WO2022024831A1 - 化成処理液及びそれを用いた化成処理方法、並びに化成皮膜 - Google Patents
化成処理液及びそれを用いた化成処理方法、並びに化成皮膜 Download PDFInfo
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- WO2022024831A1 WO2022024831A1 PCT/JP2021/026915 JP2021026915W WO2022024831A1 WO 2022024831 A1 WO2022024831 A1 WO 2022024831A1 JP 2021026915 W JP2021026915 W JP 2021026915W WO 2022024831 A1 WO2022024831 A1 WO 2022024831A1
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- chemical conversion
- ion
- ions
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- treatment liquid
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- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- WXHLLJAMBQLULT-UHFFFAOYSA-N 2-[[6-[4-(2-hydroxyethyl)piperazin-1-yl]-2-methylpyrimidin-4-yl]amino]-n-(2-methyl-6-sulfanylphenyl)-1,3-thiazole-5-carboxamide;hydrate Chemical compound O.C=1C(N2CCN(CCO)CC2)=NC(C)=NC=1NC(S1)=NC=C1C(=O)NC1=C(C)C=CC=C1S WXHLLJAMBQLULT-UHFFFAOYSA-N 0.000 description 1
- ZFQCFWRSIBGRFL-UHFFFAOYSA-B 2-hydroxypropane-1,2,3-tricarboxylate;zirconium(4+) Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O ZFQCFWRSIBGRFL-UHFFFAOYSA-B 0.000 description 1
- LYPJRFIBDHNQLY-UHFFFAOYSA-J 2-hydroxypropanoate;zirconium(4+) Chemical compound [Zr+4].CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O LYPJRFIBDHNQLY-UHFFFAOYSA-J 0.000 description 1
- BDSSZTXPZHIYHM-UHFFFAOYSA-N 2-phenoxypropanoyl chloride Chemical compound ClC(=O)C(C)OC1=CC=CC=C1 BDSSZTXPZHIYHM-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
- SJZRECIVHVDYJC-UHFFFAOYSA-N 4-hydroxybutyric acid Chemical compound OCCCC(O)=O SJZRECIVHVDYJC-UHFFFAOYSA-N 0.000 description 1
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 1
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- RBNPOMFGQQGHHO-UWTATZPHSA-N D-glyceric acid Chemical compound OC[C@@H](O)C(O)=O RBNPOMFGQQGHHO-UWTATZPHSA-N 0.000 description 1
- RGHNJXZEOKUKBD-MBMOQRBOSA-N D-mannonic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)C(O)=O RGHNJXZEOKUKBD-MBMOQRBOSA-N 0.000 description 1
- QXKAIJAYHKCRRA-FLRLBIABSA-N D-xylonic acid Chemical compound OC[C@@H](O)[C@H](O)[C@@H](O)C(O)=O QXKAIJAYHKCRRA-FLRLBIABSA-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
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 1
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 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
- 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
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- HSSJULAPNNGXFW-UHFFFAOYSA-N [Co].[Zn] Chemical compound [Co].[Zn] HSSJULAPNNGXFW-UHFFFAOYSA-N 0.000 description 1
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229940009827 aluminum acetate Drugs 0.000 description 1
- 229940118662 aluminum carbonate Drugs 0.000 description 1
- 229940063656 aluminum chloride Drugs 0.000 description 1
- 229940010048 aluminum sulfate Drugs 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- LNTHITQWFMADLM-UHFFFAOYSA-N anhydrous gallic acid Natural products OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 235000003704 aspartic acid Nutrition 0.000 description 1
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 1
- 239000006172 buffering agent Substances 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 229940043430 calcium compound Drugs 0.000 description 1
- 150000001674 calcium compounds Chemical class 0.000 description 1
- 150000001734 carboxylic acid salts Chemical class 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 150000001785 cerium compounds Chemical class 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
- 150000003841 chloride salts Chemical class 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 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
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 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
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000001514 detection method 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
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000013051 drainage agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 235000011087 fumaric 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
- 229940074391 gallic acid Drugs 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- 229940093915 gynecological organic acid Drugs 0.000 description 1
- XDBSEZHMWGHVIL-UHFFFAOYSA-M hydroxy(dioxo)vanadium Chemical compound O[V](=O)=O XDBSEZHMWGHVIL-UHFFFAOYSA-M 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 1
- 229910052912 lithium silicate Inorganic materials 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- 229940049920 malate Drugs 0.000 description 1
- BJEPYKJPYRNKOW-UWTATZPHSA-M malate ion Chemical compound [O-]C(=O)[C@H](O)CC(O)=O BJEPYKJPYRNKOW-UWTATZPHSA-M 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
- 150000002697 manganese compounds Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- LYTNHSCLZRMKON-UHFFFAOYSA-L oxygen(2-);zirconium(4+);diacetate Chemical compound [O-2].[Zr+4].CC([O-])=O.CC([O-])=O LYTNHSCLZRMKON-UHFFFAOYSA-L 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 239000004302 potassium sorbate Substances 0.000 description 1
- 235000010241 potassium sorbate Nutrition 0.000 description 1
- 229940069338 potassium sorbate Drugs 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- POWFTOSLLWLEBN-UHFFFAOYSA-N tetrasodium;silicate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-][Si]([O-])([O-])[O-] POWFTOSLLWLEBN-UHFFFAOYSA-N 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- GZCWPZJOEIAXRU-UHFFFAOYSA-N tin zinc Chemical compound [Zn].[Sn] GZCWPZJOEIAXRU-UHFFFAOYSA-N 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 150000003682 vanadium compounds Chemical class 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- XJUNLJFOHNHSAR-UHFFFAOYSA-J zirconium(4+);dicarbonate Chemical compound [Zr+4].[O-]C([O-])=O.[O-]C([O-])=O XJUNLJFOHNHSAR-UHFFFAOYSA-J 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 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
- 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
- C23C22/40—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 molybdates, tungstates or vanadates
-
- 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 liquid, a chemical conversion treatment method using the chemical conversion treatment liquid, and a chemical conversion film.
- the present inventors have completed the present invention as a result of diligent research to achieve the above-mentioned problems. That is, the present invention provides the following.
- the at least one carboxylic acid ion Carboxylic acid ion that can form a complex with trivalent chromium ion, Carboxylic acid ions that can form complexes with zirconium ions, The chemical conversion treatment liquid according to [1].
- the chemical conversion treatment liquid contains at least one organic acid or a salt thereof selected from the group consisting of a monocarboxylic acid or a salt thereof, a dicarboxylic acid or a salt thereof, an aromatic carboxylic acid or a salt thereof, an amino acid or a salt thereof, [1] to [13].
- the chemical conversion treatment liquid according to any one of the items.
