KR20210113385A - A chemical conversion treatment agent, a method for manufacturing a metal material having a chemical conversion film, and a metal material having a chemical conversion film - Google Patents
A chemical conversion treatment agent, a method for manufacturing a metal material having a chemical conversion film, and a metal material having a chemical conversion film Download PDFInfo
- Publication number
- KR20210113385A KR20210113385A KR1020217026442A KR20217026442A KR20210113385A KR 20210113385 A KR20210113385 A KR 20210113385A KR 1020217026442 A KR1020217026442 A KR 1020217026442A KR 20217026442 A KR20217026442 A KR 20217026442A KR 20210113385 A KR20210113385 A KR 20210113385A
- Authority
- KR
- South Korea
- Prior art keywords
- chemical conversion
- acid
- ion
- conversion film
- metal material
- Prior art date
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- 239000000126 substance Substances 0.000 title claims abstract description 159
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 149
- 239000007769 metal material Substances 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims description 65
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 62
- 239000000980 acid dye Substances 0.000 claims abstract description 30
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 26
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 21
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 19
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000010936 titanium Substances 0.000 claims abstract description 18
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 18
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 17
- 239000011737 fluorine Substances 0.000 claims abstract description 17
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 16
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims abstract description 16
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 15
- 239000011651 chromium Substances 0.000 claims abstract description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052802 copper Inorganic materials 0.000 claims abstract description 14
- 239000010949 copper Substances 0.000 claims abstract description 14
- 229910052742 iron Inorganic materials 0.000 claims abstract description 13
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 12
- 239000010941 cobalt Substances 0.000 claims abstract description 12
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 12
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims abstract 2
- 238000005260 corrosion Methods 0.000 abstract description 10
- 230000007797 corrosion Effects 0.000 abstract description 10
- 150000002500 ions Chemical class 0.000 description 70
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- 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
- 230000000052 comparative effect Effects 0.000 description 4
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- 239000000243 solution Substances 0.000 description 4
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- DXIGZHYPWYIZLM-UHFFFAOYSA-J tetrafluorozirconium;dihydrofluoride Chemical compound F.F.F[Zr](F)(F)F DXIGZHYPWYIZLM-UHFFFAOYSA-J 0.000 description 4
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- 239000007864 aqueous solution Substances 0.000 description 3
- OIQPTROHQCGFEF-UHFFFAOYSA-L chembl1371409 Chemical compound [Na+].[Na+].OC1=CC=C2C=C(S([O-])(=O)=O)C=CC2=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 OIQPTROHQCGFEF-UHFFFAOYSA-L 0.000 description 3
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- 238000004040 coloring Methods 0.000 description 3
- GWFAVIIMQDUCRA-UHFFFAOYSA-L copper(ii) fluoride Chemical compound [F-].[F-].[Cu+2] GWFAVIIMQDUCRA-UHFFFAOYSA-L 0.000 description 3
- 238000005238 degreasing Methods 0.000 description 3
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- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 3
- 238000005246 galvanizing Methods 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 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 3
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- NFVUDQKTAWONMJ-UHFFFAOYSA-I pentafluorovanadium Chemical compound [F-].[F-].[F-].[F-].[F-].[V+5] NFVUDQKTAWONMJ-UHFFFAOYSA-I 0.000 description 3
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- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 2
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- HMEKVHWROSNWPD-UHFFFAOYSA-N Erioglaucine A Chemical compound [NH4+].[NH4+].C=1C=C(C(=C2C=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=2C(=CC=CC=2)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC(S([O-])(=O)=O)=C1 HMEKVHWROSNWPD-UHFFFAOYSA-N 0.000 description 2
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- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 2
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- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- AQBLLJNPHDIAPN-LNTINUHCSA-K iron(3+);(z)-4-oxopent-2-en-2-olate Chemical compound [Fe+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O AQBLLJNPHDIAPN-LNTINUHCSA-K 0.000 description 1
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 1
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 description 1
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 description 1
- FZGIHSNZYGFUGM-UHFFFAOYSA-L iron(ii) fluoride Chemical compound [F-].[F-].[Fe+2] FZGIHSNZYGFUGM-UHFFFAOYSA-L 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 239000005001 laminate film Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- QDLAGTHXVHQKRE-UHFFFAOYSA-N lichenxanthone Natural products COC1=CC(O)=C2C(=O)C3=C(C)C=C(OC)C=C3OC2=C1 QDLAGTHXVHQKRE-UHFFFAOYSA-N 0.000 description 1
- SXQCTESRRZBPHJ-UHFFFAOYSA-M lissamine rhodamine Chemical compound [Na+].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=C(S([O-])(=O)=O)C=C1S([O-])(=O)=O SXQCTESRRZBPHJ-UHFFFAOYSA-M 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- NYGZLYXAPMMJTE-UHFFFAOYSA-M metanil yellow Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC(N=NC=2C=CC(NC=3C=CC=CC=3)=CC=2)=C1 NYGZLYXAPMMJTE-UHFFFAOYSA-M 0.000 description 1
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JMXROTHPANUTOJ-UHFFFAOYSA-H naphthol green b Chemical compound [Na+].[Na+].[Na+].[Fe+3].C1=C(S([O-])(=O)=O)C=CC2=C(N=O)C([O-])=CC=C21.C1=C(S([O-])(=O)=O)C=CC2=C(N=O)C([O-])=CC=C21.C1=C(S([O-])(=O)=O)C=CC2=C(N=O)C([O-])=CC=C21 JMXROTHPANUTOJ-UHFFFAOYSA-H 0.000 description 1
- CTIQLGJVGNGFEW-UHFFFAOYSA-L naphthol yellow S Chemical compound [Na+].[Na+].C1=C(S([O-])(=O)=O)C=C2C([O-])=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 CTIQLGJVGNGFEW-UHFFFAOYSA-L 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- OGUCKKLSDGRKSH-UHFFFAOYSA-N oxalic acid oxovanadium Chemical compound [V].[O].C(C(=O)O)(=O)O OGUCKKLSDGRKSH-UHFFFAOYSA-N 0.000 description 1
- DQTJHJVUOOYAMD-UHFFFAOYSA-N oxotitanium(2+) dinitrate Chemical compound [O-][N+](=O)O[Ti](=O)O[N+]([O-])=O DQTJHJVUOOYAMD-UHFFFAOYSA-N 0.000 description 1
- DUSYNUCUMASASA-UHFFFAOYSA-N oxygen(2-);vanadium(4+) Chemical compound [O-2].[O-2].[V+4] DUSYNUCUMASASA-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 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
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 235000012736 patent blue V Nutrition 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- GVKCHTBDSMQENH-UHFFFAOYSA-L phloxine B Chemical compound [Na+].[Na+].[O-]C(=O)C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C([O-])=C(Br)C=C21 GVKCHTBDSMQENH-UHFFFAOYSA-L 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 235000019237 ponceau SX Nutrition 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 235000012752 quinoline yellow Nutrition 0.000 description 1
- FZUOVNMHEAPVBW-UHFFFAOYSA-L quinoline yellow ws Chemical compound [Na+].[Na+].O=C1C2=CC=CC=C2C(=O)C1C1=NC2=C(S([O-])(=O)=O)C=C(S(=O)(=O)[O-])C=C2C=C1 FZUOVNMHEAPVBW-UHFFFAOYSA-L 0.000 description 1
- 235000012739 red 2G Nutrition 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- AZJPTIGZZTZIDR-UHFFFAOYSA-L rose bengal Chemical compound [K+].[K+].[O-]C(=O)C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C1=C2C=C(I)C(=O)C(I)=C2OC2=C(I)C([O-])=C(I)C=C21 AZJPTIGZZTZIDR-UHFFFAOYSA-L 0.000 description 1
- 229960003138 rose bengal sodium Drugs 0.000 description 1
- LGZQSRCLLIPAEE-UHFFFAOYSA-M sodium 1-[(4-sulfonaphthalen-1-yl)diazenyl]naphthalen-2-olate Chemical compound [Na+].C1=CC=C2C(N=NC3=C4C=CC=CC4=CC=C3O)=CC=C(S([O-])(=O)=O)C2=C1 LGZQSRCLLIPAEE-UHFFFAOYSA-M 0.000 description 1
- UWMZZSRDUVJJDP-UHFFFAOYSA-M sodium 2-[3-(2-methylanilino)-6-(2-methyl-4-sulfonatoanilino)xanthen-10-ium-9-yl]benzoate Chemical compound [Na+].Cc1ccccc1Nc1ccc2c(-c3ccccc3C([O-])=O)c3ccc(Nc4ccc(cc4C)S([O-])(=O)=O)cc3[o+]c2c1 UWMZZSRDUVJJDP-UHFFFAOYSA-M 0.000 description 1
- AZLXCBPKSXFMET-UHFFFAOYSA-M sodium 4-[(4-sulfophenyl)diazenyl]naphthalen-1-olate Chemical compound [Na+].C12=CC=CC=C2C(O)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 AZLXCBPKSXFMET-UHFFFAOYSA-M 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 description 1
- GTKIEPUIFBBXJQ-UHFFFAOYSA-M sodium;2-[(4-hydroxy-9,10-dioxoanthracen-1-yl)amino]-5-methylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC(C)=CC=C1NC1=CC=C(O)C2=C1C(=O)C1=CC=CC=C1C2=O GTKIEPUIFBBXJQ-UHFFFAOYSA-M 0.000 description 1
