TWI827811B - 化成處理劑、具有化成皮膜的金屬材料的製造方法以及具有化成皮膜的金屬材料 - Google Patents
化成處理劑、具有化成皮膜的金屬材料的製造方法以及具有化成皮膜的金屬材料 Download PDFInfo
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- TWI827811B TWI827811B TW109107273A TW109107273A TWI827811B TW I827811 B TWI827811 B TW I827811B TW 109107273 A TW109107273 A TW 109107273A TW 109107273 A TW109107273 A TW 109107273A TW I827811 B TWI827811 B TW I827811B
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- FPVGTPBMTFTMRT-UHFFFAOYSA-L disodium;2-amino-5-[(4-sulfonatophenyl)diazenyl]benzenesulfonate Chemical compound [Na+].[Na+].C1=C(S([O-])(=O)=O)C(N)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 FPVGTPBMTFTMRT-UHFFFAOYSA-L 0.000 description 1
- AHSJNHONMVUMLK-UHFFFAOYSA-L disodium;4',5'-diiodo-3-oxospiro[2-benzofuran-1,9'-xanthene]-3',6'-diolate Chemical compound [Na+].[Na+].O1C(=O)C2=CC=CC=C2C21C1=CC=C([O-])C(I)=C1OC1=C(I)C([O-])=CC=C21 AHSJNHONMVUMLK-UHFFFAOYSA-L 0.000 description 1
- FPAYXBWMYIMERV-UHFFFAOYSA-L disodium;5-methyl-2-[[4-(4-methyl-2-sulfonatoanilino)-9,10-dioxoanthracen-1-yl]amino]benzenesulfonate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)C1=CC(C)=CC=C1NC(C=1C(=O)C2=CC=CC=C2C(=O)C=11)=CC=C1NC1=CC=C(C)C=C1S([O-])(=O)=O FPAYXBWMYIMERV-UHFFFAOYSA-L 0.000 description 1
- 238000009820 dry lamination Methods 0.000 description 1
- SEACYXSIPDVVMV-UHFFFAOYSA-L eosin Y Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C([O-])=C(Br)C=C21 SEACYXSIPDVVMV-UHFFFAOYSA-L 0.000 description 1
- QGAYMQGSQUXCQO-UHFFFAOYSA-L eosin b Chemical compound [Na+].[Na+].O1C(=O)C2=CC=CC=C2C21C1=CC([N+]([O-])=O)=C([O-])C(Br)=C1OC1=C2C=C([N+]([O-])=O)C([O-])=C1Br QGAYMQGSQUXCQO-UHFFFAOYSA-L 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- IINNWAYUJNWZRM-UHFFFAOYSA-L erythrosin B Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C1=C2C=C(I)C(=O)C(I)=C2OC2=C(I)C([O-])=C(I)C=C21 IINNWAYUJNWZRM-UHFFFAOYSA-L 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 235000019233 fast yellow AB Nutrition 0.000 description 1
- MSNWSDPPULHLDL-UHFFFAOYSA-K ferric hydroxide Chemical compound [OH-].[OH-].[OH-].[Fe+3] MSNWSDPPULHLDL-UHFFFAOYSA-K 0.000 description 1
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 description 1