- a chemical conversion treatment method comprising contacting the chemical conversion treatment liquid according to any one of [1] to [14] with the surface of a metal substrate.
- the chemical conversion treatment method according to [15] wherein the metal substrate or the surface thereof is zinc or a zinc alloy.
- a chemical conversion film formed on the surface of a metal substrate which is formed by using the chemical conversion treatment liquid according to any one of [1] to [14].
- [18] A chemical conversion film formed on the surface of a metal substrate. (A) Ingredients selected from metallic chromium, trivalent chromium ions, and trivalent chromium compounds, and (B) Components selected from metallic zirconium, zirconium ions, and zirconium compounds, (C) Ingredients selected from metallic aluminum, aluminum ions, and aluminum compounds, and (D) Ingredients selected from metallic silicon, silicon ions, and silicon compounds, and Including (E) A chemical conversion film containing no fluorine atom, fluorine ion, or fluorine compound.
- the chemical conversion treatment liquid of the present invention contains trivalent chromium ion, zirconium ion, aluminum ion, at least one carboxylic acid ion, at least one oxidizing agent, and at least one silicon compound, and is fluorine. It does not contain ions and fluorine compounds, and does not contain hexavalent chromium ions.
- the chemical conversion treatment liquid of the present invention contains trivalent chromium ions.
- trivalent chromium ions By containing trivalent chromium ions in the chemical conversion treatment liquid, excellent corrosion resistance can be obtained.
- the content of trivalent chromium ions in the chemical conversion treatment liquid is preferably 5 to 100 mmol / L. In the present invention, the use of trivalent chromium in such a low concentration range is economically advantageous for wastewater treatment.
- the content of trivalent chromium ions in the chemical conversion treatment liquid is more preferably 7 to 97 mmol / L, further preferably 8 to 96 mmol / L, and most preferably 15 to 39 mmol / L.
- the trivalent chromium compound that provides trivalent chromium ions is not particularly limited, but is preferably water-soluble.
- the trivalent chromium compound include trivalent chromium salts such as chromium chloride, chromium sulfate, chromium nitrate, chromium phosphate, and chromium acetate.
- trivalent chromium salts such as chromium chloride, chromium sulfate, chromium nitrate, chromium phosphate, and chromium acetate.
- hexavalent chromium ions such as chromic acid and dichromate can be reduced to trivalent chromium ions with a reducing agent.
- These trivalent chromium compounds may be used alone or in combination of two or more.
- the chemical conversion treatment liquid of the present invention contains zirconium ions.
- zirconium ions By containing zirconium ions in the chemical conversion treatment liquid together with aluminum ions, the film-thickening effect of the silicon compound can be obtained, and the corrosion resistance can be further enhanced.
- the content of zirconium ion in the chemical conversion treatment liquid is preferably 0.01 to 5 mmol / L, more preferably 0.05 to 2.2 mmol / L, and further preferably 0.06 to 2.2 mmol / L. It is L, and most preferably 0.1 to 0.6 mmol / L.
- the zirconium compound that provides the zirconium ion is not particularly limited, but is preferably water-soluble.
- zirconium compound examples include inorganic zirconium compounds such as zirconium nitrate, zirconyl nitrate, ammonium zirconite nitrate, zirconyl chloride, zirconyl sulfate, zirconium carbonate, zirconyl ammonium carbonate, potassium zirconyl carbonate, sodium zirconyl carbonate, lithium zirconyl carbonate and the like, and salts thereof.
- examples thereof include organic zirconium compounds such as zirconyl acetate, zirconium lactate, zirconium tartrate, zirconium malate and zirconium citrate.
- the zirconium compound is zirconyl nitrate and zirconyl chloride. These zirconium compounds may be used alone or in combination of two or more.
- the chemical conversion treatment liquid of the present invention contains aluminum ions.
- the content of aluminum ions in the chemical conversion treatment liquid is preferably 0.01 to 0.30 g / L, more preferably 0.02 to 0.30 g / L, and further preferably 0.04 to 0. It is 11 g / L.
- the aluminum compound that provides aluminum ions is not particularly limited, but is preferably water-soluble. Examples of the aluminum compound include aluminum nitrate, aluminum chloride, aluminum sulfate, aluminum acetate, aluminum carbonate and the like. Preferably, the aluminum compound is aluminum nitrate, aluminum chloride and aluminum sulfate. These aluminum compounds may be used alone or in combination of two or more.
- the chemical conversion treatment liquid of the present invention contains at least one carboxylic acid ion.
- the total content of carboxylic acid ions in the chemical conversion treatment liquid is preferably 8 to 132 mmol / L, more preferably 12.2 to 127 mmol / L, still more preferably 20 to 52 mmol / L, and most preferably. Is 21.2 to 52 mmol / L.
- the at least one carboxylic acid ion preferably contains one or more carboxylic acid ions selected from the group consisting of a dicarboxylic acid ion, a hydroxy acid ion and an aldonic acid ion.
- Examples of the dicarboxylic acid ion include oxalate ion, malonic acid ion, adipic acid ion, suberic acid ion, phthalate ion, isophthalic acid ion, terephthalic acid ion, fumarate ion and the like.
- Examples of the hydroxy acid ion include lactic acid ion, malic acid ion, citric acid ion, tartaric acid ion, glycolate ion, hydroxybutyric acid ion, salicylate ion, gallic acid ion, kumalic acid ion and the like.
- the hydroxy acid ion preferably contains one or more hydroxy acid ions selected from the group consisting of lactic acid ion, malate ion, citric acid ion, tartrate ion and glycolic acid ion.
- the aldonic acid ion include a gluconate ion, a galactonate ion, a mannonate ion, a glycerate ion, an ascorbic acid ion, and a xylonic acid ion.
- the aldonic acid ion preferably contains one or more aldonic acid ions selected from the group consisting of gluconate ion, galactate ion and mannonate ion.
- the at least one carboxylic acid ion preferably contains a carboxylic acid ion capable of forming a complex with a trivalent chromium ion and a carboxylic acid ion capable of forming a complex with a zirconium ion.
- the trivalent chromium ion and the zirconium ion can be stabilized by forming a complex with the trivalent chromium ion and the zirconium ion.
- the molar ratio (carboxylic acid / Cr 3+ ) of the carboxylic acid ion capable of forming a complex with the trivalent chromium ion and the trivalent chromium ion is preferably 0.3 to 3.0, and more preferably 0. It is .3 to 2.2, and more preferably 0.5 to 2.0.
- the molar ratio of carboxylic acid ion to zirconium ion (carboxylic acid / Zr 4+ ) capable of forming a complex with zirconium ion is preferably 0.1 to 4.0, more preferably 0.5. It is ⁇ 4.0, more preferably 0.5 to 3.3, and most preferably 1.0 to 3.0.