- VRDAELYOGRCZQD-NFLRKZIHSA-M sodium;4-[(2z)-2-[(5e)-5-[(2,4-dimethylphenyl)hydrazinylidene]-4,6-dioxocyclohex-2-en-1-ylidene]hydrazinyl]benzenesulfonate Chemical compound [Na+].CC1=CC(C)=CC=C1N\N=C(/C(=O)C=C\1)C(=O)C/1=N\NC1=CC=C(S([O-])(=O)=O)C=C1 VRDAELYOGRCZQD-NFLRKZIHSA-M 0.000 description 1
- BFXAWOHHDUIALU-UHFFFAOYSA-M sodium;hydron;difluoride Chemical compound F.[F-].[Na+] BFXAWOHHDUIALU-UHFFFAOYSA-M 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- MPCYPRXRVWZKGF-UHFFFAOYSA-J tetrasodium 5-amino-3-[[4-[4-[(8-amino-1-hydroxy-3,6-disulfonatonaphthalen-2-yl)diazenyl]phenyl]phenyl]diazenyl]-4-hydroxynaphthalene-2,7-disulfonate Chemical compound [Na+].[Na+].[Na+].[Na+].C1=C(S([O-])(=O)=O)C=C2C=C(S([O-])(=O)=O)C(N=NC3=CC=C(C=C3)C3=CC=C(C=C3)N=NC3=C(C=C4C=C(C=C(C4=C3O)N)S([O-])(=O)=O)S([O-])(=O)=O)=C(O)C2=C1N MPCYPRXRVWZKGF-UHFFFAOYSA-J 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- CENHPXAQKISCGD-UHFFFAOYSA-N trioxathietane 4,4-dioxide Chemical compound O=S1(=O)OOO1 CENHPXAQKISCGD-UHFFFAOYSA-N 0.000 description 1
- FKVXIGHJGBQFIH-UHFFFAOYSA-K trisodium 5-amino-3-[[4-[4-[(7-amino-1-hydroxy-3-sulfonatonaphthalen-2-yl)diazenyl]phenyl]phenyl]diazenyl]-4-hydroxynaphthalene-2,7-disulfonate Chemical compound C1=CC(=CC=C1C2=CC=C(C=C2)N=NC3=C(C=C4C=CC(=CC4=C3[O-])N)S(=O)(=O)O)N=NC5=C(C6=C(C=C(C=C6C=C5S(=O)(=O)O)S(=O)(=O)[O-])N)[O-].[Na+].[Na+].[Na+] FKVXIGHJGBQFIH-UHFFFAOYSA-K 0.000 description 1
- SWGJCIMEBVHMTA-UHFFFAOYSA-K trisodium;6-oxido-4-sulfo-5-[(4-sulfonatonaphthalen-1-yl)diazenyl]naphthalene-2-sulfonate Chemical compound [Na+].[Na+].[Na+].C1=CC=C2C(N=NC3=C4C(=CC(=CC4=CC=C3O)S([O-])(=O)=O)S([O-])(=O)=O)=CC=C(S([O-])(=O)=O)C2=C1 SWGJCIMEBVHMTA-UHFFFAOYSA-K 0.000 description 1
- IBYSTTGVDIFUAY-UHFFFAOYSA-N vanadium monoxide Chemical compound [V]=O IBYSTTGVDIFUAY-UHFFFAOYSA-N 0.000 description 1
- 239000012002 vanadium phosphate Substances 0.000 description 1
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 description 1
- 229910000352 vanadyl sulfate Inorganic materials 0.000 description 1
- 229940041260 vanadyl sulfate Drugs 0.000 description 1
- PEAGNRWWSMMRPZ-UHFFFAOYSA-L woodstain scarlet Chemical compound [Na+].[Na+].OC1=CC=C2C=C(S([O-])(=O)=O)C=C(S([O-])(=O)=O)C2=C1N=NC(C=C1)=CC=C1N=NC1=CC=CC=C1 PEAGNRWWSMMRPZ-UHFFFAOYSA-L 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical compound [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- 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
- C23C22/44—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 containing also fluorides or complex fluorides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
본 발명은, 내식성이 우수하고, 착색된 화성 피막을 금속 재료의 표면 또는 표면 상에 형성 가능한 화성 처리제 등을 제공하는 것을 과제로 한다. 지르코늄, 티탄 및 하프늄으로부터 선택되는 금속 원소를 포함하는 이온 (A) 와, 크롬, 철, 코발트, 바나듐 및 구리로부터 선택되는 금속 원소를 포함하는 이온 (B) 와, 불소를 포함하는 이온 (C) 와, 산성 염료 (D) 를 함유하고, 상기 이온 (C) 의 몰농도는, 상기 이온 (A) 의 몰농도에 대해 6 배 이상인 화성 처리제에 의해 과제를 해결한다.An object of the present invention is to provide a chemical conversion treatment agent that is excellent in corrosion resistance and can form a colored chemical conversion film on the surface or surface of a metal material. An ion (A) containing a metal element selected from zirconium, titanium and hafnium, an ion (B) containing a metal element selected from chromium, iron, cobalt, vanadium and copper, and an ion containing fluorine (C) And acid dye (D) is contained, and the molar concentration of the said ion (C) solves a subject with the chemical conversion treatment agent 6 times or more with respect to the molar concentration of the said ion (A).
Description
본 발명은, 금속 재료의 표면 또는 표면 상에 화성 피막을 제조하는 화성 처리제, 그 화성 처리제를 사용한 화성 피막을 갖는 금속 재료의 제조 방법, 그 제조 방법에 의해 제조된 화성 피막을 갖는 금속 재료에 관한 것이다. The present invention relates to a chemical conversion treatment agent for producing a chemical conversion film on the surface or surface of a metal material, a method for producing a metal material having a chemical conversion film using the chemical conversion treatment agent, and a metal material having a chemical conversion film produced by the production method will be.
종래, 내식성이 우수한 화성 피막을 형성하는 것이 가능한 화성 처리제가 개발되고 있다. 예를 들어, 특허문헌 1 에는, (A) 3 가 크롬, (B) 지르코늄 이온, (C) 염소 이온, 황산 이온 및 질산 이온으로 이루어지는 군 중 1 종 이상, (D) 방향족 술폰, 및, (E) 불소 이온을 함유하는 액체 조성물을 포함하는 처리액이 개시되어 있다.Conventionally, the chemical conversion treatment agent which can form the chemical conversion film excellent in corrosion resistance is developed. For example, in Patent Document 1, (A) trivalent chromium, (B) zirconium ion, (C) at least one kind from the group consisting of chlorine ion, sulfate ion and nitrate ion, (D) aromatic sulfone, and ( E) A treatment liquid comprising a liquid composition containing fluorine ions is disclosed.
본 발명은, 내식성이 우수하고, 착색된 화성 피막을 금속 재료의 표면 또는 표면 상에 형성 가능한 화성 처리제 등을 제공하는 것을 목적으로 한다.An object of the present invention is to provide a chemical conversion treatment agent or the like that is excellent in corrosion resistance and can form a colored chemical conversion film on the surface or surface of a metal material.
본 발명자들은, 상기 과제를 해결하기 위해서 예의 연구를 거듭한 결과, 지르코늄, 티탄 및 하프늄으로부터 선택되는 금속 원소를 포함하는 이온 (A) 와, 크롬, 철, 코발트, 바나듐 및 구리로부터 선택되는 금속 원소를 포함하는 이온 (B) 와, 불소를 포함하는 이온 (C) 와, 산성 염료 (D) 를 함유하고, 상기 이온 (C) 의 몰농도는, 상기 이온 (A) 의 몰농도에 대해 6 배 이상인 화성 처리제가, 내식성이 우수하고, 착색된 화성 피막을 형성할 수 있는 것을 알아내어, 본 발명을 완성하기에 이르렀다.MEANS TO SOLVE THE PROBLEM The present inventors repeated earnest research in order to solve the said subject, As a result, the ion (A) containing a metal element selected from zirconium, titanium, and hafnium, and a metal element selected from chromium, iron, cobalt, vanadium and copper. It contains an ion (B) containing, an ion containing fluorine (C), and an acid dye (D), wherein the molar concentration of the ion (C) is 6 times the molar concentration of the ion (A) The above chemical conversion treatment agent was excellent in corrosion resistance, discovered that it could form the colored chemical conversion film, and came to complete this invention.
본 발명은, 이하의 것을 포함한다.The present invention includes the following.
[1] 지르코늄, 티탄 및 하프늄으로부터 선택되는 금속 원소를 포함하는 이온 (A) 와, 크롬, 철, 코발트, 바나듐 및 구리로부터 선택되는 금속 원소를 포함하는 이온 (B) 와, 불소를 포함하는 이온 (C) 와, 산성 염료 (D) 를 함유하고, 상기 이온 (C) 의 몰농도는, 상기 이온 (A) 의 몰농도에 대해 6 배 이상인, 화성 처리제.[1] An ion (A) containing a metal element selected from zirconium, titanium and hafnium, an ion (B) containing a metal element selected from chromium, iron, cobalt, vanadium and copper, and an ion containing fluorine A chemical conversion treatment agent containing (C) and an acid dye (D), wherein the molar concentration of the ion (C) is 6 times or more with respect to the molar concentration of the ion (A).
[2] 금속 재료의 표면 또는 표면 상에 상기 [1] 에 기재된 화성 처리제를 접촉시키는 공정을 포함하는, 화성 피막을 갖는 금속 재료의 제조 방법.[2] A method for producing a metal material having a chemical conversion film, comprising the step of contacting the chemical conversion treatment agent according to the above [1] on the surface or the surface of the metal material.
[3] 상기 [2] 에 기재된 제조 방법에 의해 얻어지는, 화성 피막을 갖는 금속 재료.[3] A metal material having a chemical conversion film obtained by the production method according to the above [2].
본 발명에 의하면, 내식성이 우수하고, 착색된 화성 피막을 금속 재료의 표면 또는 표면 상에 형성할 수 있는 화성 처리제를 제공할 수 있다. 또, 그 화성 처리제를 사용하여 금속 재료의 표면 또는 표면 상에 화성 피막을 형성하여, 화성 피막을 갖는 금속 재료를 제조하는 방법, 그 제조 방법에 의해 제조된 화성 피막을 갖는 금속 재료도 제공할 수 있다. ADVANTAGE OF THE INVENTION According to this invention, it is excellent in corrosion resistance and can provide the chemical conversion treatment agent which can form the colored chemical conversion film on the surface or surface of a metal material. In addition, a method for producing a metal material having a chemical conversion film by forming a chemical conversion film on the surface or on the surface of a metal material using the chemical conversion treatment agent, and a metal material having a chemical conversion film produced by the production method can also be provided. have.
본 발명의 실시형태에 관련된 화성 처리제는, 지르코늄, 티탄 및 하프늄으로부터 선택되는 금속 원소를 포함하는 이온 (A) 와, 크롬, 철, 코발트, 바나듐 및 구리로부터 선택되는 금속 원소를 포함하는 이온 (B) 와, 불소를 포함하는 이온 (C) 와, 산성 염료 (D) 를 함유하고, 상기 이온 (C) 의 몰농도는, 상기 이온 (A) 의 몰농도에 대해 6 배 이상이다. 이와 같은 화성 처리제를 사용함으로써, 금속 재료의 표면 또는 표면 상에, 내식성이 우수하고, 착색된 화성 피막을 제조할 수 있다. 또한, 본 실시형태에 관련된 화성 처리제는, 수성 매체에, 이온 (A) 의 공급원, 이온 (B) 의 공급원, 이온 (C) 의 공급원, 산성 염료 (D) 만이 배합된 것이어도 되고, 기타 성분이 추가로 배합된 것이어도 된다. 본 실시형태에 관련된 화성 처리제는, 인을 포함하는 화합물을 포함해도 되고, 포함하지 않아도 된다.The chemical conversion treatment agent according to the embodiment of the present invention is an ion (A) containing a metal element selected from zirconium, titanium, and hafnium, and an ion (B) containing a metal element selected from chromium, iron, cobalt, vanadium and copper. ), an ion (C) containing fluorine, and an acid dye (D), and the molar concentration of the ion (C) is 6 times or more with respect to the molar concentration of the ion (A). By using such a chemical conversion treatment agent, it is excellent in corrosion resistance and can manufacture a colored chemical conversion film on the surface or surface of a metal material. In addition, the chemical conversion treatment agent which concerns on this embodiment may mix|blend only the supply source of ions (A), the supply source of ions (B), the supply source of ions (C), and acid dye (D) with an aqueous medium, Other components These may be further blended. The chemical conversion treatment agent according to the present embodiment may or may not contain a compound containing phosphorus.
