mol/L of water-soluble titanium compound in terms of titanium as the water-soluble additive metal compound and changing the content of citric acid or oxalic acid to have respective CA1/Cr ratio or CA2/Cr ratio values listed in Table 6. Test members 5-1 to 5-8 corresponding to the chemical conversion treatment liquids 5-1 to 5-8 were obtained in the same manner in Example 1.
- The surface of each of obtained test members 5-1 to 5-8 was visually observed, then the gloss and the uniformity in appearance were evaluated in accordance with the criteria in Example 1 (A to D). For the obtained test members 5-1 to 5-8, the neutral salt spray test in conformity with JIS Z2371: 2000 (ISO 9227: 1990) was conducted, followed by visual observation of the surface of each test member after the test of 48 hours, 72 hours, and 96 hours, to obtain the white rust area ratio (unit: %) at each timing.
- As a result, showing in Table 6, it was observed that the white rust area ratio was variable by changing CA1/Cr ratio or CA2/Cr ratio.
[Table 6] Chemical conversion treatment liquid Source of Carboxylic acid, etc. CA1/Cr ratio Appearance (gloss, uniformity) White rust area ratio (%) 48h 72h 96h 5-1 Citric Acid 0.1 B 0 1 5 5-2 0.2 A 0 0 1 5-3 0.6 B 1 3 6 5-4 1 B 2 10 15 Chemical conversion treatment liquid Source of Carboxylic acid, etc. CA2/Cr ratio Appearance (gloss, uniformity) White rust area ratio (%) 48h 72h 96h 5-5 Oxalic Acid 0.2 C 0 1 1 5-6 0.6 C 0 0 1 5-7 1.4 A 0 0 0 5-8 2 B 0 1 2 - Chemical conversion treatment liquids 6-1 to 6-10 were obtained with the compositions listed in Table 1 except using, as water-soluble additive metal compound, two kinds of water-soluble additive metals from water-soluble titanium compound, water-soluble aluminum compound, water-soluble vanadium compound, and water-soluble nickel compound as listed in Table 7. The content of the water-soluble additive metal was 0.001 mol/L in terms of metal in each compound and the content of citric acid or oxalic acid was adjusted to have respective CA1/Cr ratio or CA2/Cr ratio values listed in Table 7. Test members 6-1 to 6-10 corresponding to the chemical conversion treatment liquids 6-1 to 6-10 were obtained in the same manner in Example 1.
- The surface of each of obtained test members 6-1 to 6-10 was visually observed, then the gloss and the uniformity in appearance were evaluated in accordance with the criteria in Example 1 (A to D). For the obtained test members 6-1 to 6-10, the neutral salt spray test in conformity with JIS Z2371: 2000 (ISO 9227: 1990) was conducted, followed by visual observation of the surface of each test member after the test of 48 hours, 72 hours, and 96 hours, to obtain the white rust area ratio (unit: %) at each timing. The results are shown in Table 7.
[Table 7] Chemical conversion treatment liquid Source of Carboxylic acid, etc. CA1/Cr ratio Additive metal 1 Additive metal 2 Appearance (gloss, uniformity) White rust area ratio (%) 48h 72h 96h 6-1 Citric Acid 0.2 Ti Al A 0 0 0 6-2 V C 0 0 1 6-3 Ni B 0 2 3 6-4 Al V C 0 1 3 6-5 Ni B 0 2 3 Chemical conversion treatment liquid Source of Carboxylic acid, etc. CA2/Cr ratio Additive metal 1 Additive metal 2 Appearance (gloss, uniformity) White rust area ratio (%) 48h 72h 96h 6-6 Oxalic Acid 1.4 Ti Al A 0 0 0 6-7 V C 0 0 1 6-8 Ni B 0 0 1 6-9 Al V C 0 2 4 6-10 Ni A 0 3 5
Claims (15)
- A reactive-type chemical conversion treating acidic composition comprising a water-soluble trivalent chromium-containing substance, a water-soluble titanium-containing substance, and a carboxylic acid compound, the acidic composition being free from a water-soluble cobalt-containing substance.
- The reactive-type chemical conversion treating acidic composition according to claim 1, wherein the content of the water-soluble trivalent chromium-containing substance in the composition is 0.01 mol/L or more and 0.15 mol/L or less in terms of chromium, the content of the water-soluble titanium-containing substance in the composition is 0.0001 mol/L or more and 1 mol/L or less in terms of titanium, and the content of the carboxylic acid compound in the composition is 0.001 mol/L or more and 0.2 mol/L or less in terms of carboxylic acid.