- the carboxylic acid ion capable of forming a complex with the trivalent chromium ion preferably contains one or more dicarboxylic acid ions selected from the group consisting of oxalate ion and malonic acid ion.
- the carboxylic acid ion capable of forming a complex with trivalent chromium ion is particularly preferably oxalic acid.
- the carboxylic acid ion capable of forming a complex with the zirconium ion is preferably citric acid, lactic acid, gluconic acid or the like.
- the carboxylic acid or a salt thereof that provides the carboxylic acid ion is not particularly limited, but is preferably water-soluble.
- carboxylic acids examples include oxalic acid, malonic acid, adipic acid, suberic acid, phthalic acid, isophthalic acid, terephthalic acid, fumaric acid, lactic acid, malic acid, citric acid, tartrate acid, glycolic acid, hydroxybutyric acid and salicylic acid. , Glycoic acid, kumalic acid, gluconic acid, galactic acid, mannonic acid, glyceric acid, ascorbic acid, xylonic acid and the like.
- carboxylic acid salt include alkali metal salts such as potassium and sodium, alkaline earth metal salts such as calcium and magnesium, and ammonium salts. These carboxylic acids or salts thereof may be used alone or in combination of two or more.
- the chemical conversion treatment liquid of the present invention may contain at least one oxidizing agent.
- an oxidizing agent in the chemical conversion treatment liquid, the formation of a chemical conversion film can be promoted, and a better appearance and corrosion resistance can be obtained.
- the total content of the oxidizing agent in the chemical conversion treatment liquid is preferably 0.5 to 30 g / L, and more preferably 1.0 to 10 g / L.
- the oxidizing agent is not particularly limited, but is preferably water-soluble.
- the oxidizing agent examples include nitrate, nitrite, sulfuric acid, sulfite, persulfate, phosphoric acid, hydrochloric acid, bromic acid, chloric acid, hypochlorous acid, hydrogen peroxide, permanganic acid, metavanadic acid, tungsten acid and molybdenum acid. , And their salts and the like.
- the oxidant is preferably nitric acid and salts thereof that provide nitrate ions.
- the nitrate compound that provides nitrate ions is not particularly limited, but is preferably water-soluble.
- nitrate examples include ammonium nitrate, sodium nitrate, potassium nitrate, lithium nitrate, chromium nitrate, aluminum nitrate, zirconyl nitrate, cobalt nitrate and the like. These nitric acids and salts thereof may be used alone or in combination of two or more.
- the total content of nitric acid and nitrate that provides nitrate ions in the chemical conversion treatment liquid is preferably 1.5 to 20 g / L, more preferably 1.5 to 17.9 g / L as nitrate ions. More preferably, it is 2.8 to 7.6 g / L.
- the chemical conversion treatment liquid of the present invention contains at least one silicon compound.
- the total content of the silicon compound in the chemical conversion treatment liquid is preferably 0.5 to 11 g / L, more preferably 0.6 to 9.8 g / L, and further preferably 2 to 8. It is 5 g / L.
- the silicon compound is not particularly limited, but is preferably water-soluble. Examples of the silicon compound include colloidal silica, silane coupling agent, sodium silicate, sodium orthosilicate, sodium metasilicate, potassium silicate, potassium metasilicate, lithium silicate, alkyl silicates and the like.
- the silicon compound is preferably colloidal silica.
- the colloidal silica is not particularly limited, and examples thereof include spherical colloidal silica and chain colloidal silica.
- the spherical colloidal silica is not particularly limited, and for example, Nissan Chemical Industries, Ltd. Snowtex XS, Snowtex S, Snowtex 30, Snowtex YL, Snowtex ZL, Snowtex OXS, Snowtex OS, Snowtex O, Snow.
- the chain colloidal silica is not particularly limited, and examples thereof include Snowtex UP and Snowtex OUP manufactured by Nissan Chemical Industries, Ltd. All of these are available as commercial products. Particularly preferred is spherical colloidal silica. These silicon compounds may be used alone or in combination of two or more.
- the chemical conversion treatment liquid of the present invention is a fluorine-free chemical conversion treatment liquid that does not contain fluorine ions and fluorine compounds. Fluorine ions or fluorine compounds are known to stabilize zirconium ions in a chemical conversion treatment solution and contribute to the film thickening effect of the silicon compound.
- the zirconium ion is stabilized by containing at least one kind of carboxylic acid ion. Further, by containing zirconium ion and aluminum ion, a film-thickening effect due to the silicon compound can be obtained, and corrosion resistance can be further enhanced.
- does not contain fluorine ions and fluorine compounds means that the measured value by a general fluorine analysis method is not more than the detection limit value.
- the analysis method include an ion chromatograph method and a lanthanum-alizarin complexone absorptiometry method.
- the chemical conversion treatment liquid of the present invention does not contain hexavalent chromium ions. Further, the chemical conversion treatment liquid of the present invention can form an excellent corrosion resistant film even if it does not contain cobalt ions or cobalt compounds. Therefore, the chemical conversion treatment liquid of the present invention preferably does not contain cobalt ions and cobalt compounds. However, it may further contain cobalt ions or cobalt compounds. When a cobalt ion or a cobalt compound is contained, the content thereof in the chemical conversion treatment liquid is preferably 300 mmol / L or less, more preferably 100 mmol / L or less, and further preferably 50 mmol / L or less as Co. be.
- the cobalt compound that provides the cobalt ion is not particularly limited, but is preferably water-soluble.
- Examples of the cobalt compound include cobalt nitrate, cobalt chloride, and cobalt sulfate. These cobalt compounds may be used alone or in combination of two or more.
- the chemical conversion treatment liquid of the present invention may contain a preservative to prevent mold.
- the preservative is not particularly limited, and examples thereof include sorbic acid and its salt, isothiazolinone derivative, dehydroacetic acid and its salt, benzoic acid and its salt and the like. These preservatives may be used alone or in combination of two or more.
- the content of the preservative in the chemical conversion treatment liquid may be an appropriately required amount according to its efficacy.
- the content thereof in the chemical conversion treatment liquid is preferably 100 mg / L or less, and more preferably 1 to 5 mg / L.
- the chemical conversion treatment liquid of the present invention is a water-soluble metal salt containing a metal selected from the group consisting of V, Ti, W, Zr, Mn, Mo, Ta, Ce, Sr and Fe in order to further improve corrosion resistance. May include.
- the water-soluble metal salt include nitrates, chloride salts, sulfates and the like. These water-soluble metal salts may be used alone or in combination of two or more.
- the content of the water-soluble metal salt in the chemical conversion treatment liquid is preferably 0.1 g / L to 1.5 g / L, and more preferably 0.2 g / L to 1.0 g / L.