＜이온 (A)＞ <Ion (A)>
본 실시형태에 관련된 화성 처리제는, 지르코늄, 티탄 및 하프늄으로부터 선택되는 금속 원소를 포함하는 이온 (A) (이하, 간단히 이온 (A) 라고도 한다) 를 함유한다. 이온 (A) 로서는, 예를 들어, 지르코늄, 티탄 또는 하프늄의 금속 이온 ; 지르코늄, 티탄 또는 하프늄을 포함하는 착물 이온 ; 지르코늄, 티탄 또는 하프늄의 산화물 이온 ; 등을 들 수 있다. 이들 이온은, 화성 처리제에 1 종 또는 2 종 이상 포함되어 있어도 된다.The chemical conversion treatment agent according to the present embodiment contains an ion (A) (hereinafter simply referred to as an ion (A)) containing a metal element selected from zirconium, titanium, and hafnium. Examples of the ion (A) include a metal ion of zirconium, titanium, or hafnium; a complex ion containing zirconium, titanium, or hafnium; oxide ions of zirconium, titanium, or hafnium; and the like. One type or two or more types of these ions may be contained in a chemical conversion treatment agent.
화성 처리제 중의 이온 (A) 의 농도는 특별히 제한되는 것은 아니지만, 금속 환산 질량 농도 (2 종 이상의 이온 (A) 를 포함하는 경우에는, 합계 금속 환산 질량 농도를 의미한다.) 로서, 통상 5 mg/L 이상이며, 바람직하게는 20 mg/L 이상이며, 또, 통상 2000 mg/L 이하이며, 바람직하게는 1000 mg/L 이하이다.Although the concentration in particular of the ion (A) in a chemical conversion treatment agent is not restrict|limited, As a metal conversion mass concentration (When 2 or more types of ions (A) are included, it means a total metal conversion mass concentration.), Usually 5 mg/ L or more, preferably 20 mg/L or more, and usually 2000 mg/L or less, and preferably 1000 mg/L or less.
이온 (A) 의 공급원으로서는, 수성 매체에 혼합했을 때에, 이온 (A) 를 제공할 수 있는 화합물이면 특별히 제한되는 것은 아니다. 예를 들어, 헥사플루오로지르코늄산, 황산지르코늄, 옥시황산지르코늄, 황산지르코늄암모늄, 질산지르코늄, 옥시질산지르코늄, 질산지르코늄암모늄, 아세트산지르코닐, 락트산지르코닐, 지르코늄테트라아세틸아세토네이트, 지르코늄트리부톡시아세틸아세토네이트, 테트라노르말프로폭시지르코늄질산지르코닐, 탄산지르코늄, 수산화지르코늄, 산화지르코늄, 헥사플루오로티탄산, 질산티탄, 옥시질산티탄, 질산티탄암모늄, 질산티타닐, 황산티탄, 옥시황산티탄, 황산티탄암모늄, 수산화티탄, 산화티탄, 티탄불화암모늄, 헥사플루오로하프늄산, 질산하프늄, 산화하프늄 등을 들 수 있다. 이들이 염의 형태를 취할 수 있는 경우에는 그 염이어도 된다. 또한, 이들 공급원은, 1 종만 사용해도 되지만, 2 종 이상을 병용해도 된다.The source of the ion (A) is not particularly limited as long as it is a compound capable of providing the ion (A) when mixed with an aqueous medium. For example, hexafluoro zirconic acid, zirconium sulfate, zirconium oxysulfate, zirconium ammonium sulfate, zirconium nitrate, zirconium oxynitrate, zirconium nitrate ammonium, zirconyl acetate, zirconyl lactate, zirconium tetraacetylacetonate, zirconium tributoxy Acetylacetonate, tetranormal propoxy zirconium zirconyl nitrate, zirconium carbonate, zirconium hydroxide, zirconium oxide, hexafluorotitanic acid, titanium nitrate, titanium oxynitrate, ammonium titanium nitrate, titanyl nitrate, titanium sulfate, titanium oxysulfate, sulfuric acid and titanium ammonium, titanium hydroxide, titanium oxide, ammonium titanium fluoride, hexafluorohafnitric acid, hafnium nitrate, and hafnium oxide. If they can take the form of a salt, the salt may be used. In addition, although only 1 type may be used for these supply sources, they may use 2 or more types together.
＜산성 염료 (D)＞ <Acid dye (D)>
본 실시형태에 관련된 화성 처리제는, 산성 염료 (D) 를 함유한다. 본 명세서에 있어서 「산성 염료」란, 산성기를 갖는 수용성 염료 및 그 산성기가 반응하여 염을 구성할 수 있는 수용성 염료를 의미한다. 그 산성기로서는, 예를 들어, 술포기, 카르복시기, 페놀성하이드록시기, 인산기 등을 들 수 있다. 산성 염료는, 1 종 또는 2 종 이상의 산성기를 갖는 것을 사용해도 된다. 또, 염으로서는, 예를 들어, 알칼리 금속염 ; 알칼리 토금속염 ; 암모늄염 ; 알루미늄, 주석, 크롬, 구리, 코발트, 니켈, 철 등의 금속 원소와의 염 등을 들 수 있다. 또한, 상기 「수용성 염료」란, 20 ℃ 의 물 100 g 에 0.01 g 이상 용해하는 염료인 것을 의미한다. 또, 20 ℃ 의 물 100 g 에 0.02 g 이상 용해하는 염료인 것이 바람직하고, 0.2 g 이상 용해하는 염료인 것이 보다 바람직하다. 산성 염료는, 수성 매체 중에 있어서 어떠한 형태로 용해되어 있어도 되고, 예를 들어, 이온화하고 있지 않은 형태여도 되고, 일부 또는 전부의 관능기가 이온화한 형태여도 되고, 착물 이온화한 형태여도 되고, 기타 형태여도 된다. 이들은, 화성 처리제에 1 종 또는 2 종 이상 포함되어 있어도 된다.The chemical conversion treatment agent according to the present embodiment contains an acid dye (D). As used herein, the term "acidic dye" refers to a water-soluble dye having an acidic group and a water-soluble dye capable of forming a salt by reacting the acidic group. As the acidic group, a sulfo group, a carboxy group, a phenolic hydroxyl group, a phosphoric acid group etc. are mentioned, for example. As an acid dye, you may use what has 1 type, or 2 or more types of acidic groups. Moreover, as a salt, For example, alkali metal salt; alkaline earth metal salt; ammonium salt; Salts with metal elements, such as aluminum, tin, chromium, copper, cobalt, nickel, and iron, etc. are mentioned. In addition, the said "water-soluble dye" means that it is a dye which melt|dissolves 0.01 g or more in 100 g of 20 degreeC water. Moreover, it is preferable that it is a dye which melt|dissolves 0.02 g or more in 100 g of 20 degreeC water, and it is more preferable that it is a dye which melt|dissolves 0.2 g or more. The acid dye may be dissolved in any form in the aqueous medium, for example, may be in a form that is not ionized, may be in a form in which some or all of the functional groups are ionized, may be in a form in which complex ionization is performed, or may be in other forms. do. These may be contained 1 type(s) or 2 or more types in chemical conversion treatment agent.
산성 염료 (D) 를 화성 처리제에 배합함으로써, 착색된 화성 피막을 금속 재료의 표면 또는 표면 상에 형성할 수 있다. 또, 그 화성 피막은, 산성 염료 (D) 를 포함하지 않는 화성 처리제에 의해 형성된 화성 피막보다, 우수한 내식성을 갖는다.By mix|blending an acid dye (D) with a chemical conversion agent, a colored chemical conversion film can be formed on the surface or surface of a metal material. Moreover, this chemical conversion film has the corrosion resistance superior to the chemical conversion film formed with the chemical conversion treatment agent which does not contain an acid dye (D).
화성 처리제에 있어서의 산성 염료 (D) 의 배합량 (농도) 은, 특별히 제한되는 것은 아니지만, 통상 200 mg/L 이상이며, 또, 통상 30000 mg/L 이하이며, 10000 mg/L 이하인 것이 바람직하고, 2000 mg 이하인 것이 보다 바람직하다.The compounding amount (concentration) of the acid dye (D) in the chemical conversion agent is not particularly limited, but is usually 200 mg/L or more, and is usually 30000 mg/L or less, preferably 10000 mg/L or less, It is more preferable that it is 2000 mg or less.