- The reactive-type chemical conversion treating acidic composition according to claim 1 or 2, further comprising at least one acid compound from the group consisting of citric acid compound and oxalic acid compound.
- The reactive-type chemical conversion treating acidic composition according to any one of claims 1 to 3, wherein first ratio, which is ratio of the content of citric acid compound in terms of citric acid (unit: mol/L) to the content of water-soluble trivalent chromium-containing substance in terms of chromium (unit: mol/L), is 0.05 or more and 0.8 or less.
- The reactive-type chemical conversion treating acidic composition according to claim 4 wherein the first ratio is 0.1 or more and 0.6 or less.
- The reactive-type chemical conversion treating acidic composition according to any one of claims 1 to 5, wherein second ratio, which is ratio of the content of oxalic acid compound in terms of oxalic acid (unit: mol/L) to the content of water-soluble trivalent chromium-containing substance in terms of chromium (unit: mol/L), is 0.05 or more and 2 or less.
- The reactive-type chemical conversion treating acidic composition according to claim 6, wherein the second ratio is 0.1 or more and 1.7 or less.
- The reactive-type chemical conversion treating acidic composition according to any one of claims 1 to 7, wherein the composition is free from water-soluble vanadium-containing substance, water-soluble fluorine-containing substance, or film-forming organic component.
- The reactive-type chemical conversion treating acidic composition according to any one of claims 1 to 8, further comprising organic phosphoric acid compound of 0.001 mol/L or more and 1 mol/L or less in terms of phosphorus.
- The reactive-type chemical conversion treating acidic composition according to claim 9, further comprising water-soluble zinc-containing substance of 0.005 mol/L or more and 0.1 mol/L or less in terms of zinc.
- The reactive-type chemical conversion treating acidic composition according to any one of claims 1 to 10, further comprising water-soluble aluminum-containing substance of 0.0001 mol/L or more and 0.1 mol/L or less in terms of aluminum.
- A production method of a member having a surface provided thereon with a chemical conversion coating, the production method comprising: a contacting step that causes the acidic composition according to any one of claims 1 to 11 to contact with a base material having a metal-based surface thereby forming a chemical conversion coating on the metal-based surface of the base material; and a washing step that washes the base material having been subjected to the contacting step to obtain a member having a surface provided thereon with the chemical conversion coating.
- The production method of a member according to claim 12, wherein the metal-based surface is either one surface selected from the group consisting of a surface of the zinc-based plated film formed using a chloride bath, a surface of the plated film obtainable by forming a zinc-based plated film using a zincate bath and subjecting this to baking treatment, and a surface of the zinc-based plated film formed using a zincate bath without baking treatment.
- The production method of a member according to claim 13, wherein the metal-based surface is the surface of the zinc-based plated film formed using a zincate bath without baking treatment, and the carboxylic acid compound includes oxalic acid compound.
- A use of a reactive-type chemical conversion treating acidic composition comprising contacting the acidic composition according to any one of claims 1 to 11 to a base material having metal-based surface to form the chemical conversion coating on the metal-based surface of the base material.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2013011384 | 2013-01-24 | ||
JP2014000267A JP6216936B2 (en) | 2013-01-24 | 2014-01-06 | Method for producing member having reactive composition and acidic coating for chemical conversion treatment and chemical coating on its surface |
Publications (2)
Publication Number | Publication Date |
---|---|
EP2759621A1 true EP2759621A1 (en) | 2014-07-30 |
EP2759621B1 EP2759621B1 (en) | 2021-06-02 |
Family
ID=49989604
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP14152315.9A Active EP2759621B1 (en) | 2013-01-24 | 2014-01-23 | Reactive-type chemical conversion treatment composition and production method of member with chemical conversion coated surface |
Country Status (2)
Country | Link |
---|---|
EP (1) | EP2759621B1 (en) |
JP (1) | JP6216936B2 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3045563A1 (en) * | 2015-01-16 | 2016-07-20 | Nihon Hyomen Kagaku Kabushiki Kaisha | Treatment liquid for trivalent chromium conversion coating and method of treatment of metal substrate |
CN114875395A (en) * | 2022-03-31 | 2022-08-09 | 潍坊国一铝材有限公司 | Electrophoretic galvanized iron product and surface treatment method thereof |
CN115413300A (en) * | 2021-03-31 | 2022-11-29 | 油研工业股份有限公司 | Chemical conversion treatment liquid and method for producing member having chemical conversion coating film on member surface |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106835103B (en) * | 2017-02-10 | 2018-10-23 | 章丘市天健表面技术材料厂 | A kind of titanizing liquid and the preparation method and application thereof |