- GNBHRKFJIUUOQI-UHFFFAOYSA-N fluorescein Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC=C(O)C=C1OC1=CC(O)=CC=C21 GNBHRKFJIUUOQI-UHFFFAOYSA-N 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- GGJOARIBACGTDV-UHFFFAOYSA-N germanium difluoride Chemical compound F[Ge]F GGJOARIBACGTDV-UHFFFAOYSA-N 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 229910000449 hafnium oxide Inorganic materials 0.000 description 1
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 1
- TZNXTUDMYCRCAP-UHFFFAOYSA-N hafnium(4+);tetranitrate Chemical compound [Hf+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O TZNXTUDMYCRCAP-UHFFFAOYSA-N 0.000 description 1
- 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
- CTHCTLCNUREAJV-UHFFFAOYSA-N heptane-2,4,6-trione Chemical compound CC(=O)CC(=O)CC(C)=O CTHCTLCNUREAJV-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229940097275 indigo Drugs 0.000 description 1
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-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
- 229910000155 iron(II) phosphate 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
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- SDEKDNPYZOERBP-UHFFFAOYSA-H iron(ii) phosphate Chemical compound [Fe+2].[Fe+2].[Fe+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O SDEKDNPYZOERBP-UHFFFAOYSA-H 0.000 description 1
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 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
- 239000002609 medium Substances 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
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 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
- WIWVNQBYNTWQOW-UHFFFAOYSA-L oxovanadium(2+);diacetate Chemical compound [V+2]=O.CC([O-])=O.CC([O-])=O WIWVNQBYNTWQOW-UHFFFAOYSA-L 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 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
- 235000012736 patent blue V Nutrition 0.000 description 1
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- 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
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 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