산성 염료 (D) 로서는, 공지된 산성 염료이면 특별히 제한되는 것은 아니다. 예를 들어, 아조 산성 염료, 트리아릴메탄 산성 염료, 인디고이드 산성 염료, 안트라퀴논 산성 염료, 크산텐 산성 염료, 퀴놀린 산성 염료, 니트로 산성 염료, 시아닌 산성 염료 등을 들 수 있다. 이들은 1 종 또는 2 종 이상을 조합하여 사용하는 것이 가능하고, 2 종 이상을 병용하는 경우, 임의로 조합할 수도 있다. 산성 염료 (D) 의 구체예로서, 컬러 인덱스명으로, 푸드 레드 1, 푸드 레드 6, 애시드 레드 1, 애시드 레드 2, 애시드 레드 9, 애시드 레드 13, 애시드 레드 18, 애시드 레드 26, 애시드 레드 27, 애시드 레드 29, 애시드 레드 33, 애시드 레드 51, 애시드 레드 52, 애시드 레드 60, 애시드 레드 73, 애시드 레드 87, 애시드 레드 88, 애시드 레드 91, 애시드 레드 92, 애시드 레드 94, 애시드 레드 95, 애시드 레드 112, 애시드 레드 114, 애시드 레드 289, 애시드 바이올렛 9, 애시드 바이올렛 43, 애시드 오렌지 7, 애시드 오렌지 20, 애시드 오렌지 24, 애시드 옐로 1, 애시드 옐로 3, 애시드 옐로 11, 애시드 옐로 23, 애시드 옐로 36, 애시드 옐로 40, 애시드 옐로 73, 푸드 옐로 3, 푸드 그린, 애시드 그린 25, 애시드 그린 5, 애시드 그린 1, 애시드 그린 3, 푸드 블루 2, 애시드 블루 3, 애시드 블루 5, 애시드 블루 9, 애시드 블루 74, 다이렉트 블루 1, 다이렉트 블루 2, 다이렉트 블루 6, 다이렉트 블루 14, 리액티브 블루 21, 애시드 블랙 1 등을 들 수 있다.As an acid dye (D), if it is a well-known acid dye, it will not restrict|limit especially. For example, an azo acid dye, a triarylmethane acid dye, an indigoid acid dye, an anthraquinone acid dye, a xanthene acid dye, a quinoline acid dye, a nitro acid dye, a cyanine acid dye, etc. are mentioned. These can be used 1 type or in combination of 2 or more type, and when using 2 or more types together, they can also be combined arbitrarily. Specific examples of the acid dye (D) are Food Red 1, Food Red 6, Acid Red 1, Acid Red 2, Acid Red 9, Acid Red 13, Acid Red 18, Acid Red 26, Acid Red 27 by color index name. , Acid Red 29, Acid Red 33, Acid Red 51, Acid Red 52, Acid Red 60, Acid Red 73, Acid Red 87, Acid Red 88, Acid Red 91, Acid Red 92, Acid Red 94, Acid Red 95, Acid Red 112, Acid Red 114, Acid Red 289, Acid Violet 9, Acid Violet 43, Acid Orange 7, Acid Orange 20, Acid Orange 24, Acid Yellow 1, Acid Yellow 3, Acid Yellow 11, Acid Yellow 23, Acid Yellow 36 , Acid Yellow 40, Acid Yellow 73, Food Yellow 3, Food Green, Acid Green 25, Acid Green 5, Acid Green 1, Acid Green 3, Food Blue 2, Acid Blue 3, Acid Blue 5, Acid Blue 9, Acid Blue 74, Direct Blue 1, Direct Blue 2, Direct Blue 6, Direct Blue 14, Reactive Blue 21, Acid Black 1, and the like.
＜이온 (B)＞ <Ion (B)>
본 실시형태에 관련된 화성 처리제는, 크롬, 철, 코발트, 바나듐 및 구리로부터 선택되는 금속 원소를 포함하는 이온 (B) (이하, 간단히 이온 (B) 라고도 한다) 를 함유한다. 이온 (B) 로서는, 예를 들어, 크롬, 철, 코발트, 바나듐 또는 구리의 금속 이온 ; 크롬, 철, 코발트, 바나듐 또는 구리를 포함하는 착물 이온 ; 바나듐의 산화물 이온 ; 등을 들 수 있다. 이들 이온은, 화성 처리제에 1 종 또는 2 종 이상 포함되어 있어도 된다.The chemical conversion treatment agent according to the present embodiment contains an ion (B) (hereinafter simply referred to as an ion (B)) containing a metal element selected from chromium, iron, cobalt, vanadium, and copper. Examples of the ion (B) include metal ions of chromium, iron, cobalt, vanadium, or copper; complex ions containing chromium, iron, cobalt, vanadium or copper; oxide ions of vanadium; and the like. One type or two or more types of these ions may be contained in a chemical conversion treatment agent.
화성 처리제에 있어서의 이온 (B) 의 농도는, 특별히 제한되는 것은 아니지만, 금속 환산 질량 농도 (2 종 이상의 이온 (B) 를 포함하는 경우에는, 합계 금속 환산 질량 농도를 의미한다.) 로서, 통상 5 mg/L 이상이며, 바람직하게는 20 mg/L 이상이며, 또, 통상 2000 mg/L 이하이며, 바람직하게는 1000 mg/L 이하이다.The concentration of the ion (B) in the chemical conversion treatment agent is not particularly limited, but is usually a metal equivalent mass concentration (when two or more types of ions (B) are included, it means a total metal equivalent mass concentration.) It is 5 mg/L or more, Preferably it is 20 mg/L or more, Moreover, it is 2000 mg/L or less normally, Preferably it is 1000 mg/L or less.
이온 (B) 의 공급원으로서는, 수성 매체에 혼합했을 때에, 이온 (B) 를 제공할 수 있는 화합물이면 특별히 제한되는 것은 아니다. 예를 들어, 불화크롬 (III), 인산크롬 (III), 질산크롬 (III), 황산크롬 (III), 염화크롬 (III), 아세트산크롬 (III), 옥살산크롬 (III), 숙신산크롬 (III) ; 불화철 (II), 불화철 (III), 수산화철 (II), 수산화철 (III), 질산철 (II), 질산철 (III), 철 (III) 아세틸아세토네이트, 염화철 (II), 염화철 (III), 시트르산철 (III), 산화철 (II), 산화철 (III), 헥사시아노철 (II), 헥사시아노철 (III), 헥사시아노철 (II) 산, 헥사시아노철 (III) 산칼륨, 황산암모늄철 (II), 황산암모늄철 (III), 인산철 (II) ; 불화코발트, 황산코발트, 질산코발트, 아세트산코발트, 탄산코발트, 인산코발트, 염화코발트 ; 산화바나듐 (II), 산화바나듐 (IV), 산화바나듐 (V), 메타바나드산나트륨, 메타바나드산칼륨, 메타바나드산암모늄, 바나듐비스아세틸아세토나토, 바나딜디아세틸아세토나토, 불화바나듐, 인산바나듐, 황산바나딜, 황화바나듐, 옥살산바나딜, 바나듐옥시트리이소프로폭시드, 바나듐옥시트리부톡시드, 바나듐옥시트리에톡시드, 바나듐옥시트리이소부톡시드, 바나듐옥시트리에탄올아미네이트, 바나듐옥시시트르산암모늄, 바나듐트리부톡시스테아레이트, 바나딜아세틸아세토나토, 테트라프로폭시바나듐, 테트라부톡시바나듐 ; 질산구리, 황산구리, 염화구리, 산화구리, 불화구리 등을 들 수 있다. 이들이 염의 형태를 취할 수 있는 경우에는 그 염이어도 된다. 또한, 이들 공급원은, 1 종만 사용해도 되지만, 2 종 이상을 병용해도 된다. 단, 이온 (B) 의 공급원은, 산성 염료 (D) 와는 상이한 화합물이다.The source of the ion (B) is not particularly limited as long as it is a compound capable of providing the ion (B) when mixed with an aqueous medium. For example, chromium (III) fluoride, chromium (III) phosphate, chromium (III) nitrate, chromium (III) sulfate, chromium (III) chloride, chromium (III) acetate, chromium (III) oxalate, chromium (III) succinate ) ; Ferrous (II) fluoride, iron (III) fluoride, iron (II) hydroxide, iron (III) hydroxide, iron (II) nitrate, iron (III) nitrate, iron (III) acetylacetonate, iron (II) chloride, iron (III) chloride ), iron (III) citrate, iron (II) oxide, iron (III) oxide, iron hexacyano iron (II), iron hexacyano iron (III), iron hexacyano iron (II) acid, iron hexacyano iron (III) potassium acid, iron ammonium sulfate (II), iron ammonium sulfate (III), iron phosphate (II); cobalt fluoride, cobalt sulfate, cobalt nitrate, cobalt acetate, cobalt carbonate, cobalt phosphate, and cobalt chloride; Vanadium (II) oxide, vanadium (IV) oxide, vanadium (V) oxide, sodium metavanadate, potassium metavanadate, ammonium metavanadate, vanadium bisacetylacetonato, vanadyldiacetylacetonato, vanadium fluoride , vanadium phosphate, vanadyl sulfate, vanadium sulfide, vanadyl oxalate, vanadium oxytriisopropoxide, vanadium oxytributoxide, vanadium oxytriethoxide, vanadium oxytriisobutoxide, vanadium oxytriethanolaminate, vanadium ammonium oxycitrate, vanadium tributoxystearate, vanadylacetylacetonato, tetrapropoxyvanadium, tetrabutoxyvanadium; Copper nitrate, copper sulfate, copper chloride, copper oxide, copper fluoride, etc. are mentioned. If they can take the form of a salt, the salt may be used. In addition, although only 1 type may be used for these supply sources, they may use 2 or more types together. However, the source of the ion (B) is a compound different from the acid dye (D).
＜불소를 포함하는 이온 (C)＞ <Ion containing fluorine (C)>
본 실시형태에 관련된 화성 처리제는, 불소를 포함하는 이온 (C) (이하, 간단히 이온 (C) 라고도 한다) 를 함유한다. 이온 (C) 로서는, 예를 들어, 불화물 이온 ; 화성 처리제 중에 존재하는 금속 이온에 결합 또는 배위한 이온 ; 등을 들 수 있다. 이들 이온은, 화성 처리제에 1 종 또는 2 종 이상 포함되어 있어도 된다.The chemical conversion treatment agent according to the present embodiment contains fluorine-containing ions (C) (hereinafter also simply referred to as ions (C)). As an ion (C), For example, a fluoride ion; an ion that binds or coordinates to a metal ion present in the chemical conversion agent; and the like. One type or two or more types of these ions may be contained in a chemical conversion treatment agent.
화성 처리제에 있어서의 이온 (C) 의 농도는, 불소 환산 몰농도로서 지르코늄, 티탄 및 하프늄의 합계 금속 환산 몰농도의 6 배 이상이면 되고, 상한값은 200 배 이하인 것이 바람직하다.The concentration of the ions (C) in the chemical conversion agent may be 6 times or more of the total metal equivalent molar concentration of zirconium, titanium, and hafnium in terms of fluorine, and the upper limit is preferably 200 times or less.