- the chemical conversion treatment liquid of the present invention may contain a friction modifier for adjusting the friction on the surface of the formed chemical conversion film.
- the friction modifier is not particularly limited, and examples thereof include surfactants such as anionic surfactants, nonionic surfactants and cationic surfactants, and organic polymers such as polyethylene and polypropylene. These friction modifiers may be used alone or in combination of two or more.
- the content of the friction modifier in the chemical conversion treatment liquid is preferably 1 mg / L to 5 g / L, and more preferably 5 mg / L to 2 g / L.
- the chemical conversion treatment liquid of the present invention contains an organic acid or a salt thereof other than the carboxylic acid or a salt thereof that provides at least one of the carboxylic acid ions as a buffering agent, a film accelerator, a drainage agent, an Fe dissolution inhibitor and the like. But it may be.
- the organic acid or a salt thereof contains at least one organic acid or a salt thereof selected from the group consisting of a monocarboxylic acid or a salt thereof, a dicarboxylic acid or a salt thereof, an aromatic carboxylic acid or a salt thereof, an amino acid or a salt thereof.
- Examples of the monocarboxylic acid include formic acid and acetic acid.
- Examples of the dicarboxylic acid include succinic acid, glutaric acid, maleic acid and the like.
- Examples of the aromatic carboxylic acid include sulfosalicylic acid and cinnamic acid.
- Examples of amino acids include glutamic acid, aspartic acid, glycine and the like.
- Examples of the salt include alkali metal salts such as potassium and sodium, alkaline earth metal salts such as calcium and magnesium, and ammonium salts. These organic acids or salts thereof may be used alone or in combination of two or more.
- the content of the organic acid or a salt thereof in the chemical conversion treatment liquid is preferably 0.1 g / L to 20 g / L, and more preferably 0.2 g / L to 10 g / L.
- the pH of the chemical conversion treatment solution of the present invention is preferably in the range of 1.5 to 3.5, more preferably in the range of 2.1 to 2.9.
- an inorganic acid such as nitric acid or hydrochloric acid or an alkaline agent such as an organic acid, ammonia, an ammonium salt, a caustic alkali, sodium carbonate, potassium carbonate or ammonium carbonate may be used.
- an organic acid such as nitric acid or hydrochloric acid
- an alkaline agent such as an organic acid, ammonia, an ammonium salt, a caustic alkali, sodium carbonate, potassium carbonate or ammonium carbonate
- the residue of the above components in the chemical conversion treatment liquid of the present invention is water.
- the method for forming a chemical conversion film on a metal substrate by using the chemical conversion treatment liquid of the present invention is not particularly limited, and a known method can be applied.
- the surface of the metal base material is brought into contact with the chemical conversion treatment liquid by a method such as immersing the metal base material in the chemical conversion treatment liquid.
- the temperature of the chemical conversion treatment liquid at that time is preferably 15 to 50 ° C, more preferably 25 to 40 ° C.
- the soaking time is preferably 10 to 90 seconds, more preferably 15 to 50 seconds.
- the metal base material used in the present invention is not particularly limited, and is, for example, various metals such as iron, nickel, copper, zinc, and aluminum, alloys thereof, or a metal whose surface is coated with a metal, and its shape.
- the examples are not particularly limited, and examples thereof include plate-shaped products such as steel plates and plated steel plates, and various shaped products such as rectangular bodies, cylinders, cylinders, and spherical objects.
- various shaped products include fastener parts such as bolts, nuts and washers, pipe parts such as fuel pipes, cast iron parts such as brake calipers and common rails, as well as connectors, plugs, housings, caps and seatbelt anchors. Can be mentioned.
- the metal that coats the surface of the metal substrate is not particularly limited, but zinc or a zinc alloy is preferable, and zinc or a zinc alloy plating is applied by a conventional method for coating.
- an acidic / neutral bath such as a sulfuric acid bath, a borofluoride bath, a potassium chloride bath, a sodium chloride bath, an ammonium chloride eclectic bath, a cyan bath, a zincate bath, or a pyrophosphate bath is used. Any of the alkaline baths such as, etc. may be used.
- the zinc alloy plating may be either an acidic bath or an alkaline bath.
- the zinc alloy plating examples include zinc-iron alloy plating, zinc-nickel alloy plating, zinc-cobalt alloy plating, and tin-zinc alloy plating.
- Zinc-nickel alloy plating is preferred.
- the thickness of the plating deposited on the substrate can be arbitrary, but it is preferably 1 ⁇ m or more, preferably 5 to 25 ⁇ m.
- pretreatment for example, washing with water, or washing with water and then nitric acid activity treatment is performed, and then the chemical conversion treatment solution of the present invention is used. Then, for example, a chemical conversion treatment is performed by a method such as a dipping treatment.
- the plating surface In order to activate the plating surface, it may be immersed in a dilute nitric acid solution (5% nitric acid or the like), a dilute sulfuric acid solution, a dilute hydrochloric acid solution, a dilute hydrofluoric acid solution or the like before the chemical conversion treatment. Conditions and processing operations other than the above can be performed according to the conventional hexavalent chromate processing method.
- the chemical conversion film formed by using the chemical conversion treatment liquid of the present invention preferably contains (1) neither metallic cobalt, cobalt ion, and a cobalt compound, and / or (2) fluorine atom, fluorine ion, and. Contains none of the fluorine compounds.
- the chemical conversion film of the present invention is a chemical conversion film formed on the surface of a metal base material, and comprises (a) a component selected from metallic chromium, a trivalent chromium ion, and a trivalent chromium compound, and (b) a metal.
- it does not contain any of fluorine atoms, fluorine ions, and fluorine compounds.
- the chemical conversion film preferably does not contain any of metallic cobalt, cobalt ions, and cobalt compounds.
- the content of the component (a) in the chemical conversion film is preferably 0.5 to 5 wt%, more preferably 1.7 to 3 wt% in terms of chromium.
- the content of the component (b) in the chemical conversion film is preferably 0.05 to 5 wt%, more preferably 0.1 to 3 wt% in terms of zirconium.
- the content of the component (c) in the chemical conversion film is preferably more than 0 wt% and 5 wt% or less, and more preferably more than 0 wt% and 3 wt% or less in terms of aluminum.
- the content of the component (d) in the chemical conversion film is preferably 2 to 20 wt%, more preferably 7 to 15 wt% in terms of silicon.
- the film thickness of the chemical conversion film of the present invention is preferably 0.1 to 1.5 ⁇ m, more preferably 0.2 to 1.2 ⁇ m.