- 229920002647 polyamide Polymers 0.000 description 1
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- 239000004645 polyester resin Substances 0.000 description 1
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- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
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- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane 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
- 238000007781 pre-processing Methods 0.000 description 1
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-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
- 238000007761 roller coating Methods 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
- 238000005507 spraying Methods 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- AWDBHOZBRXWRKS-UHFFFAOYSA-N tetrapotassium;iron(6+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+6].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] AWDBHOZBRXWRKS-UHFFFAOYSA-N 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
- 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
- YXZRCLVVNRLPTP-UHFFFAOYSA-J turquoise blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Cu+2].NC1=NC(Cl)=NC(NC=2C=C(NS(=O)(=O)C3=CC=4C(=C5NC=4NC=4[N-]C(=C6C=CC(=CC6=4)S([O-])(=O)=O)NC=4NC(=C6C=C(C=CC6=4)S([O-])(=O)=O)NC=4[N-]C(=C6C=CC(=CC6=4)S([O-])(=O)=O)N5)C=C3)C(=CC=2)S([O-])(=O)=O)=N1 YXZRCLVVNRLPTP-UHFFFAOYSA-J 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
- VLOPEOIIELCUML-UHFFFAOYSA-L vanadium(2+);sulfate Chemical compound [V+2].[O-]S([O-])(=O)=O VLOPEOIIELCUML-UHFFFAOYSA-L 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
- 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
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Abstract
本發明的目的為提供化成處理劑等，其可於金屬材料之表面或是表面上形成具有優異的耐腐蝕性且經著色的化成皮膜。化成處理劑包含：離子(A)，其包含選自鋯、鈦及鉿之金屬元素；離子(B)，其包含選自鉻、鐵、鈷、釩及銅之金屬元素；離子(C)，其包含氟；以及酸性染料(D)，其中，所述離子(C)的莫耳濃度係為相對於所述離子(A)的莫耳濃度的6倍以上。藉此化成處理劑來解決問題。
Description
本發明係關於：於金屬材料的表面或是表面上製造化成皮膜的化成處理劑；使用該化成處理劑來製造具有化成皮膜的金屬材料的方法；藉由該製造方法所製造的具有化成皮膜的金屬材料。
習知技術中已開發出可形成具有優異耐腐蝕性的化成皮膜的化成處理劑。例如，於專利文獻1當中揭示了一種包含液體組合物的處理液，該液體組合物包含：(A)三價鉻；(B) 鋯離子；(C)由氯離子、硫酸根離子以及硝酸根離子所組成群組當中的一種以上(D)芳香族碸；以及(E)氟離子。