이온 (C) 의 공급원으로서는, 수성 매체에 혼합했을 때에, 이온 (C) 를 제공할 수 있는 화합물이면 특별히 제한되는 것은 아니다. 예를 들어, 불화수소산, 불화암모늄, 불화수소암모늄, 불화게르마늄, 불화알루미늄, 불화칼륨, 불화수소칼륨, 불화나트륨, 불화수소나트륨 등의 불소 함유 화합물을 들 수 있다. 또, 헥사플루오로지르코늄산, 헥사플루오로티탄산, 헥사플루오로하프늄산 등의, 이온 (A) 의 공급원만 (불소 함유 화합물에도 해당한다) 에 의해 공급되어도 되고, 불화크롬 (III), 불화철 (II), 불화철 (III), 불화코발트, 불화바나듐, 불화구리 등의, 이온 (B) 의 공급원만 (불소 함유 화합물에도 해당한다) 에 의해 공급되어도 되고, 이온 (A) 의 공급원 및 이온 (B) 의 공급원에 의해 공급되어도 되고, 이온 (A) 의 공급원 및 이온 (B) 의 공급원 이외의 불소 함유 화합물에 의해 공급되어도 되고, 이온 (A) 의 공급원 및/또는 이온 (B) 의 공급원과 그 이외의 불소 함유 화합물을 배합함으로써 공급되어도 된다. 또한, 헥사플루오로지르코늄산, 헥사플루오로티탄산, 헥사플루오로하프늄산 등의, 지르코늄, 티탄 또는 하프늄과, 불소를 함유하는 화합물을 사용하여 화성 처리제를 조제하는 경우에는, 이온 (A) 와, 이온 (C) 를 공급할 수 있다. 또, 불화크롬 (III), 불화철 (II), 불화철 (III), 불화코발트, 불화바나듐, 불화구리 등의, 크롬, 철, 코발트, 바나듐, 또는 구리와, 불소를 함유하는 화합물을 사용하여 화성 처리제를 조제하는 경우에는, 이온 (B) 와, 이온 (C) 를 공급할 수 있다. 또한, 각종 불소 함유 화합물은 1 종만을 사용해도 되지만, 2 종 이상을 병용해도 된다. The source of the ion (C) is not particularly limited as long as it is a compound capable of providing the ion (C) when mixed with an aqueous medium. For example, fluorine-containing compounds, such as hydrofluoric acid, ammonium fluoride, ammonium hydrogen fluoride, germanium fluoride, aluminum fluoride, potassium fluoride, potassium hydrogen fluoride, sodium fluoride, and sodium hydrogen fluoride, are mentioned. In addition, only the source of the ion (A), such as hexafluorozirconic acid, hexafluorotitanic acid, or hexafluorohafniic acid, may be supplied by (also applicable to a fluorine-containing compound), chromium (III) fluoride, iron fluoride (II), iron (III) fluoride, cobalt fluoride, vanadium fluoride, copper fluoride, etc., only the source of the ion (B) may be supplied by (also applicable to the fluorine-containing compound), the source of the ion (A) and the ion It may be supplied by the source of (B), or may be supplied by a fluorine-containing compound other than the source of ions (A) and the source of ions (B), and may be supplied by the source of ions (A) and/or source of ions (B). You may supply by mix|blending a fluorine-containing compound other than this. Further, when the chemical conversion treatment agent is prepared using a compound containing zirconium, titanium or hafnium, and fluorine, such as hexafluorozirconic acid, hexafluorotitanic acid, and hexafluorohafniic acid, ions (A) and Ions (C) can be supplied. In addition, a compound containing chromium, iron, cobalt, vanadium, or copper and fluorine, such as chromium (III) fluoride, iron (II) fluoride, iron (III) fluoride, cobalt fluoride, vanadium fluoride, and copper fluoride, is used. When preparing a chemical conversion treatment agent by doing this, an ion (B) and an ion (C) can be supplied. In addition, although only 1 type may be used for various fluorine-containing compounds, they may use 2 or more types together.
＜수성 매체＞ <Aqueous medium>
수성 매체로서는, 물 또는 물과 수혼화성 유기 용매의 혼합물 (수성 매체의 체적을 기준으로 하여 50 체적% 이상의 물을 함유하는 것) 이면 특별히 제한되는 것은 아니다. 수혼화성 유기 용매로서는, 물과 혼화하는 것이면 특별히 제한되는 것이 아니고, 예를 들어, 아세톤, 메틸에틸케톤 등의 케톤계 용매 ; N,N'-디메틸포름아미드, 디메틸아세트아미드 등의 아미드계 용매 ; 메탄올, 에탄올, 이소프로판올 등의 알코올계 용매 ; 에틸렌글리콜모노부틸에테르, 에틸렌글리콜모노헥실에테르 등의 에테르계 용매 ; 1-메틸-2-피롤리돈, 1-에틸-2-피롤리돈 등의 피롤리돈계 용매 등을 들 수 있다. 이들 수혼화성 유기 용매는 1 종을 물과 혼합시켜도 되고, 2 종 이상을 물에 혼합시켜도 된다.The aqueous medium is not particularly limited as long as it is water or a mixture of water and a water-miscible organic solvent (containing 50% by volume or more of water based on the volume of the aqueous medium). The water-miscible organic solvent is not particularly limited as long as it is miscible with water, and examples thereof include ketone solvents such as acetone and methyl ethyl ketone; amide solvents such as N,N'-dimethylformamide and dimethylacetamide; Alcohol solvents, such as methanol, ethanol, and isopropanol; ether solvents such as ethylene glycol monobutyl ether and ethylene glycol monohexyl ether; and pyrrolidone solvents such as 1-methyl-2-pyrrolidone and 1-ethyl-2-pyrrolidone. These water-miscible organic solvents may mix 1 type with water, and may mix 2 or more types with water.
＜기타 성분＞ ＜Other ingredients＞
기타 성분으로서는, 예를 들어, 알루미늄, 마그네슘 및 아연으로부터 선택되는 금속을 함유하는 이온의 공급원 (E), 질산 이온의 공급원 (F), 피처리물의 젖음성을 조정하는 계면 활성제, 소포제로 칭해지는 계면 활성제 등의 첨가제, pH 조정제 등의, 화성 처리제에 사용되는 공지된 첨가제, 아크릴계 수지, 폴리에스테르계 수지, 에폭시계 수지, 폴리올레핀계 수지, 페놀계 수지, 폴리비닐계 수지, 폴리우레탄계 수지, 폴리이미드계 수지, 폴리아미드계 수지 등의 공지된 수용성 수지나 수분산성 수지 등을 들 수 있지만, 이들에 제한되는 것은 아니다. 또한, 이들 기타 성분은, 본 발명의 효과를 저해하지 않는 범위에서 포함하고 있어도 된다.As other components, for example, a source of ions containing a metal selected from aluminum, magnesium and zinc (E), a source of nitrate ions (F), a surfactant for adjusting the wettability of the object to be treated, and an interface called an antifoaming agent Additives such as activators, known additives used in chemical conversion treatment agents such as pH adjusters, acrylic resins, polyester resins, epoxy resins, polyolefin resins, phenolic resins, polyvinyl resins, polyurethane resins, polyimides Well-known water-soluble resins, such as a polyamide-type resin, water-dispersible resin, etc. are mentioned, but are not limited to these. In addition, you may contain these other components in the range which does not impair the effect of this invention.
＜화성 처리제의 pH＞ <pH of chemical treatment agent>
본 실시형태에 관련된 화성 처리제의 pH 는 특별히 제한되지 않지만, 통상 산성 ~ 중성의 영역이며, 구체적으로는 pH 가 1.0 ~ 7.0 의 범위 내인 것이 바람직하고, 1.5 ~ 6.0 의 범위 내인 것이 보다 바람직하고, 2.0 ~ 5.5 의 범위 내인 것이 특히 바람직하다. 여기서, 본 명세서에 있어서의 화성 처리제의 pH 값은, pH 미터를 사용하여 50 ℃ 에서 측정한 값을 의미한다.Although the pH in particular of the chemical conversion treatment agent which concerns on this embodiment is not restrict|limited, Usually, it is an acidic-neutral range, Specifically, it is preferable that pH exists in the range of 1.0-7.0, It is more preferable that it exists in the range of 1.5-6.0, 2.0 It is particularly preferred to be in the range of ~ 5.5. Here, the pH value of the chemical conversion treatment agent in this specification means the value measured at 50 degreeC using the pH meter.
화성 처리제의 pH 는, 예를 들어, 염산, 황산, 질산, 불화수소산, 붕산, 유기산 등의 산 성분 ; 수산화리튬, 수산화칼륨, 수산화나트륨, 수산화칼슘, 수산화마그네슘, 수산화바륨, 알칼리 금속염, 암모니아, 암모늄염, 아민류 등의 알칼리 성분 ; 등의 pH 조정제를 사용하여 조정할 수 있지만, 이들 성분에 제한되는 것은 아니다. 또한, pH 조정제는, 1 종 또는 2 종 이상을 사용해도 된다.The pH of the chemical conversion treatment agent may be, for example, an acid component such as hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, boric acid or an organic acid; alkali components such as lithium hydroxide, potassium hydroxide, sodium hydroxide, calcium hydroxide, magnesium hydroxide, barium hydroxide, alkali metal salts, ammonia, ammonium salts, and amines; Although it can adjust using these pH adjusters, it is not limited to these components. In addition, you may use 1 type(s) or 2 or more types as a pH adjuster.
＜화성 처리제의 제조 방법＞ <The manufacturing method of chemical conversion treatment agent>
본 실시형태에 관련된 화성 처리제는, 이온 (A) 의 공급원과, 이온 (B) 의 공급원과, 이온 (C) 의 공급원과, 산성 염료 (D) 를 원료로 하여, 수성 매체에 소정량 배합함으로써 제조 가능하다. 상기의 각 원료를, 예를 들어, 상기의 순서로 수성 매체에 배합함으로써 본 실시형태에 관련된 화성 처리제를 제조할 수 있다. 또한, 기타 성분을 배합하는 경우에는, 예를 들어, 상기의 각 원료를 수성 매체에 배합한 후, 기타 성분을 배합함으로써 제조할 수 있다.The chemical conversion treatment agent according to the present embodiment contains a supply source of ions (A), a supply source of ions (B), a supply source of ions (C), and an acid dye (D) as raw materials, and mixes a predetermined amount with an aqueous medium. can be manufactured. The chemical conversion treatment agent which concerns on this embodiment can be manufactured by mix|blending each said raw material with an aqueous medium in said procedure, for example. Moreover, when mix|blending other components, after mix|blending each said raw material with an aqueous medium, for example, it can manufacture by mix|blending other components.