WO2022209019A1 (en) * | 2021-03-31 | 2022-10-06 | ユケン工業株式会社 | Chemical conversion treatment liquid, and method for manufacturing member in which chemical conversion film is provided on surface |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003171778A (en) * | 2001-12-06 | 2003-06-20 | Nippon Hyomen Kagaku Kk | Method for forming protective film of metal, and protective film of metal |
JP2010196174A (en) | 2009-01-30 | 2010-09-09 | Yuken Industry Co Ltd | Composition for chemical conversion coating, and member equipped with chemical conversion coating film comprising the composition |
EP2264221A1 (en) * | 2006-12-28 | 2010-12-22 | United Technologies Corporation | Process for forming a halogen-free trivalent chromium conversion coating |
US20110008645A1 (en) * | 2008-03-11 | 2011-01-13 | Mark Andre Schneider | Process for coating metallic surfaces with a passivating agent, the passivating agent and its use |
CA2810747A1 (en) * | 2010-09-10 | 2012-03-15 | Chemetall Gmbh | Method for coating metallic surfaces with a coating agent containing a polymer, the coating agent, and use thereof |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS501934A (en) * | 1973-05-10 | 1975-01-10 | ||
JP4074320B2 (en) * | 2005-01-24 | 2008-04-09 | 株式会社放電精密加工研究所 | Non-chromium anticorrosion treatment method for metal member having zinc surface |
JP2006274321A (en) * | 2005-03-28 | 2006-10-12 | Mihara Sangyo:Kk | Surface treatment film |
CN102268667B (en) * | 2007-08-03 | 2016-08-10 | 迪普索尔化学株式会社 | Trivalent chromium corrosion resistance chemical composition coating and trivalent chromium chemical conversion treatment solution |
US9315902B2 (en) * | 2008-09-29 | 2016-04-19 | Yuken Industry Co., Ltd. | Composition for chemical conversion treatment and method of manufacturing a member having a black film formed from the composition |
JP5838415B2 (en) * | 2011-04-01 | 2016-01-06 | ユケン工業株式会社 | Composition for chemical conversion treatment and method for producing member comprising chemical conversion film formed by the composition |
-
2014
- 2014-01-06 JP JP2014000267A patent/JP6216936B2/en active Active
- 2014-01-23 EP EP14152315.9A patent/EP2759621B1/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003171778A (en) * | 2001-12-06 | 2003-06-20 | Nippon Hyomen Kagaku Kk | Method for forming protective film of metal, and protective film of metal |
EP2264221A1 (en) * | 2006-12-28 | 2010-12-22 | United Technologies Corporation | Process for forming a halogen-free trivalent chromium conversion coating |
US20110008645A1 (en) * | 2008-03-11 | 2011-01-13 | Mark Andre Schneider | Process for coating metallic surfaces with a passivating agent, the passivating agent and its use |
JP2010196174A (en) | 2009-01-30 | 2010-09-09 | Yuken Industry Co Ltd | Composition for chemical conversion coating, and member equipped with chemical conversion coating film comprising the composition |
CA2810747A1 (en) * | 2010-09-10 | 2012-03-15 | Chemetall Gmbh | Method for coating metallic surfaces with a coating agent containing a polymer, the coating agent, and use thereof |
Non-Patent Citations (1)
Title |
---|
"DEQUEST 2010", 2010, THERMPHOS JAPAN LTD |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3045563A1 (en) * | 2015-01-16 | 2016-07-20 | Nihon Hyomen Kagaku Kabushiki Kaisha | Treatment liquid for trivalent chromium conversion coating and method of treatment of metal substrate |
CN105803437A (en) * | 2015-01-16 | 2016-07-27 | 日本表面化学株式会社 | Treatment liquid for trivalent chromium conversion coating and treatment method of metal substrate |
US10260151B2 (en) | 2015-01-16 | 2019-04-16 | Nippon Hyomen Kagaku Kabushiki Kaisha | Treatment liquid for trivalent chromium conversion coating and treatment method of metal substrate |
CN105803437B (en) * | 2015-01-16 | 2019-12-24 | 日本表面化学株式会社 | Trivalent chromium chemical conversion coating treatment liquid and method for treating metal substrate |
CN115413300A (en) * | 2021-03-31 | 2022-11-29 | 油研工业股份有限公司 | Chemical conversion treatment liquid and method for producing member having chemical conversion coating film on member surface |
EP4108805A4 (en) * | 2021-03-31 | 2023-09-20 | Yuken Industry Co., Ltd. | Chemical conversion treatment liquid, and method for manufacturing member in which chemical conversion film is provided on surface |
CN115413300B (en) * | 2021-03-31 | 2023-11-21 | 油研工业股份有限公司 | Chemical conversion treatment liquid and method for producing member having chemical conversion coating film on surface of member |
CN114875395A (en) * | 2022-03-31 | 2022-08-09 | 潍坊国一铝材有限公司 | Electrophoretic galvanized iron product and surface treatment method thereof |
Also Published As
Publication number | Publication date |
---|---|
JP2014159627A (en) | 2014-09-04 |
EP2759621B1 (en) | 2021-06-02 |
JP6216936B2 (en) | 2017-10-25 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2336390B1 (en) | Composition for chemical conversion treatment and process for production of member having black coating by using the composition | |
US9797044B2 (en) | Aqueous acidic composition for forming chromium-containing chemical conversion coating on iron-based member, and iron-based member having chemical conversion coating formed using the composition | |
JP5130226B2 (en) | Aqueous reaction solution and method for passivating workpieces with zinc or zinc alloy surfaces | |
EP2759621B1 (en) | Reactive-type chemical conversion treatment composition and production method of member with chemical conversion coated surface | |
KR20060126752A (en) | Chrome-free passivating solution | |
EP2492372A1 (en) | Aqueous solution and method for the formation of a passivation layer | |