[先前技術文獻]
[專利文獻]
[專利文獻1] 日本特開2015-38255號公報
[發明所欲解決問題]
本發明目的為提供可於金屬材料之表面或表面上形成具有優異耐腐蝕性且經著色的化成皮膜之化成處理劑等。
[解決問題之手段]
本案發明人為了解決上述問題反覆致力研究的結果，發現一種化成處理劑，其可形成具有優異耐腐蝕性且經著色的化成皮膜，進而完成本發明，該化成處理劑包含：離子(A)，其包含選自鋯、鈦及鉿之金屬元素；離子(B)，其包含選自鉻、鐵、鈷、釩及銅之金屬元素；離子(C)，其包含氟；以及酸性染料(D)，且所述離子(C)的莫耳濃度係為相對於所述離子(A)的莫耳濃度的6倍以上。
本發明包含以下內容。
[1]一種化成處理劑，其包含：離子(A)，其包含選自鋯、鈦及鉿之金屬元素；離子(B)，其包含選自鉻、鐵、鈷、釩及銅之金屬元素；離子(C)，其包含氟；以及酸性染料(D)，其中，所述離子(C)的莫耳濃度係為相對於所述離子(A)的莫耳濃度的6倍以上。
[2] 一種具有化成皮膜的金屬材料的製造方法，其包含使如[1]所述之化成處理劑接觸金屬材料之表面或是表面上。
[3] 一種具有化成皮膜的金屬材料，其係藉由如[2]所述之製造方法而獲得。
[發明功效]
根據本發明可提供一種可於金屬材料之表面或是表面上形成具有耐腐蝕性且經著色的化成皮膜之化成處理劑。此外，本發明還提供使用該化成處理劑而在金屬材料之表面或是表面上形成化成皮膜，以製造具有化成皮膜的金屬材料的方法；以及具有藉由所述製造方法所製造的化成皮膜的金屬材料。
本發明實施型態之化成處理劑係包含：離子(A)，其包含選自鋯、鈦及鉿之金屬元素；離子(B)，其包含選自鉻、鐵、鈷、釩及銅之金屬元素；離子(C)，其包含氟；以及酸性染料(D)，其中，所述離子(C)的莫耳濃度係為相對於所述離子(A)的莫耳濃度的6倍以上。藉由使用如此的化成處理劑，可於金屬材料之表面或是表面上製造具有優異耐腐蝕性且經著色的化成皮膜。此外，本實施型態之化成處理劑可為於水性介質中僅摻入離子(A)的供給源；離子(B)的供給源；離子(C)的供給源；酸性染料(D)，或是亦可進一步摻入其他成分。本實施型態之化成處理劑可為包含或是不包含含磷的化合物。
＜離子(A)＞
本實施型態之化成處理劑包含了含有選自鋯、鈦及鉿之金屬元素的離子(A)(以下或僅稱離子(A))。作為離子(A)可列舉例如：鋯、鈦及鉿之金屬離子；包含鋯、鈦及鉿之錯離子；鋯、鈦及鉿的氧化物離子等。此等離子亦可於化成處理劑當中包含1種或是2種以上。
化成處理劑當中的離子(A)的濃度並無特別限制，惟金屬換算質量濃度(當包含2種以上的離子(A)時係指合計金屬換算質量濃度)通常為5mg/L以上；又以20mg/L以上為較佳，此外通常為2000mg/L以下；又以1000mg/L以下為較佳。
作為離子(A)的供給源，只要是在與水性介質混合時可提供離子(A)的化合物即可，並無特別限制。可列舉例如：六氟鋯酸、硫酸鋯、硫酸氧鋯、硫酸鋯銨、硝酸鋯、硝酸氧鋯、硝酸鋯銨、乙酸氧鋯、乳酸鋯、四乙醯丙酮鋯、三丁氧基乙醯丙酮鋯、四正丙氧基鋯硝酸氧鋯、碳酸鋯、氫氧化鋯、氧化鋯、六氟鈦酸、硝酸鈦、硝酸氧鈦、硝酸鈦銨、硝酸鈦、硫酸鈦、硫酸氧鈦、硫酸鈦銨、氫氧化鈦、氧化鈦、氟化鈦銨、六氟鉿酸、硝酸鉿、氧化鉿等。當可取得此等成分的鹽形態時亦可為其鹽。此外，此等供給源可僅使用1種，亦可組合使用2種以上。
＜酸性染料(D)＞
本實施型態之化成處理劑係包含酸性染料(D)。於本說明書當中，「酸性染料」係指具有酸性基的水溶性染料及該酸性基反應而可形成鹽的水溶性染料。作為所述酸性基，可列舉例如磺基、羧基、酚性羥基、磷酸基等。酸性染料可使用具有1種或2種以上的酸性基的染料。此外，作為鹽，可列舉例如：鹼金屬鹽；鹼土金屬鹽；銨鹽；具有金屬元素如鋁、錫、鉻、銅、鈷、鎳、鐵等的鹽。此外，所述「水溶性染料」係指於20℃的水100g中溶解0.01g以上的染料。此外，以於20℃的水100g中溶解0.02g以上的染料為較佳；又以溶解0.2g以上的染料為更佳。酸性染料於水性介質當中以任何形態溶解皆可，例如，可為並未離子化的型態；亦可為一部分或是全部的官能基呈離子化的型態；亦可為呈錯離子化的型態；亦可為其他的形態。此等可於化成處理劑當中包含1種或是2種以上。
藉著將酸性染料(D)摻入至化成處理劑當中，可於金屬材料之表面或是表面上形成經著色的化成皮膜。此外，相較於藉由不含酸性染料(D)的化成處理劑而形成的化成皮膜，所述化成皮膜係具有優異的耐腐蝕性。
化成處理劑當中的酸性染料(D)的摻入量(濃度)並無特別限制，通常為200mg/L以上，此外，通常為30000mg/L以下；以10000mg/L以下為較佳；又以2000mg/L以下為更佳。