＜화성 피막의 제조 방법＞ <Method for producing chemical conversion film>
본 실시형태에 관련된 화성 피막의 제조 방법은, 금속 재료의 표면 또는 표면 상에 본 실시형태에 관련된 화성 처리제를 접촉시키는 접촉 공정을 포함한다. 이로써, 금속 재료의 표면 또는 표면 상에 화성 피막이 형성된다. 화성 처리제의 금속 재료에 대한 접촉 방법으로서는, 종래부터 있는 접촉 방법, 예를 들어, 침지 처리법, 혹은, 스프레이 처리법, 흘리기 처리법 등의 처리법, 또는 이들의 조합 등의 방법을 들 수 있지만 이들에 제한되는 것은 아니다.The manufacturing method of the chemical conversion film which concerns on this embodiment includes the contact process of making the chemical conversion treatment agent which concerns on this embodiment contact on the surface or surface of a metal material. Thereby, a chemical conversion film is formed on the surface or surface of a metal material. As a method of contacting the chemical conversion agent to the metal material, a conventional contact method, for example, an immersion treatment method, a treatment method such as a spray treatment method, a spill treatment method, or a combination thereof. it is not
상기 접촉 공정은, 소정의 온도 범위에서 일정 시간 실시하는 것이 바람직하다. 접촉 온도는 10 ℃ 이상 90 ℃ 이하의 범위 내인 것이 바람직하고, 20 ℃ 이상 85 ℃ 이하의 범위 내인 것이 보다 바람직하지만, 이들 온도 범위에 제한되는 것은 아니다. 또, 접촉 시간은 20 ~ 700 초간의 범위 내인 것이 바람직하고, 30 ~ 600 초간의 범위 내인 것이 보다 바람직하지만, 이들 시간에 제한되는 것은 아니다.It is preferable to carry out the said contacting process for a fixed time in a predetermined temperature range. The contact temperature is preferably in the range of 10°C or more and 90°C or less, and more preferably in the range of 20°C or more and 85°C or less, but is not limited to these temperature ranges. Moreover, it is preferable to exist in the range for 20 to 700 second, and, as for contact time, it is more preferable to exist in the range for 30 to 600 second, It is not restrict|limited to these time.
또, 접촉 공정 전에, 전처리 공정을 실시해도 된다. 전처리 공정으로서는, 예를 들어, 산세 공정 ; 탈지 공정 ; 알칼리 세정 공정 ; 크로메이트 화성 처리 공정 ; 인산아연, 인산철 등의 인산염을 사용한 인산염 화성 처리 공정 ; 비스무트 치환 도금 공정, 지르코늄 화성 처리 공정, 티탄 화성 처리 공정, 하프늄 화성 처리 공정, 바나듐 화성 처리 공정 등을 들 수 있다. 이들 중에서도 적어도 탈지 공정을 실시하는 것이 바람직하다. 또한, 이들 전처리 공정은, 1 의 공정을 실시해도 되지만, 2 이상의 공정을 조합하여 순차 실시해도 된다. 2 이상의 공정의 조합으로서는, 인산염 화성 처리 공정과, 크로메이트 화성 처리 공정, 비스무트 치환 도금 공정, 지르코늄 화성 처리 공정, 티탄 화성 처리 공정, 하프늄 화성 처리 공정 또는 바나듐 화성 처리 공정의 조합을 들 수 있다. 전처리 공정으로서 실시되는 지르코늄 화성 처리 공정은, 본 실시형태에 관련된 화성 처리제를 사용해도 되고, 본 실시형태에 관련된 화성 처리제와는 상이한 화성 처리제를 사용해도 된다. 또한, 상기 각종 전처리 공정을 실시하는 경우에는, 각종 전처리 공정 후에 수세 처리 공정을 실시해도 된다. 각종 전처리 공정을 복수 실시하는 경우에는, 각각의 공정 후, 혹은, 일부의 공정 후에 수세 처리 공정을 실시해도 된다. 또, 수세 처리 공정을 실시한 경우에는, 그 후에 금속 재료의 표면을 건조시키는 건조 공정을 실시해도 된다.Moreover, you may implement a pretreatment process before a contact process. As a pretreatment process, For example, pickling process; degreasing process; alkali cleaning process; chromate chemical conversion process; Phosphate chemical conversion treatment process using phosphates, such as zinc phosphate and iron phosphate; Bismuth substitution plating process, zirconium chemical conversion treatment process, titanium chemical conversion treatment process, hafnium chemical conversion treatment process, vanadium chemical conversion treatment process, etc. are mentioned. Among these, it is preferable to perform a degreasing process at least. In addition, although the process of 1 may be implemented for these pre-processing processes, you may implement it sequentially combining two or more processes. As a combination of two or more steps, a combination of a phosphate chemical conversion treatment process, a chromate chemical conversion treatment process, a bismuth substitution plating process, a zirconium chemical conversion treatment process, a titanium chemical conversion treatment process, a hafnium chemical conversion treatment process, or a vanadium chemical conversion treatment process is mentioned. The zirconium chemical conversion treatment process implemented as a pretreatment process may use the chemical conversion treatment agent which concerns on this embodiment, and may use a chemical conversion treatment agent different from the chemical conversion treatment agent which concerns on this embodiment. In addition, when implementing the said various pre-processing processes, you may implement a water washing treatment process after various pre-treatment processes. When performing two or more various pretreatment processes, you may implement a water washing treatment process after each process or after some processes. Moreover, when performing a water washing treatment process, you may implement the drying process of drying the surface of a metal material after that.
또, 본 실시형태에 관련된 화성 피막의 제조 방법에 있어서, 접촉 공정 후에, 예를 들어, 알칼리 세정 공정, 수세 공정, 크로메이트 화성 처리, 인산아연 화성 처리 공정, 비스무트 치환 도금 공정, 인철화성 처리 공정, 지르코늄 화성 처리 공정, 티탄 화성 처리 공정, 하프늄 화성 처리 공정, 건조 공정 등의 후처리 공정을 실시해도 된다. 이들 후처리 공정으로서는, 1 의 공정을 단독으로 실시해도 되고, 2 이상의 공정을 조합하여 순차 실시해도 된다. 후처리 공정으로서 실시되는 지르코늄 화성 처리 공정은, 본 실시형태에 관련된 화성 처리제를 사용해도 되고, 본 실시형태에 관련된 화성 처리제와는 상이한 화성 처리제를 사용해도 된다. 또한, 상기 각종 후처리 공정을 실시하는 경우에는, 각종 후처리 공정 후에 수세 처리 공정을 실시해도 된다. 각종 후처리 공정을 복수 실시하는 경우에는, 각각의 공정 후, 혹은, 일부의 공정 후에 수세 처리 공정을 실시해도 된다. 또, 수세 처리 공정을 실시한 경우에는, 그 후에 금속 재료의 표면을 건조시키는 건조 공정을 실시해도 된다. 건조 공정은, 통상 50 ~ 180 ℃, 바람직하게는 80 ~ 150 ℃ 에서, 통상 5 ~ 20 분간, 바람직하게는 10 ~ 15 분간 실시해도 된다.In addition, in the method for producing a chemical conversion film according to the present embodiment, after the contacting step, for example, an alkali cleaning step, a water washing step, a chromate chemical conversion treatment, a zinc phosphate chemical conversion treatment step, a bismuth substitution plating step, a phosphite conversion treatment step, You may implement post-processing processes, such as a zirconium chemical conversion treatment process, a titanium chemical conversion treatment process, a hafnium chemical conversion treatment process, and a drying process. As these post-processing processes, the process of 1 may be implemented independently, and you may implement it sequentially combining two or more processes. The zirconium chemical conversion treatment process implemented as a post-treatment process may use the chemical conversion treatment agent which concerns on this embodiment, and may use a chemical conversion treatment agent different from the chemical conversion treatment agent which concerns on this embodiment. In addition, when implementing the said various post-processing process, you may implement a water washing treatment process after various post-processing processes. When performing two or more various post-processing processes, you may implement a water washing treatment process after each process or after some processes. Moreover, when performing a water washing treatment process, you may implement the drying process of drying the surface of a metal material after that. A drying process is 50-180 degreeC normally, Preferably it is 80-150 degreeC, and it is 5 to 20 minutes normally, Preferably you may implement for 10 to 15 minutes.
금속 재료로서는, 예를 들어, 철강 재료 (예를 들어, 냉간 압연 강판, 열간 압연 강판, 고장력 강판, 공구강, 합금 공구강, 구상화 흑연 주철, 회주철 등) ; 도금 재료, 예를 들어, 아연 도금재 (예를 들어, 전기 아연 도금, 용융 아연 도금 등), 아연 합금 도금재 (예를 들어, 합금화 용융 아연 도금, Zn-Al 합금 도금, Zn-Al-Mg 합금 도금, 전기 아연 합금 도금 등), 알루미늄 도금재 등 ; 알루미늄재 또는 알루미늄 합금재 (예를 들어, 1000 계, 2000 계, 3000 계, 4000 계, 5000 계, 6000 계, 7000 계, 알루미늄 주물, 알루미늄 합금 주물, 다이캐스트재 등) ; 마그네슘재 또는 마그네슘 합금재 ; 아연재 또는 아연 합금재 ; 구리재 또는 구리 합금재 ; 크롬재 또는 크롬 합금재 ; 니켈재 또는 니켈 합금재 ; 주석재 또는 주석 합금재 등을 들 수 있다.As a metal material, For example, steel material (For example, a cold-rolled steel plate, a hot-rolled steel plate, a high-tensile-strength steel plate, tool steel, alloy tool steel, spheroidal graphite cast iron, gray cast iron, etc.); Plating material, for example, zinc plating material (eg electro galvanizing, hot-dip galvanizing, etc.), zinc alloy plating material (eg alloying hot-dip galvanizing, Zn-Al alloy plating, Zn-Al-Mg alloy plating, electro zinc alloy plating, etc.), aluminum plating material, etc.; an aluminum material or an aluminum alloy material (For example, 1000 series, 2000 series, 3000 series, 4000 series, 5000 series, 6000 series, 7000 series, aluminum casting, aluminum alloy casting, die-casting material, etc.); Magnesium material or magnesium alloy material; zinc material or zinc alloy material; a copper material or a copper alloy material; chromium or chromium alloy; Nickel material or nickel alloy material; A tin material or a tin alloy material is mentioned.
본 실시형태에 관련된, 화성 피막을 갖는 금속 재료는, 금속 재료의 표면 또는 표면 상에, 본 실시형태에 관련된 화성 처리제를 접촉시켜, 금속 재료의 표면 또는 표면 상에 화성 피막을 제조함으로써 얻어진다. 제조된 화성 피막은, 그 화성 피막에 함유되는, 지르코늄, 티탄, 하프늄, 크롬, 철, 코발트, 바나듐 및 구리의 전체 합계 질량이, 단위면적당 5 mg/㎡ 이상인 것이 바람직하고, 10 mg/㎡ 이상인 것이 보다 바람직하고, 20 mg/㎡ 이상인 것이 특히 바람직하다. 또한, 상한값으로서는, 특별히 제한은 없지만, 200 mg/㎡ 이하인 것이 바람직하다. 또한, 이 화성 피막에 있어서의, 지르코늄, 티탄, 하프늄, 크롬, 철, 코발트, 바나듐 및 구리의 질량은, 예를 들어, 형광 X 선 분석 장치를 사용함으로써 측정할 수 있다.The metal material which has a chemical conversion film which concerns on this embodiment is made to contact the chemical conversion treatment agent which concerns on this embodiment on the surface or surface of a metal material, and is obtained by manufacturing a chemical conversion film on the surface or surface of a metal material. The prepared chemical conversion film preferably has a total total mass of zirconium, titanium, hafnium, chromium, iron, cobalt, vanadium and copper contained in the chemical conversion film of 5 mg/m 2 or more per unit area, and 10 mg/m 2 or more It is more preferable, and it is especially preferable that it is 20 mg/m<2> or more. In addition, although there is no restriction|limiting in particular as an upper limit, It is preferable that it is 200 mg/m<2> or less. In addition, the mass of zirconium, titanium, hafnium, chromium, iron, cobalt, vanadium, and copper in this chemical conversion film can be measured by using a fluorescent X-ray analyzer, for example.