- Examples 1 to 31 and Comparative Examples 1 to 12 (Test pieces)
- an M8 hexagonal bolt (material: iron) coated with zincate bath galvanized (NZ-110 manufactured by Dipsol) having a thickness of 8 ⁇ m was used as the galvanized test piece.
- the galvanized test piece was immersed in a 1% aqueous nitric acid solution at room temperature for 10 seconds, and then rinsed thoroughly with running tap water to clean the surface.
- the following chemical conversion treatment was performed on the galvanized test piece.
- the chemical conversion-treated test piece was thoroughly washed with tap water and ion-exchanged water, and then allowed to stand in an electric drying furnace maintained at 80 ° C. for 10 minutes to dry.
- (Chemical conversion treatment liquid) The following three types of stock solutions were prepared in advance, and these stock solutions were mixed to prepare chemical conversion treatment solutions shown in Tables 1 to 5 (compounds or product names used in Examples and Comparative Examples are shown in Tables 6 and 7. ). After mixing, the pH was adjusted with caustic soda.
- the stock solution 1 was prepared by mixing the following compounds. Trivalent chromium compound, Aluminum compounds (Note that Comparative Examples 1 and 3 do not contain an aluminum compound, and in Comparative Examples 4 to 11, a cerium compound, a vanadium compound, a calcium compound, a magnesium compound, a titanium compound, a manganese compound, and a nickel compound, respectively, instead of the aluminum compound. , And iron compounds were used.),.
- Carboxylic acid A The nitrate (only in Examples 17 and 19) and the aqueous stock solution 2 were prepared by mixing the following compounds (note that the stock solution 2 is not used in Comparative Example 12).
- the film thickness of the chemical conversion film was measured by an X-ray photoelectron spectroscopy analyzer.
- the film thickness of each example was 0.2 to 1.2 ⁇ m.
- Comparative Example 1 is a chemical conversion treatment liquid containing no aluminum ion and a silicon compound, and is inferior in corrosion resistance.
- Comparative Example 2 is a chemical conversion treatment liquid containing aluminum ions but not a silicon compound, and is inferior in corrosion resistance (aluminum ions alone do not improve corrosion resistance, and it is considered that aluminum ions have no effect of imparting corrosion resistance).
- Comparative Example 3 is a chemical conversion treatment liquid containing a silicon-containing compound but not containing aluminum ions, and is inferior in corrosion resistance (in the absence of aluminum ions, it is considered that the film-thickening effect of the silicon compound is not exhibited).
- Comparative Examples 4 to 11 are chemical conversion treatment liquids containing a silicon compound but to which metal ions other than aluminum ions are added, and are inferior in corrosion resistance (metal ions other than aluminum ions do not improve the corrosion resistance).
- Comparative Example 12 is a chemical conversion treatment liquid containing aluminum ions and silicon compounds but not zirconium ions, and is inferior in corrosion resistance.
Abstract
Description
すなわち、本発明は、以下を提供する。
[1]
3価クロムイオンと、
ジルコニウムイオンと、
アルミニウムイオンと、
少なくとも1種のカルボン酸イオンと、
少なくとも1種のケイ素化合物と、
を含み、
フッ素イオン及びフッ素化合物を含まない化成処理液。
[2]
前記少なくとも1種のカルボン酸イオンが、