作為酸性染料(D)，只要是習知的酸性染料即可，可不特別限制。可列舉例如：偶氮酸性染料、三芳基甲烷酸性染料、靛類酸性染料、蒽醌酸性染料、二苯并吡喃(xanthene)酸性染料、喹啉酸性染料、硝基酸性染料及花青酸性染料等。此等係可使用1種或是組合使用2種以上，當組合使用2種以上時，可任意地組合。作為酸性染料(D)的具體例，以顏色索引名稱來說，可列舉：食品紅1、食品紅6、酸性紅1、酸性紅2、酸性紅9、酸性紅13、酸性紅18、酸性紅26、酸性紅27、酸性紅29、酸性紅33、酸性紅51、酸性紅52、酸性紅60、酸性紅73、酸性紅87、酸性紅88、酸性紅91、酸性紅92、酸性紅94、酸性紅95、酸性紅112、酸性紅114、酸性紅289、酸性紫9、酸性紫43、酸性橙7、酸性橙20、酸性橙24、酸性黃1、酸性黃3、酸性黃11、酸性黃23、酸性黃36、酸性黃40、酸性黃73、食品黃3、食品綠、酸性綠25、酸性綠5、酸性綠1、酸性綠3、食品藍2、酸性藍3、酸性藍5、酸性藍9、酸性藍74、直接藍1、直接藍2、直接藍6、直接藍14、活性藍21、酸性黑1等。
＜離子(B)＞
本實施形態之化成處理劑也包含了含有選自鉻、鐵、鈷、釩以及銅的金屬元素之離子(B)(以下或僅稱離子(B))。作為離子(B)可列舉例如：如鉻、鐵、鈷、釩或銅的金屬離子；含有鉻、鐵、鈷、釩或銅的錯離子；以及釩的氧化物離子等。此等離子可於化成處理劑當中含有1種或2種以上。
化成處理劑當中的離子(B)的濃度並無特別限制，惟作為金屬換算質量濃度(當包含2種以上的離子(B)時係指合計金屬換算質量濃度)通常為5mg/L以上，以20mg/L以上為較佳，此外，通常為2000mg/L以下，以1000mg/L以下為較佳。
作為離子(B)的供給源，只要是在與水性介質混合時可提供離子(B)的化合物即可，並無特別限制。可列舉例如：氟化鉻(III)、磷酸鉻(III)、硝酸鉻(III)、硫酸鉻(III)、氯化鉻(III)、醋酸鉻(III)、草酸鉻(III)、琥珀酸鉻(III)、氟化鐵(II)、氟化鐵(III)、氫氧化鐵(II)、氫氧化鐵(III)、硝酸鐵(II)、硝酸鐵(III)、乙醯丙酮鐵(III)、氯化鐵(II)、氯化鐵(III)、檸檬酸鐵(III)、氧化鐵(II)、氧化鐵(III)、六氰鐵(II)、六氰鐵(III)、六氰鐵(II)酸、六氰鐵(III)酸鉀、硫酸鐵(II)銨、硫酸鐵(III)銨、磷酸鐵(II)、氟化鈷、硫酸鈷、硝酸鈷、醋酸鈷、碳酸鈷、磷酸鈷、氯化鈷、氧化釩(II)、氧化釩(IV)、氧化釩(V)、偏釩酸鈉、偏釩酸鉀、偏釩酸銨、雙乙醯丙酮釩、二乙醯丙酮氧釩、氟化釩、磷酸釩、硫酸氧釩、硫化釩、草酸釩、三異丙氧基釩、氧基三氧化釩、氧基三乙氧基釩、三異丁氧基釩、釩氧三乙醇胺、檸檬酸釩銨、三丁氧基硬脂酸釩、乙醯丙酮氧釩、四丙氧基釩、四丁氧基釩、硝酸銅、硫酸銅、氯化銅、氧化銅、氟化銅等。當可取得此等成分的鹽形態時亦可為其鹽。此外，此等供給源可僅使用1種，亦可組合使用2種以上。惟離子(B)的供給源係為不同於酸性染料(D)的化合物。
＜含有氟的離子(C)＞
本實施形態之化成處理劑係包含了含有氟的離子(C)(以下或僅稱離子(C))。作為離子(C)，可列舉例如：氟離子；與存在於化成處理劑中的金屬離子結合或配位的離子等。此等離子可於化成處理劑當中包含1種或2種以上。
化成處理劑當中的離子(C)的濃度，只要是氟換算莫耳濃度為鋯、鈦及鉿的合計金屬換算莫耳濃度的6倍以上即可，且上限值係以200倍以下為較佳。
作為離子(C)的供給源，只要是在與水性介質混合時可提供離子(C)的化合物即可，並無特別限制。可列舉例如：如氫氟酸、氟化銨、氟化氫銨、氟化鍺、氟化鋁、氟化鉀、氟化氫鉀、氟化鈉、氟化氫鈉等的含氟化合物。此外，亦可僅由如六氟鋯酸、六氟鈦酸、六氟鉿酸等的離子(A)的供給源(其亦屬含氟化合物)來提供；亦可僅由如氟化鉻(III)、氟化鐵(II)、氟化鐵(III)、氟化鈷、氟化釩、氟化銅等的離子(B)的供給源(其亦屬含氟化合物)來提供；亦可由離子(A)的供給源及離子(B)的供給源來提供；亦可由離子(A)的供給源及離子(B)的供給源之外的含氟化合物來提供；亦可藉由摻入離子(A)的供給源及/或離子(B)的供給源以及其他的含氟化合物來提供。此外，當在使用如六氟鋯酸、六氟鈦酸、六氟鉿酸等這類含有鋯、鈦或鉿、氟的化合物來製備化成處理劑時，可供給離子(A)、離子(C)。此外，當在使用如氟化鉻(III)、氟化鐵(II)、氟化鐵(III)、氟化鈷、氟化釩、氟化銅等這類含有鉻、鐵、鈷、釩或銅、氟的化合物來製備化成處理劑時，可提供離子(B)、離子(C)。此外，各種含氟化合物可僅使用1種，亦可組合使用2種以上。
＜水性介質＞
作為水性介質，只要是水，或是水與水混溶性有機溶劑的混合物(以水性介質的體積為基準，含有50體積%以上的水)即可，並無特別限制。作為水混溶性有機溶劑，只要是與水混合者即可，並無特別限制，可列舉例如：如丙酮、甲基乙基酮等的酮類溶劑；如N, N’-二甲基甲醯胺、二甲基乙醯胺等的醯胺溶劑；如甲醇、乙醇、異丙醇等的醇類溶劑；如乙二醇單丁醚、乙二醇單己醚等的醚類溶劑；如1-甲基-2-吡咯烷酮、1-乙基-2-吡咯烷酮等的吡咯烷酮類溶劑。此等水混溶性有機溶劑可使用1種與水混合；亦可使用2種以上與水混合。
＜其他成分＞
作為其他成分，可列舉例如：包含選自鋁、鎂以及鋅的金屬的離子的供給源(E)；硝酸根離子源(F)；如用於調整待處理物的潤濕性的表面活性劑、被稱作消泡劑的表面活性劑等的添加劑；如pH調節劑等使用於化成處理劑的習知的添加劑；如丙烯酸樹脂、聚酯系樹脂、環氧系樹脂、聚烯烴系樹脂、酚醛系樹脂、聚乙烯系樹脂、聚氨酯基樹脂、聚醯亞胺系樹脂、聚醯胺系樹脂等習知的水溶性樹脂或是水分散性樹脂，惟並不受限於此等例。此外，此等其他成分可在不損害本發明功效的範圍內包含其中。