제조된 화성 피막은, 그 화성 피막에 함유되는, 산성 염료의 합계 탄소 환산 질량 (이하, 간단히 염료 부착량이라고도 한다) 이, 단위면적당 10 mg/㎡ 이상인 것이 바람직하고, 20 mg/㎡ 이상인 것이 보다 바람직하고, 50 mg/㎡ 이상인 것이 특히 바람직하다. 또한, 상한값으로서는, 특별히 제한은 없지만, 200 mg/㎡ 이하인 것이 바람직하다. 또한, 이 화성 피막에 있어서의, 산성 염료의 질량은, 예를 들어, TOC (전체 유기 탄소계) 를 사용함으로써 측정할 수 있다. In the produced chemical conversion film, the total carbon equivalent mass of the acid dye contained in the chemical conversion film (hereinafter also simply referred to as dye adhesion amount) is preferably 10 mg/m 2 or more per unit area, and more preferably 20 mg/m 2 or more. and 50 mg/m 2 or more is particularly preferred. In addition, although there is no restriction|limiting in particular as an upper limit, It is preferable that it is 200 mg/m<2> or less. In addition, the mass of the acid dye in this chemical conversion film can be measured by using TOC (total organic carbon system), for example.
본 실시형태에 관련된, 화성 피막을 갖는 금속 재료는, 본 실시형태에 관련된 화성 처리제를 접촉시킴으로써 얻어진 화성 피막의 위 혹은 아래에, 1 또는 2 이상의 상기 각종 피막 (예를 들어, 크로메이트 화성 피막, 인산염 화성 피막, 비스무트 치환 도금 피막 등) 을 가지고 있어도 된다. The metal material having a chemical conversion film according to the present embodiment is one or two or more of the above various films (eg, chromate chemical conversion film, phosphate salt) on or below the chemical conversion film obtained by contacting the chemical conversion treatment agent according to the present embodiment. A chemical conversion film, a bismuth substitution plating film, etc.) may have.
본 실시형태에 관련된, 화성 피막을 갖는 금속 재료의 표면 상에, 도료를 사용하여 도장함으로써 도막을 형성시킴으로써, 화성 피막 및 도막을 갖는 도장 금속 재료를 제조할 수 있다. 도료로서는, 특별히 제한되지 않지만, 유색의 도료를 사용해도 되고, 산성 염료 (D) 에 의해 부여된 색을 바꾸지 않도록, 투명의 도료를 사용해도 된다. 도장 방법으로서는, 특별히 제한은 없지만, 롤 코트법, 유동 침지 도장법, 정전 분체 도장법, 전착 도장법, 용제 도장법 등, 공지된 방법을 적용할 수 있다. 또, 드라이 라미네이트법이나 압출 라미네이트법 등에 의해, 라미네이트 필름을 첩부해도 된다. 도장 금속 재료는, 본 실시형태에 관련된, 화성 피막을 갖는 금속 재료의 표면 상에 도막을 갖는 것이어도 되고, 그 화성 피막 상에 추가로 형성된, 1 또는 2 이상의 상기 각종 피막 (예를 들어, 크로메이트 화성 피막, 인산염 화성 피막, 비스무트 치환 도금 피막, 바나듐 화성 피막 등) 의 표면 상에 도막을 갖는 것이어도 된다. 또한, 도막은 1 층으로 이루어지는 것이어도 되고, 2 층 이상으로 이루어지는 것이어도 된다. 도막의 두께는, 특별히 제한되는 것은 아니고, 도장 금속 재료의 사용 용도에 따라 적절히 설정된다.The coating metal material which has a chemical conversion film and a coating film can be manufactured by forming a coating film by coating using a coating material on the surface of the metal material which has a chemical conversion film which concerns on this embodiment. Although it does not restrict|limit especially as a paint, A colored paint may be used and a transparent paint may be used so that the color provided by the acid dye (D) may not be changed. Although there is no restriction|limiting in particular as a coating method, Well-known methods, such as the roll coating method, the fluid immersion coating method, the electrostatic powder coating method, the electrodeposition coating method, the solvent coating method, are applicable. Moreover, you may stick a laminate film by the dry lamination method, the extrusion lamination method, etc. The coating metal material may have a coating film on the surface of the metal material having a chemical conversion film according to the present embodiment, and one or two or more of the above various films (eg, chromate) that are further formed on the chemical conversion film. What has a coating film on the surface of a chemical conversion film, a phosphate chemical conversion film, a bismuth substitution plating film, a vanadium chemical conversion film, etc.) may be sufficient. Moreover, what consists of one layer may consist of a coating film, and what consists of two or more layers may be sufficient as it. The thickness in particular of a coating film is not restrict|limited, According to the use use of a coating metal material, it is set suitably.
실시예Example
이하, 실시예에 의해 본 발명의 효과를 상세하게 설명하지만, 본 발명은 이하의 실시예에 의해 제한되는 것은 아니다.Hereinafter, the effects of the present invention will be described in detail by way of examples, but the present invention is not limited by the following examples.
＜금속 재료＞<Metal material>
금속 재료로서, JIS H 4000 : 2014 에 규격된 알루미늄판 (A1050 : 두께 : 0.8 mm), JIS G 3302 : 2010 에 규격된 용융 아연 도금 강판 (GI : 두께 : 0.6 mm, 도금 부착량 : 편면 50 g/㎡), JIS G 3321 : 2012 에 규격된 용융 알루미늄-아연 도금 강판 (GL : 두께 : 0.4 mm, 도금 부착량 : 편면 75 g/㎡), JIS G3313 : 2010 에 규격된 전기 아연 도금 강판 (EG : 두께 0.8 mm, 도금 부착량 : 편면 45 g/㎡) 을, 각각 세로 150 mm × 가로 70 mm 의 사이즈로 절단했다.As a metal material, aluminum plate (A1050: thickness: 0.8 mm) compliant with JIS H 4000: 2014, hot-dip galvanized steel plate compliant with JIS G 3302: 2010 (GI: thickness: 0.6 mm, coating weight: 50 g/single side) m2), hot-dip aluminum-galvanized steel sheet specified in JIS G 3321: 2012 (GL: thickness: 0.4 mm, coating weight: 75 g/m2 on one side), electrogalvanized steel sheet specified in JIS G3313: 2010 (EG: thickness) 0.8 mm, plating adhesion amount: 45 g/m<2> of one side) was cut|disconnected to the size of 150 mm long x 70 mm width, respectively.
＜화성 처리제의 조제에 사용한 각 성분＞ <Each component used for preparation of chemical conversion treatment agent>
화성 처리제의 조제에 있어서는, 이온 (A) 의 공급원으로서, A1 : 헥사플루오로지르코늄산 (모리타 화학 공업 (주)), A2 : 황산지르코늄 (닛폰 경금속 (주)), 또는 A3 : 티탄불화암모늄 (모리타 화학 공업 (주)) 을 ; 이온 (B) 의 공급원으로서, B1 : 질산크롬 (닛폰 화학 공업 (주)), B2 : 황산크롬 (닛폰 화학 공업 (주)), B3 : 질산철 (후지 필름 와코 순약 (주)), B4 : 황산구리 (후지 필름 와코 순약 (주)) 를 ; 이온 (C) 의 공급원으로서, C1 : 불화수소산 (모리타 화학 공업 (주)), C2 : 불화알루미늄 (모리타 화학 공업 (주)) 을 ; 염료 (D) 로서, D1 : 푸드 옐로 No.5 (토쿄 화성 공업 (주) ; 푸드 옐로 3), D2 : 애시드 옐로 23 (토쿄 화성 공업 (주)), D3 : 애시드 레드 27 (토쿄 화성 공업 (주)), D4 : 애시드 블루 74 (토쿄 화성 공업 (주)), D5 : 애시드 블루 9 (토쿄 화성 공업 (주)), D6 : 스미픽스 터쿼이즈 블루 G(N) (스미토모 화학 (주) ; 리액티브 블루 21) 의 산성 염료, D7 : 베이직 블루 9 (후지 필름 와코 순약 (주)), D8 : 베이직 바이올렛 10 (후지 필름 와코 순약 (주)), D9 : 베이직 바이올렛 3 (후지 필름 와코 순약 (주)) 의 염기성 염료를 ; 각각 사용했다. 또한, 상기 A1 및 A3 은, 이온 (C) 의 공급원으로서도 사용했다.In the preparation of the chemical conversion agent, as a source of ions (A), A1: hexafluorozirconic acid (Morita Chemical Industry Co., Ltd.), A2: zirconium sulfate (Nippon Light Metals Co., Ltd.), or A3: ammonium titanium fluoride ( Morita Chemical Industry Co., Ltd.); As a source of ions (B), B1: chromium nitrate (Nippon Chemical Industry Co., Ltd.), B2: chromium sulfate (Nippon Chemical Industry Co., Ltd.), B3: iron nitrate (Fujifilm Wako Pure Chemical Industries, Ltd.), B4: copper sulfate (Fujifilm Wako Pure Chemical Industries, Ltd.); As a supply source of an ion (C), C1: hydrofluoric acid (Morita Chemical Industry Co., Ltd.), C2: aluminum fluoride (Morita Chemical Industry Co., Ltd.); As the dye (D), D1: Food Yellow No. 5 (Tokyo Chemical Industry Co., Ltd.; Food Yellow 3), D2: Acid Yellow 23 (Tokyo Chemical Industry Co., Ltd.), D3: Acid Red 27 (Tokyo Chemical Industry Co., Ltd.) Note), D4: Acid Blue 74 (Tokyo Chemical Industry Co., Ltd.), D5: Acid Blue 9 (Tokyo Chemical Industry Co., Ltd.), D6: Sumifix Turquoise Blue G(N) (Sumitomo Chemical Co., Ltd.); Reactive Blue 21) acid dye, D7: Basic Blue 9 (Fujifilm Wako Pure Pharmaceutical Co., Ltd.), D8: Basic Violet 10 (Fujifilm Wako Pure Pharmaceutical Co., Ltd.), D9: Basic Violet 3 (Fujifilm Wako Pure Pharmaceutical Co., Ltd.) Note)) of basic dyes; each was used In addition, said A1 and A3 were also used as a supply source of ion (C).