3価クロムイオンと錯体を形成することができるカルボン酸イオンと、
ジルコニウムイオンと錯体を形成することができるカルボン酸イオンと、
を含む、[1]に記載の化成処理液。
[3]
前記少なくとも1種のカルボン酸イオンが、ジカルボン酸イオン、ヒドロキシ酸イオン及びアルドン酸イオンからなる群より選ばれる1種以上のカルボン酸イオンを含む、[1]又は[2]に記載の化成処理液。
[4]
前記ジカルボン酸イオンがシュウ酸イオン及びマロン酸イオンからなる群より選ばれる1種以上のジカルボン酸イオンを含む、[3]に記載の化成処理液。
[5]
前記ヒドロキシ酸イオンが乳酸イオン、リンゴ酸イオン、クエン酸イオン、酒石酸イオン及びグリコール酸イオンからなる群より選ばれる1種以上のヒドロキシ酸イオンを含む、[3]に記載の化成処理液。
[6]
前記アルドン酸イオンがグルコン酸イオン、ガラクトン酸イオン及びマンノン酸イオンからなる群より選ばれる1種以上のアルドン酸イオンを含む、[3]に記載の化成処理液。
[7]
さらに、少なくとも1種の酸化剤を含む、[1]~[6]のいずれか1項に記載の化成処理液。
[8]
前記少なくとも1種の酸化剤が硝酸イオンを提供する硝酸及び硝酸塩を含む、[7]に記載の化成処理液。
[9]
コバルトイオン及びコバルト化合物、及び/又は6価クロムイオンを含まない、[1]~[8]のいずれか1項に記載の化成処理液。
[10]
さらに、ソルビン酸及びその塩、イソチアゾリノン誘導体、デヒドロ酢酸及びその塩、並びに安息香酸及びその塩からなる群より選ばれる1種以上の防腐剤を含む、[1]~[9]のいずれか1項に記載の化成処理液。
[11]
さらに、V、Ti、W、Zr、Mn、Mo、Ta、Ce、Sr及びFeからなる群より選ばれる金属を含む水溶性金属塩を1種以上含む、[1]~[10]のいずれか1項に記載の化成処理液。
[12]
さらに、界面活性剤及び有機ポリマーからなる群より選ばれる1種以上の摩擦調整剤を含む、[1]~[11]のいずれか1項に記載の化成処理液。
[13]
前記少なくとも1種のケイ素化合物がコロイダルシリカを含む、[1]~[12]のいずれか1項に記載の化成処理液。
[14]
さらに、モノカルボン酸又はその塩、ジカルボン酸又はその塩、芳香族カルボン酸又はその塩、アミノ酸又はその塩からなる群より選ばれる有機酸又はその塩を1種以上含む、[1]~[13]のいずれか1項に記載の化成処理液。
[15]
[1]~[14]のいずれか1項に記載の化成処理液を金属基材の表面と接触させることを含む化成処理方法。
[16]
前記金属基材又はその表面が亜鉛又は亜鉛合金である、[15]に記載の化成処理方法。
[17]
金属基材の表面に形成された化成皮膜であって、[1]~[14]のいずれか1項に記載の化成処理液を用いて形成された化成皮膜。
[18]
金属基材の表面に形成された化成皮膜であって、
(a)金属クロム、三価クロムイオン、及び三価クロム化合物から選ばれる成分と、
(b)金属ジルコニウム、ジルコニウムイオン、及びジルコニウム化合物から選ばれる成分と、
(c)金属アルミニウム、アルミニウムイオン、及びアルミニウム化合物から選ばれる成分と、
(d)金属ケイ素、ケイ素イオン、及びケイ素化合物から選ばれる成分と、
を含み、
(e)フッ素原子、フッ素イオン、及びフッ素化合物のいずれも含有しない
化成皮膜。
[19]
化成皮膜中の、成分(a)の含有量が、クロム換算で0.5~5wt%である、[18]に記載の化成皮膜。
[20]
化成皮膜中の、成分(d)の含有量が、ケイ素換算で2~20wt%である、[18]又は[19]に記載の化成皮膜。
[21]
化成皮膜中の、成分(b)の含有量が、ジルコニウム換算で0.05~5wt%である、[18]~[20]のいずれか1項に記載の化成皮膜。
[22]
化成皮膜中の、成分(c)の含有量が、アルミニウム換算で0wt%よりも多く5wt%以下である、[18]~[21]のいずれか1項に記載の化成皮膜。
[23]
化成皮膜の膜厚が0.1~1.5μmである、[17]~[22]のいずれか1項に記載の化成皮膜。
[24]
前記金属基材又はその表面が亜鉛又は亜鉛合金である、[17]~[23]のいずれか1項に記載の化成皮膜。
[25]
金属コバルト、コバルトイオン、及びコバルト化合物のいずれも含有しない[17]~[24]のいずれか1項に記載の化成皮膜。
ジカルボン酸イオンとしては、例えばシュウ酸イオン、マロン酸イオン、アジピン酸イオン、スベリン酸イオン、フタル酸イオン、イソフタル酸イオン、テレフタル酸イオン、フマル酸イオンなどが挙げられる。
ヒドロキシ酸イオンとしては、例えば乳酸イオン、リンゴ酸イオン、クエン酸イオン、酒石酸イオン、グリコール酸イオン、ヒドロキシ酪酸イオン、サリチル酸イオン、没食子酸イオン、クマル酸イオンなどが挙げられる。ヒドロキシ酸イオンは、好ましくは乳酸イオン、リンゴ酸イオン、クエン酸イオン、酒石酸イオン及びグリコール酸イオンからなる群より選ばれる1種以上のヒドロキシ酸イオンを含む。
アルドン酸イオンとしては、グルコン酸イオン、ガラクトン酸イオン、マンノン酸イオン、グリセリン酸イオン、アスコルビン酸イオン、キシロン酸イオンなどが挙げられる。アルドン酸イオンは、好ましくはグルコン酸イオン、ガラクトン酸イオン及びマンノン酸イオンからなる群より選ばれる1種以上のアルドン酸イオンを含む。
前記少なくとも1種のカルボン酸イオンは、好ましくは3価クロムイオンと錯体を形成することができるカルボン酸イオンと、ジルコニウムイオンと錯体を形成することができるカルボン酸イオンとを含む。これにより、3価クロムイオン及びジルコニウムイオンとの錯体形成により3価クロムイオン及びジルコニウムイオンを安定化することができる。3価クロムイオンと錯体を形成することができるカルボン酸イオンと3価クロムイオンとのモル比(カルボン酸/Cr3+)は、好ましくは0.3~3.0であり、より好ましくは0.3~2.2であり、さらに好ましくは0.5~2.0である。また、ジルコニウムイオンと錯体を形成することができるカルボン酸イオンとジルコニウムイオンとのモル比(カルボン酸/Zr4+)は、好ましくは0.1~4.0であり、より好ましくは0.5~4.0であり、さらに好ましくは0.5~3.3であり、最も好ましくは1.0~3.0である。3価クロムイオンと錯体を形成することができるカルボン酸イオンは、好ましくはシュウ酸イオン及びマロン酸イオンからなる群より選ばれる1種以上のジカルボン酸イオンを含む。3価クロムイオンと錯体を形成することができるカルボン酸イオンは、特に好ましくはシュウ酸である。ジルコニウムイオンと錯体を形成することができるカルボン酸イオンは、好ましくはクエン酸、乳酸、グルコン酸などである。
カルボン酸イオンを提供するカルボン酸又はその塩は、特に限定されるものではないが、水溶性であることが好ましい。このようなカルボン酸としては、例えばシュウ酸、マロン酸、アジピン酸、スベリン酸、フタル酸、イソフタル酸、テレフタル酸、フマル酸、乳酸、リンゴ酸、クエン酸、酒石酸、グリコール酸、ヒドロキシ酪酸、サリチル酸、没食子酸、クマル酸、グルコン酸、ガラクトン酸、マンノン酸、グリセリン酸、アスコルビン酸、キシロン酸などが挙げられる。また、カルボン酸の塩としては、例えばカリウム、ナトリウムなどのアルカリ金属の塩、カルシウム、マグネシウムなどのアルカリ土類金属の塩、アンモニウム塩などが挙げられる。これらのカルボン酸又はその塩は、単独で用いてもよいし、2種以上組み合わせて用いてもよい。