＜化成處理劑的pH＞
本實施形態之化成處理劑的pH並無特別限制，惟通常為酸性～中性區間，具體而言，pH係以1.0～7.0範圍內為較佳；1.5～6.0範圍內為更佳；又以2.0～5.5範圍內為最佳。於此，本說明書中的化成處理劑的pH值係指使用pH測量器於50℃下所測得的值。
化成處理劑的pH係可使用例如：如鹽酸、硫酸、硝酸、氫氟酸、硼酸、有機酸等的酸成分；如氫氧化鋰、氫氧化鉀、氫氧化鈉、氫氧化鈣、氫氧化鎂、氫氧化鋇、鹼金屬鹽、氨、銨鹽、胺類等的鹼成分；等pH調整劑來調整，惟不限於此等成分。此外，pH調整劑亦可使用1種或2種以上。
＜化成處理劑的製造方法＞
本實施形態之化成處理劑係可藉由以離子(A)的供給源、離子(B)的供給源、離子(C)的供給源、酸性染料(D)為原料，摻入預定量至水性介質中來製造。可藉由將所述各原料以例如上述順序摻入水性介質中來製造本實施形態之化成處理劑。此外，當摻入其他成分時，可藉由例如將所述各原料摻入水性介質中之後再摻入其他成分來進行製造。
＜化成皮膜的製造方法＞
本實施形態之化成皮膜的製造方法包含接觸步驟，其為使本實施形態之化成處理劑接觸金屬材料之表面或是表面上。藉此使得化成皮膜形成於金屬材料之表面或是表面上。作為使化成處理劑接觸金屬材料的方法，可為習知技術中的所有接觸方法，可列舉例如：浸漬處理法、或是噴塗處理法、淋塗處理法等處理法，或是將此等作組合等方法，但並不受限於此等方法。
所述接觸步驟係以於特定範圍內進行一定的時間為較佳。接觸溫度係以10℃以上且90℃以下範圍內為較佳；並以20℃以上且85℃以下範圍內為更佳，惟並不受此等溫度範圍的限制。此外，接觸時間係以20～700秒之間範圍內為較佳；又以30～600秒之間範圍內為更佳，惟並不受此等時間限制。
此外，可於接觸步驟之前進行預處理步驟。預處理步驟可列舉例如：酸洗步驟；脫脂步驟；鹼洗步驟；鉻酸鹽化成處理步驟；使用如磷酸鋅、磷酸鐵等的磷酸鹽之磷酸鹽化成處理步驟；鉍取代鍍覆步驟；鋯化成處理步驟；鈦化成處理步驟；鉿化成處理步驟；釩化成處理步驟等。於此等步驟當中以至少進行脫脂步驟為較佳。此外，此等的預處理步驟可進行1個步驟，亦可組合2個以上步驟依序進行。2個以上步驟之組合可舉例以磷酸鹽化成處理步驟搭配：鉻酸鹽化成處理步驟、鉍取代鍍覆步驟、鋯化成處理步驟、鈦化成處理步驟、鉿化成處理步驟、或是釩化成處理步驟的組合。作為預處理步驟而實施的鋯化成處理步驟可使用本實施形態之化成處理劑，亦可使用與本實施形態之化成處理劑不同的化成處理劑。此外，當進行所述各種預處理步驟時，亦可於各種預處理步驟之後進行水洗處理步驟。當進行複數個各種預處理步驟時，可於各個步驟之後或是一部分的步驟之後進行水洗處理步驟。此外，當進行水洗處理步驟時，亦可於其後進行乾燥金屬材料之表面的乾燥步驟。
此外，於本實施形態之化成皮膜的製造方法當中，可於接觸步驟之後進行後處理步驟，例如鹼洗步驟、水洗步驟、鉻酸鹽化成處理、磷酸鋅化成處理步驟、鉍取代鍍覆步驟、磷鐵化成處理步驟、鋯化成處理步驟、鈦化成處理步驟、鉿化成處理步驟、乾燥步驟等。此等的後處理步驟可單獨進行1個步驟，亦可組合2個以上步驟依序進行。作為後處理步驟而實施的鋯化成處理步驟係可使用本實施形態之化成處理劑，亦可使用不同於本實施形態之化成處理劑的化成處理劑。此外，當進行上述各種後處理步驟時，亦可於各種後處理步驟之後進行水洗處理步驟。於進行複數個各種後處理步驟時，亦可於各個步驟之後或是於一部分的步驟之後進行水洗處理步驟。此外，當進行水洗處理步驟時，亦可於其後進行乾燥金屬材料之表面的乾燥步驟。乾燥步驟通常為50～180℃；又以80～150℃為較佳，通常進行5～20分鐘；又以進行10～15分鐘為較佳。
金屬材料可列舉例如：鋼鐵材料(例如冷軋鋼板、熱軋鋼板、高強度鋼板、工具鋼、合金工具鋼、球化石墨鑄鐵、灰口鑄鐵等)；鍍覆材料，例如鍍鋅材料(例如電鍍鋅、熱浸鍍鋅等)、鍍覆鋅合金材料(例如熱浸鍍合金化鋅、鍍覆Zn-Al合金、鍍覆Zn-Al-Mg合金、電鍍鋅合金等)、鍍鋁材料等；鋁材料或鋁合金材料(例如1000系列、2000系列、3000係列、4000系列、5000系列、6000系列、7000系列、鋁鑄件、鋁合金鑄件、壓鑄材料等)；鎂材料或鎂合金材料；鋅材料或鋅合金材料；銅材料或銅合金材料；鉻材料或是鉻合金材料；鎳材料或是鎳合金材料；錫材料或是錫合金材料等。
本實施形態之具有化成皮膜的金屬材料，係可藉由使本實施形態之化成處理劑接觸金屬材料之表面或表面上，以於金屬材料之表面或表面上製造化成皮膜之方式來獲得。所製造的化成皮膜，包含於該化成皮膜當中的鋯、鈦、鉿、鉻、鐵、鈷、釩及銅的總合計質量係以每單位面積5mg/m2
以上為較佳；以10g/m2
以上為更佳；又以20g/m2
以上為最佳。此外，其上限值雖無特別限制，以200mg/m2
以下為較佳。此外，此化成皮膜當中的鋯、鈦、鉿、鉻、鐵、鈷、釩及銅的質量係可使用例如螢光X射線分析裝置來進行測量。