＜화성 처리제의 조제＞ <Preparation of chemical conversion treatment agent>
표 1 에 나타내는 바와 같이, 각 성분의 소정량을 물에 배합한 후, 암모니아로 소정의 pH 로 조정함으로써, 실시예 1 ~ 21 및 비교예 1 ~ 8 의 화성 처리제를 조제했다.As shown in Table 1, after mix|blending the predetermined amount of each component with water, the chemical conversion treatment agent of Examples 1-21 and Comparative Examples 1-8 was prepared by adjusting to predetermined pH with ammonia.
＜화성 피막을 갖는 금속 재료의 제조＞ <Manufacture of a metal material having a chemical conversion film>
각종 금속 재료 (A1050, GI, GL 및 EG) 를, 50 ℃ 로 조정한 탈지제 (FC-4424 ; 니혼 파커라이징 주식회사 ; 20 g/L 의 농도가 되도록 물에 용해한 수용액을 사용) 에 120 초간 침지함으로써 탈지했다. 그 후, 30 초간 스프레이 수세했다. 계속해서, 각종 화성 처리제 (실시예 1 ~ 21 및 비교예 1 ~ 8 의 화성 처리제) 에, 표 1 에 나타내는 조건으로 금속 재료를 침지시켜, 금속 재료의 표면 또는 표면 상에 화성 피막을 제조했다. 얻어진 화성 피막을 갖는 금속 재료의 표면 상을 수돗물, 탈이온수의 순서로 세정하고, 150 ℃ 에서 10 분간 건조하여, 시험판을 얻었다.Degreasing various metal materials (A1050, GI, GL and EG) by immersing them in a degreasing agent adjusted to 50°C (FC-4424; Nippon Parkerizing Co., Ltd.; an aqueous solution dissolved in water to a concentration of 20 g/L) for 120 seconds. did. After that, it was spray-washed for 30 seconds. Then, the metal material was immersed in various chemical conversion treatment agents (the chemical conversion treatment agent of Examples 1-21 and Comparative Examples 1-8) under the conditions shown in Table 1, and the chemical conversion film was manufactured on the surface or surface of the metal material. The surface of the obtained metal material having a chemical conversion film was washed with tap water and deionized water in this order, and dried at 150°C for 10 minutes to obtain a test plate.
＜성능 평가＞ <Performance evaluation>
제작한 시험판을 사용하여 이하의 성능 평가를 실시했다. 결과를 표 2 에 나타낸다. The following performance evaluation was performed using the produced test board. A result is shown in Table 2.
(1) 부착량 (1) Amount of adhesion
제작한 시험판의 화성 피막의 부착량 (전체 금속 합계 부착량) 에 대해, 화성 피막에 포함되는 지르코늄, 티탄, 크롬, 철 및 구리의 전체 합계 질량을, 주식회사 리가쿠 제조 주사형 형광 X 선 분석 장치 ZSX primusII 를 사용하여 측정했다. 또, 염료 부착량을, 주식회사 시마즈 제작소 제조 전체 유기 탄소계 TOC-LCSH 를 사용하여 측정한 전체 유기 탄소량으로부터 환산하여 구했다.The total total mass of zirconium, titanium, chromium, iron, and copper contained in the chemical conversion film was measured with respect to the adhesion amount of the chemical conversion film of the produced test plate (total metal adhesion amount), a scanning fluorescence X-ray analyzer ZSX primusII manufactured by Rigaku Corporation. was measured using Moreover, the amount of dye adhesion was calculated|required in conversion from the total organic carbon amount measured using the Shimadzu Corporation total organic carbon type TOC-LCSH.
(2) 착색성 (2) Colorability
제작한 시험판의 착색을 육안 판정했다.Coloring of the produced test plate was visually evaluated.
＜판정 기준＞<Judgment Criteria>
Y···착색이 확인된다.Y... coloring is confirmed.
N···착색이 확인되지 않는다.N... Coloring is not confirmed.
(3) 내식성 (3) Corrosion resistance
각 시험판의 내식성은, JIS Z 2371 : 2015 에 준한 중성 염수 분무 시험을 실시하고, 화성 피막을 갖는 평가에 대해, 발생한 녹 면적이 10 % 에 이를 때까지의 시간을 측정했다. 또한, 화성 피막을 갖는 평가면에 있어서의 녹 면적은, 육안으로 녹을 확인한 지점의 합계 면적으로서 측정했다.The corrosion resistance of each test plate performed the neutral salt spray test according to JIS Z 2371:2015, and measured the time until the generated rust area reached 10% about the evaluation with a chemical conversion film. In addition, the rust area in the evaluation surface which has a chemical conversion film was measured as the total area of the point where rust was confirmed visually.
(4) 내산성 (4) acid resistance
각 시험판을 pH2 로 조정한 질산 수용액 (25 ℃) 에 5 분간 침지하고, 화성 피막의 탈색의 유무를 육안으로 확인하고, 이하의 평가 기준에 따라 내산성 (질산 수용액) 을 평가했다.Each test plate was immersed in an aqueous nitric acid solution (25°C) adjusted to pH2 for 5 minutes, the presence or absence of discoloration of the chemical conversion film was visually confirmed, and acid resistance (aqueous nitric acid solution) was evaluated according to the following evaluation criteria.
＜평가 기준＞<Evaluation criteria>
Y···탈색되어 있지 않다Y...not discolored
N···탈색되어 있다N...is discolored
또, 실시예 4 또는 15 의 화성 처리제를 사용하여 상기 서술한 바와 같이 화성 피막을 형성시킨 각 시험판을, 5 % 혹은 10 % 의 아세트산 수용액, 또는 5 % 혹은 10 % 의 시트르산 수용액 (각 25 ℃) 에 5 분간 침지하고, 화성 피막의 탈색의 유무를 육안으로 확인하고, 동일한 평가 기준에 따라 평가했다. 그 결과, 어느 수용액에 있어서도 탈색되지 않는 것이 밝혀졌다. 또한, 아세트산 및 시트르산을 사용한 내산성 평가 결과는, 표 2 에는 나타내고 있지 않다.Further, each test plate having a chemical conversion film formed as described above using the chemical conversion treatment agent of Example 4 or 15 was subjected to a 5% or 10% aqueous acetic acid solution, or a 5% or 10% aqueous citric acid solution (25°C each). was immersed for 5 minutes, the presence or absence of discoloration of the chemical conversion film was visually confirmed, and evaluation was performed according to the same evaluation criteria. As a result, it became clear that it did not decolorize also in any aqueous solution. In addition, the acid resistance evaluation result using acetic acid and citric acid is not shown in Table 2.
(5) 내알칼리성 (5) alkali resistance
각 시험판을 pH12 로 조정한 수산화나트륨 수용액 (25 ℃) 에 5 분간 침지하고, 화성 피막의 탈색의 유무를 육안으로 평가했다. Each test plate was immersed for 5 minutes in the sodium hydroxide aqueous solution (25 degreeC) adjusted to pH12, and the presence or absence of discoloration of the chemical conversion film was evaluated visually.
＜평가 기준＞<Evaluation criteria>
Y···탈색되어 있지 않다Y...not discolored
N···탈색되어 있다N...is discolored
표 2 에 나타내는 바와 같이, 실시예 (실시예 1 ~ 21) 의 화성 처리제를 사용한 경우, 비교예 (비교예 1 ~ 8) 의 화성 처리제를 사용한 경우와 비교해, 보다 우수한 내식성을 갖고, 착색된 화성 피막을 금속 재료의 표면 또는 표면 상에 형성할 수 있다. 또, 그 화성 피막은, 내산성 및 내알칼리성이 우수하다. 또한, 본 실시형태의 화성 처리제를 사용한 경우, 화성 피막의 색미 (화성 피막을 형성하기 전의 금속 재료의 색미와, 화성 피막을 형성한 후의 금속 재료의 색미의 차 : 색차) 와 그 화성 피막의 부착량이 상관을 나타낸다. 즉, 화성 피막의 색미를 육안으로 확인함으로써, 그 화성 피막의 부착량을 관리할 수 있다. 또, 금속 재료의 표면 또는 표면 상에, 색불균일이 없고 부착량이 균일한 화성 피막을 형성할 수 있다.As shown in Table 2, when the chemical conversion agent of Examples (Examples 1-21) is used, compared with the case where the chemical conversion agent of Comparative Examples (Comparative Examples 1-8) is used, it has more excellent corrosion resistance and is colored chemical conversion A film can be formed on the surface or on the surface of a metallic material. Moreover, the chemical conversion film is excellent in acid resistance and alkali resistance. In addition, when the chemical conversion treatment agent of this embodiment is used, the color taste of the chemical conversion film (difference between the color taste of the metallic material before formation of the chemical conversion film and the color taste of the metallic material after the chemical conversion film is formed: color difference) and the amount of the chemical conversion film deposited represents this correlation. That is, by visually confirming the color taste of the chemical conversion film, the amount of adhesion of the chemical conversion film can be managed. Moreover, a chemical conversion film with no color unevenness and uniform amount of adhesion can be formed on the surface or surface of a metallic material.
또한, 본 발명에 대해서는, 구체적인 실시예를 참조하여 상세하게 설명되지만, 본 발명의 취지 및 범위로부터 벗어나는 일 없이, 여러 가지의 변경, 개변을 실시할 수 있는 것은 당업자에게는 분명하다.In addition, although this invention is demonstrated in detail with reference to a specific Example, it is clear for those skilled in the art that various changes and modifications can be implemented without deviating from the meaning and scope of this invention.
Claims (3)
상기 이온 (C) 의 몰농도는, 상기 이온 (A) 의 몰농도에 대해 6 배 이상인, 화성 처리제.An ion (A) containing a metal element selected from zirconium, titanium and hafnium, an ion (B) containing a metal element selected from chromium, iron, cobalt, vanadium and copper, and an ion containing fluorine (C) and an acid dye (D);
The molar concentration of the said ion (C) is 6 times or more with respect to the molar concentration of the said ion (A), The chemical conversion treatment agent.
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| PCT/JP2020/008697 WO2020179734A1 (en) | 2019-03-05 | 2020-03-02 | Chemical conversion agent, method for producing metal material having chemical conversion coating, and metal material having chemical conversion coating |
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