また、本発明の化成処理液は、コバルトイオン又はコバルト化合物を含有せずとも優れた耐食性皮膜を形成させることができる。したがって、本発明の化成処理液は、好ましくはコバルトイオン及びコバルト化合物を含まない。しかしながら、さらにコバルトイオン又はコバルト化合物を含有させてもよい。コバルトイオン又はコバルト化合物を含有させる場合、化成処理液中のその含有量は、Coとして、好ましくは300mmol/L以下であり、より好ましくは100mmol/L以下であり、さらに好ましくは50mmol/L以下である。コバルトイオンを提供するコバルト化合物は、特に限定されるものではないが、水溶性であることが好ましい。コバルト化合物としては、例えば硝酸コバルト、塩化コバルト、硫酸コバルトなどが挙げられる。これらのコバルト化合物は、単独で用いてもよいし、2種以上組み合わせて用いてもよい。
モノカルボン酸としては、例えばギ酸、酢酸などが挙げられる。
ジカルボン酸としては、例えばコハク酸、グルタル酸、マレイン酸などが挙げられる。
芳香族カルボン酸としては、例えばスルホサリチル酸、ケイ皮酸などが挙げられる。
アミノ酸としては、例えばグルタミン酸、アスパラギン酸、グリシンなどが挙げられる。
塩としては、例えばカリウム、ナトリウムなどのアルカリ金属の塩、カルシウム、マグネシウムなどのアルカリ土類金属の塩、アンモニウム塩などが挙げられる。
これらの有機酸又はその塩は、単独で用いてもよいし、2種以上組み合わせて用いてもよい。化成処理液中の有機酸又はその塩の含有量は、好ましくは0.1g/L~20g/Lであり、より好ましくは0.2g/L~10g/Lである。
本発明の化成処理液における上記成分の残分は水である。
本発明で用いる金属基材としては、特に制限はなく、例えば鉄、ニッケル、銅、亜鉛、アルミニウムなどの各種金属及びこれらの合金、あるいはそれらの表面を金属で被覆したものであって、その形状としては特に制限はなく、例えば鋼板、めっき鋼板などの板状物や、直方体、円柱、円筒、球状物などの形状品など種々のものが挙げられる。形状品として具体的には、例えばボルト、ナット、ワッシャーなどの締結部品、燃料パイプなどのパイプ部品、ブレーキキャリパー、コモンレールなどの鋳鉄部品の他、コネクタ、プラグ、ハウジング、口金、シートベルトアンカーなど種々のものが挙げられる。
前記金属基材の表面を被覆する金属としては、特に制限はないが、亜鉛又は亜鉛合金が好ましく、常法により亜鉛又は亜鉛合金めっきを施して被覆する。前記金属基材上に亜鉛めっきを析出させるには、硫酸浴、ホウフッ化浴、塩化カリウム浴、塩化ナトリウム浴、塩化アンモニウム折衷浴等の酸性・中性浴、シアン浴、ジンケート浴、ピロリン酸浴等のアルカリ性浴のいずれでも良い。また、亜鉛合金めっきは、酸性浴、アルカリ性浴のいずれでもよい。
また、亜鉛合金めっきとしては、亜鉛-鉄合金めっき、亜鉛-ニッケル合金めっき、亜鉛-コバルト合金めっき、錫-亜鉛合金めっき等が挙げられる。好ましくは、亜鉛-ニッケル合金めっきである。基材上に析出するめっきの厚みは任意とすることができるが、1μm以上、好ましくは5~25μm厚とするのがよい。
本発明では、このようにして基材上にめっきを析出させた後、必要に応じて適宜、前処理、例えば水洗、または水洗後、硝酸活性処理してから、本発明の化成処理液を用いて、例えば浸漬処理等の方法で化成処理を行う。めっき表面を活性化するために、化成処理前に希硝酸溶液(5%硝酸など)又は希硫酸溶液、希塩酸溶液、希フッ酸溶液などに浸漬させてもよい。上記以外の条件や処理操作は、従来の6価クロメート処理方法に準じて行うことができる。
化成皮膜中の、成分(a)の含有量は、クロム換算で、好ましくは0.5~5wt%であり、より好ましくは1.7~3wt%である。
化成皮膜中の、成分(b)の含有量は、ジルコニウム換算で、好ましくは0.05~5wt%であり、より好ましくは0.1~3wt%である。
化成皮膜中の、成分(c)の含有量は、アルミニウム換算で、好ましくは0wt%よりも多く5wt%以下であり、より好ましくは0wt%よりも多く3wt%以下である。
化成皮膜中の、成分(d)の含有量は、ケイ素換算で、好ましくは2~20wt%であり、より好ましくは7~15wt%である。
本発明の化成皮膜の膜厚は、好ましくは0.1~1.5μmであり、より好ましくは0.2~1.2μmである。
次に、実施例及び比較例により本発明を説明するが、本発明はこれらによって限定されるものではない。
(試験片)
亜鉛めっき試験片として、M8六角ボルト(材質:鉄)にジンケート浴亜鉛めっき(ディップソール製NZ-110)を厚さ8μm施したものを使用した。亜鉛めっきが施された試験片を常温の1%硝酸水溶液に10秒浸漬し、次いで水道水の流水で十分に濯ぎ、表面を清浄化した。次いで、亜鉛めっき試験片に以下の化成処理を行った。化成処理を行った試験片は、水道水とイオン交換水にて十分に洗浄したのち、80℃に保った電気乾燥炉にて10分間静置し乾燥させた。
予め下記の3種類の原液を調製し、これらの原液を混合して表1~5に示す化成処理液を調製した(実施例及び比較例で用いた化合物又は製品名を表6及び7に示す)。また、混合後、pHを苛性ソーダで調整した。
原液1は、以下の化合物を混合して調製した。
3価クロム化合物、
アルミニウム化合物(なお、比較例1及び3ではアルミニウム化合物を含まず、比較例4~11では、それぞれアルミニウム化合物の代わりにセリウム化合物、バナジウム化合物、カルシウム化合物、マグネシウム化合物、チタニウム化合物、マンガン化合物、ニッケル化合物、及び鉄化合物を用いた。)、
カルボン酸A、
硝酸塩(実施例17及び19のみ)、及び
水
原液2は、以下の化合物を混合して調製した(なお、比較例12では原液2を使用しない。)。
ジルコニウム化合物、
カルボン酸B、及び
水
原液3は、以下の化合物を混合して調製した。
ケイ素化合物(なお、比較例1及び2ではケイ素化合物を含まない。)、及び
水
調製した化成処理液を用い、前記試験片に対し表1~5に示す条件で浸漬処理を行った。
化成皮膜の外観は、均一性及び光沢の観点から評価した。結果を表1~5に示す。なお、評価基準は以下の通りである。
〇良:光沢のある均一な外観
△可:やや光沢の低い均一な外観
×不可:曇りのある光沢の低い不均一な外観
化成処理された試験片はJIS Z―2371に準じて中性塩水噴霧試験(以下NSS)を行い、白錆5%未満発生時間で耐食性を評価した。結果を表1~5に示す。
化成処理液における沈殿の有無で評価した。結果を表1~5に示す。なお、評価基準は以下の通りである。
○沈殿なし
△沈殿あり:本発明の効果に影響のない沈殿(許容範囲)
×沈殿あり:本発明の効果を阻害する沈殿(使用不可:一時的には沈殿しないが、経時で沈殿するものも含む)
化成皮膜の元素組成は、化成皮膜断面のエネルギー分散型X線分析装置(日本電子(株)JSM-6610LA)を用いて測定した(表8~11)。
化成皮膜の膜厚は、X線光電子分光分析装置により測定した。各実施例の膜厚は、0.2~1.2μmであった。
Claims (25)
- 3価クロムイオンと、
ジルコニウムイオンと、
アルミニウムイオンと、
少なくとも1種のカルボン酸イオンと、
少なくとも1種のケイ素化合物と、
を含み、
フッ素イオン及びフッ素化合物を含まない化成処理液。 - 前記少なくとも1種のカルボン酸イオンが、
3価クロムイオンと錯体を形成することができるカルボン酸イオンと、
ジルコニウムイオンと錯体を形成することができるカルボン酸イオンと、
を含む、請求項1に記載の化成処理液。 - 前記少なくとも1種のカルボン酸イオンが、ジカルボン酸イオン、ヒドロキシ酸イオン及びアルドン酸イオンからなる群より選ばれる1種以上のカルボン酸イオンを含む、請求項1又は2に記載の化成処理液。
- 前記ジカルボン酸イオンがシュウ酸イオン及びマロン酸イオンからなる群より選ばれる1種以上のジカルボン酸イオンを含む、請求項3に記載の化成処理液。