於所製造的化成皮膜當中，包含於該化成皮膜中的酸性染料的合計碳換算質量(以下或僅稱為染料附著量)係以每單位面積10mg/m2
以上為較佳；又以20mg/m2
以上為更佳，又以50mg/m2
以上為最佳。此外，其上限值並無特別限制，以200mg/m2
以下為較佳。此外，此化成皮膜當中的酸性染料的質量係可藉由總有機碳量測計(TOC)來進行測量。
本實施形態之具有化成皮膜的金屬材料當中，亦可於藉由使本實施形態之化成處理劑接觸而獲得的化成皮膜之上方或下方具有1或2個以上的所述各種皮膜(例如鉻酸鹽化成皮膜、磷酸鹽化成皮膜、鉍取代鍍覆皮膜等)。
可藉由於本實施形態之具有化成皮膜的金屬材料之表面上，使用塗料進行塗裝以形成塗膜，藉此來製造具有化成皮膜及塗膜的塗裝金屬材料。塗料並無特別限制，只要是使用有色塗料即可，亦可使用透明塗料以使得由酸性染料(D)所賦予的顏色不會改變。塗裝方法並無特別限制，可適用如輥塗法、液浸塗裝法、靜電粉末塗裝法、電著塗裝法；溶劑塗裝法等習知的方法。此外，亦可藉由乾式層壓法或擠出層壓法來貼合層壓膜。塗裝金屬材料可為於本實施形態之具有化成皮膜的金屬材料的表面上具有塗膜；亦可為於該化成皮膜上進一步形成的1個或2個以上的所述各種皮膜(例如鉻酸鹽化成皮膜、磷酸鹽化成皮膜、鉍取代鍍覆皮膜、釩化成皮膜等)的表面上具有塗膜。此外，塗膜可由1層形成；亦可由2層以上形成。塗膜的厚度並無特別限制，可根據塗裝金屬材料的使用用途而適當地進行設定。
[實施例]
以下根據實施例來詳細說明本發明之功效，惟本發明並不受以下實施例所限制。
＜金屬材料＞
將下述者分別以長150mm*寬70mm尺寸進行裁切：日本工業規格(JIS) H 4000：2014規格的鋁板(A1050：厚度：0.8mm)；JIS G 3302：2010規格的熱浸鍍鋅鋼板(GI：厚度：0.6mm，鍍覆附著量：單面50g/m2
)；JIS G 3321：2012規格的熱浸鍍鋁-鋅鋼板(GL：厚度：0.4mm、鍍覆附著量：單面75/m2
)；JIS G3313：2010規格的電鍍鋅鋼板(EG：厚度0.8mm、鍍覆附著量：單面45g/m2
)。
＜使用於製備化成處理劑的各種成分＞
於化成處理劑的製備上係分別地使用A1：六氟鋯酸(森田化學工業(股))、A2：硫酸鋯(日本輕金屬(股))、以及A3：氟化鈦銨(森田化學工業(股))來作為離子(A)的供給源；分別地使用B1：硝酸鉻(日本化學工業(股))、B2：硫酸鉻(日本化學工業(股))、B3：硝酸鐵(富士薄膜和光純藥(股))、B4：硫酸銅(富士薄膜和光純藥(股))來作為離子(B)的供給源；分別地使用C1：氫氟酸(森田化學工業(股))、C2：氟化鋁(森田化學工業(股))來作為離子(C)的供給源；分別地使用D1：食品黃No.5(東京化成工業(股)；食品黃3)、D2：酸性黃23(東京化成工業(股))、D3：酸性紅27(東京化成工業(股))、D4：酸性藍74(東京化成工業(股))、D5：酸性藍9(東京化成工業(股))、D6：索米菲克斯綠松石藍G(N)(住友化學(股))；活性藍-21)等酸性染料、D7：鹼性藍9(富士薄膜和光純藥(股))、D8：鹼性紫10(富士薄膜和光純藥(股))、D9：鹼性紫3(富士薄膜和光純藥(股))等鹼性染料來作為離子(D)的供給源。此外，所述A1及A3可作為離子(C)的供給源來使用。
＜製備化成處理劑＞
如表1所示，將各個成分的特定量摻入水中之後，藉著用氨來調整至預定的pH，以製備實施例1～21及比較例1～8的化成處理劑。
＜製備具有化成皮膜的金屬材料＞
藉由將各種金屬材料(A1050，GI, GL以及EG)浸漬於調整至50℃的脫脂劑(FC-4424；日本帕卡瀨精股份有限公司；使用溶解於水的水溶液並使其呈20g/L濃度)中120秒，以進行脫脂。其後，進行30秒的噴霧清洗。接著，於表1所示條件下，將金屬材料浸漬於各種化成處理劑(實施例1～21及比較例1～8的化成處理劑)，以於金屬材料之表面或表面上製造化成皮膜。將所得到的具有化成皮膜的金屬材料之表面上依序以自來水、去離子水來清洗，並於150℃下乾燥10分鐘，得到試驗板。
[表1]
| 金屬材料 | 離子(A) | 離子(B) | 離子(C ) | 染料(D) | 接觸條件 | |||||||
| 供給源 | 濃度mg/L | 供給源 | 濃度mg/L | 供給源 | 相對於離子(A)的莫耳濃度倍數 | 種類 | 質量濃度mg/L | 溫度℃ | pH | 時間 s | ||
| 實施例1 | A1050 | A1 | 5 | B1 | 5 | A1 | 6 | D1 | 200 | 30 | 2.5 | 600 |
| 實施例2 | A1050 | A1 | 1000 | B1 | 1000 | A1 | 6 | D1 | 2000 | 80 | 5.0 | 30 |
| 實施例3 | A1050 | A1 | 100 | B1 | 150 | A1 | 6 | D1 | 500 | 50 | 4.0 | 120 |
| 實施例4 | A1050 | A1 | 100 | B1 | 150 | A1, C1 | 15 | D1 | 500 | 50 | 4.0 | 120 |