CN102011118B (en) | Trivalent chromium passivating agent for zinc and zinc alloy coatings | |
US9915006B2 (en) | Reactive-type chemical conversion treatment composition and production method of member with chemical conversion coated surface | |
EP2385154A1 (en) | Composition for chemical conversion coating, and member equipped with chemical conversion coating film comprising the composition | |
JP6882340B2 (en) | By contacting an aqueous treatment solution for forming a chemical conversion film on a zinc surface or a zinc alloy surface, a concentrate for preparing the aqueous treatment solution, a kit containing the concentrate, and the aqueous treatment solution. Method of forming a chemical conversion film on a workpiece having a zinc film or a zinc alloy film | |
US11851766B2 (en) | Chemical conversion treatment liquid and production method for member having surface provided with chemical conversion film | |
EP3239355B1 (en) | Trivalent chromium chemical conversion liquid for zinc or zinc alloy bases | |
KR20140044785A (en) | Processes and compositions for improving corrosion performance of zirconium oxide pretreated zinc surfaces | |
US9435047B2 (en) | Process for corrosion protection of iron containing materials | |
WO2022209019A1 (en) | Chemical conversion treatment liquid, and method for manufacturing member in which chemical conversion film is provided on surface | |
JP2005179738A (en) | Method of producing surface treated steel sheet |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20140123 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
AX | Request for extension of the european patent |
Extension state: BA ME |
|
R17P | Request for examination filed (corrected) |
Effective date: 20150129 |
|
RBV | Designated contracting states (corrected) |
Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: EXAMINATION IS IN PROGRESS |
|
17Q | First examination report despatched |
Effective date: 20171219 |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: GRANT OF PATENT IS INTENDED |
|
INTG | Intention to grant announced |
Effective date: 20201221 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE PATENT HAS BEEN GRANTED |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: REF Ref document number: 1398496 Country of ref document: AT Kind code of ref document: T Effective date: 20210615 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 602014077837 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG9D |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: HR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20210602 Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20210902 Ref country code: LT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20210602 Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20210602 |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: MP Effective date: 20210602 |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: MK05 Ref document number: 1398496 Country of ref document: AT Kind code of ref document: T Effective date: 20210602 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20210903 Ref country code: LV Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20210602 Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20210602 Ref country code: RS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20210602 Ref country code: NO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20210902 Ref country code: PL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20210602 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20210602 Ref country code: NL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20210602 Ref country code: RO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20210602 Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20211004 Ref country code: AT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20210602 Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20210602 Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20210602 Ref country code: SM Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20210602 Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20210602 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 602014077837 Country of ref document: DE |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20210602 |
|
26N | No opposition filed |
Effective date: 20220303 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20210602 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MC Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20210602 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20220123 |
|
REG | Reference to a national code |
Ref country code: BE Ref legal event code: MM Effective date: 20220131 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20220123 Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20220123 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20220131 Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20220131 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20220131 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20220131 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20220123 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20230120 Year of fee payment: 10 Ref country code: DE Payment date: 20230123 Year of fee payment: 10 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: HU Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO Effective date: 20140123 |