- 前記ヒドロキシ酸イオンが乳酸イオン、リンゴ酸イオン、クエン酸イオン、酒石酸イオン及びグリコール酸イオンからなる群より選ばれる1種以上のヒドロキシ酸イオンを含む、請求項3に記載の化成処理液。
- 前記アルドン酸イオンがグルコン酸イオン、ガラクトン酸イオン及びマンノン酸イオンからなる群より選ばれる1種以上のアルドン酸イオンを含む、請求項3に記載の化成処理液。
- さらに、少なくとも1種の酸化剤を含む、請求項1~6のいずれか1項に記載の化成処理液。
- 前記少なくとも1種の酸化剤が硝酸イオンを提供する硝酸及び硝酸塩を含む、請求項7に記載の化成処理液。
- コバルトイオン及びコバルト化合物、及び/又は6価クロムイオンを含まない、請求項1~8のいずれか1項に記載の化成処理液。
- さらに、ソルビン酸及びその塩、イソチアゾリノン誘導体、デヒドロ酢酸及びその塩、並びに安息香酸及びその塩からなる群より選ばれる1種以上の防腐剤を含む、請求項1~9のいずれか1項に記載の化成処理液。
- さらに、V、Ti、W、Zr、Mn、Mo、Ta、Ce、Sr及びFeからなる群より選ばれる金属を含む水溶性金属塩を1種以上含む、請求項1~10のいずれか1項に記載の化成処理液。
- さらに、界面活性剤及び有機ポリマーからなる群より選ばれる1種以上の摩擦調整剤を含む、請求項1~11のいずれか1項に記載の化成処理液。
- 前記少なくとも1種のケイ素化合物がコロイダルシリカを含む、請求項1~12のいずれか1項に記載の化成処理液。
- さらに、モノカルボン酸又はその塩、ジカルボン酸又はその塩、芳香族カルボン酸又はその塩、アミノ酸又はその塩からなる群より選ばれる有機酸又はその塩を1種以上含む、請求項1~13のいずれか1項に記載の化成処理液。
- 請求項1~14のいずれか1項に記載の化成処理液を金属基材の表面と接触させることを含む化成処理方法。
- 前記金属基材又はその表面が亜鉛又は亜鉛合金である、請求項15に記載の化成処理方法。
- 金属基材の表面に形成された化成皮膜であって、請求項1~14のいずれか1項に記載の化成処理液を用いて形成された化成皮膜。
- 金属基材の表面に形成された化成皮膜であって、
(a)金属クロム、三価クロムイオン、及び三価クロム化合物から選ばれる成分と、
(b)金属ジルコニウム、ジルコニウムイオン、及びジルコニウム化合物から選ばれる成分と、
(c)金属アルミニウム、アルミニウムイオン、及びアルミニウム化合物から選ばれる成分と、
(d)金属ケイ素、ケイ素イオン、及びケイ素化合物から選ばれる成分と、
を含み、
(e)フッ素原子、フッ素イオン、及びフッ素化合物のいずれも含有しない
化成皮膜。 - 化成皮膜中の、成分(a)の含有量が、クロム換算で0.5~5wt%である、請求項18に記載の化成皮膜。
- 化成皮膜中の、成分(d)の含有量が、ケイ素換算で2~20wt%である、請求項18又は19に記載の化成皮膜。
- 化成皮膜中の、成分(b)の含有量が、ジルコニウム換算で0.05~5wt%である、請求項18~20のいずれか1項に記載の化成皮膜。
- 化成皮膜中の、成分(c)の含有量が、アルミニウム換算で0wt%よりも多く5wt%以下である、請求項18~21のいずれか1項に記載の化成皮膜。
- 化成皮膜の膜厚が0.1~1.5μmである、請求項17~22のいずれか1項に記載の化成皮膜。
- 前記金属基材又はその表面が亜鉛又は亜鉛合金である、請求項17~23のいずれか1項に記載の化成皮膜。
- 金属コバルト、コバルトイオン、及びコバルト化合物のいずれも含有しない請求項17~24のいずれか1項に記載の化成皮膜。
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JP2006316334A (ja) * | 2005-05-16 | 2006-11-24 | Million Kagaku Kk | アルミニウム合金用ノンクロメート化成処理液およびこの化成処理液によるアルミニウム合金の化成処理方法 |
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JP2019052351A (ja) | 2017-09-14 | 2019-04-04 | ディップソール株式会社 | 亜鉛又は亜鉛合金基材用3価クロム化成処理液及びそれを用いた化成処理方法 |
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IT1393946B1 (it) * | 2009-04-21 | 2012-05-17 | Np Coil Dexter Ind Srl | Processo di trattamento in continuo di patinatura/satinatura chimica di leghe zinco-titanio |
JP2013249528A (ja) * | 2012-06-04 | 2013-12-12 | Dipsol Chemicals Co Ltd | アルミ変性コロイダルシリカを含有した3価クロム化成処理液 |
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JP2006316334A (ja) * | 2005-05-16 | 2006-11-24 | Million Kagaku Kk | アルミニウム合金用ノンクロメート化成処理液およびこの化成処理液によるアルミニウム合金の化成処理方法 |
JP2007239017A (ja) * | 2006-03-08 | 2007-09-20 | Nippon Paint Co Ltd | アルミニウム系金属材料の表面処理方法 |
WO2016104703A1 (ja) | 2014-12-26 | 2016-06-30 | ディップソール株式会社 | 亜鉛又は亜鉛合金基材用3価クロム化成処理液及び化成皮膜 |
JP2019052351A (ja) | 2017-09-14 | 2019-04-04 | ディップソール株式会社 | 亜鉛又は亜鉛合金基材用3価クロム化成処理液及びそれを用いた化成処理方法 |
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JP7133889B1 (ja) * | 2021-03-31 | 2022-09-09 | ユケン工業株式会社 | 化成処理液および化成皮膜をその表面に備える部材の製造方法 |
US11851766B2 (en) | 2021-03-31 | 2023-12-26 | Yuken Industry Co., Ltd. | Chemical conversion treatment liquid and production method for member having surface provided with chemical conversion film |
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JPWO2022024831A1 (ja) | 2022-02-03 |
US20230304160A1 (en) | 2023-09-28 |
TW202212629A (zh) | 2022-04-01 |
EP4190941A4 (en) | 2024-01-03 |
EP4190941A1 (en) | 2023-06-07 |
JP7368012B2 (ja) | 2023-10-24 |
CN116018427A (zh) | 2023-04-25 |
MX2022016568A (es) | 2023-06-02 |
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