| 實施例5 | A1050 | A2 | 100 | B1 | 150 | C1 | 15 | D1 | 500 | 50 | 4.0 | 120 |
| 實施例6 | A1050 | A2 | 100 | B1 | 150 | C2 | 15 | D1 | 500 | 50 | 4.0 | 120 |
| 實施例7 | A1050 | A3 | 100 | B1 | 150 | A3 | 6 | D1 | 500 | 50 | 4.0 | 120 |
| 實施例8 | A1050 | A1 | 100 | B2 | 150 | A1, C1 | 15 | D1 | 500 | 50 | 4.0 | 120 |
| 實施例9 | A1050 | A1 | 100 | B3 | 150 | A1, C1 | 15 | D1 | 500 | 50 | 4.0 | 120 |
| 實施例10 | A1050 | A1 | 100 | B4 | 150 | A1, C1 | 15 | D1 | 500 | 50 | 4.0 | 120 |
| 實施例11 | A1050 | A1 | 100 | B1 | 150 | A1, C1 | 15 | D2 | 500 | 50 | 4.0 | 120 |
| 實施例12 | A1050 | A1 | 100 | B1 | 150 | A1, C1 | 15 | D3 | 500 | 50 | 4.0 | 120 |
| 實施例13 | A1050 | A1 | 100 | B1 | 150 | A1, C1 | 15 | D4 | 500 | 50 | 4.0 | 120 |
| 實施例14 | A1050 | A1 | 100 | B1 | 150 | A1, C1 | 15 | D5 | 500 | 50 | 4.0 | 120 |
| 實施例15 | A1050 | A1 | 100 | B1 | 150 | A1, C1 | 15 | D6 | 500 | 50 | 4.0 | 120 |
| 實施例16 | GI | A1 | 100 | B3 | 150 | A1, C2 | 12 | D2 | 500 | 50 | 4.0 | 120 |
| 實施例17 | GI | A1 | 100 | B4 | 150 | A1, C2 | 12 | D3 | 500 | 50 | 4.0 | 120 |
| 實施例18 | GL | A2 | 100 | B3 | 150 | C2 | 12 | D3 | 500 | 50 | 4.0 | 120 |
| 實施例19 | GL | A2 | 100 | B4 | 150 | C2 | 12 | D4 | 500 | 50 | 4.0 | 120 |
| 實施例20 | EG | A3 | 100 | B3 | 150 | A3 | 6 | D4 | 500 | 50 | 4.0 | 120 |
| 實施例21 | EG | A3 | 100 | B4 | 150 | A3 | 6 | D5 | 500 | 50 | 4.0 | 120 |
| 比較例1 | A1050 | A1 | 100 | B1 | 150 | A1, C1 | 15 | -- | -- | 30 | 4.0 | 120 |
| 比較例2 | GI | A1 | 100 | B3 | 150 | A1, C2 | 12 | -- | -- | 50 | 4.0 | 120 |
| 比較例3 | A1050 | -- | -- | B1 | 150 | C1 | 15 | D2 | 500 | 50 | 4.0 | 120 |
| 比較例4 | A1050 | A1 | 100 | -- | -- | A1, C1 | 15 | D2 | 500 | 50 | 4.0 | 120 |
| 比較例5 | A1050 | A2 | 100 | B1 | 150 | -- | -- | D3 | 500 | 50 | 4.0 | 120 |
| 比較例6 | A1050 | A1 | 100 | B1 | 150 | A1, C1 | 15 | D7 | 500 | 50 | 4.0 | 120 |
| 比較例7 | A1050 | A1 | 100 | B1 | 150 | A1, C1 | 15 | D8 | 500 | 50 | 4.0 | 120 |
| 比較例8 | A1050 | A1 | 100 | B1 | 150 | A1, C1 | 15 | D9 | 500 | 50 | 4.0 | 120 |
＜性能評價＞
使用製作好的試驗板來進行以下的性能評價。將結果表示於表2。
(1)附著量
針對製作好的試驗板的化成皮膜的附著量(全部金屬合計附著量)，使用理學股份有限公司製造的掃描型螢光X射線分析裝置ZSX primusII來測量化成皮膜中所包含的鋯、鈦、鉻、鐵及銅之全部合計質量。此外，由使用島津製作所股份有限公司製造的總有機碳測量計TOC-LCSH所測量到的總有機碳量經換算而求得染料附著量。
(2)著色性。
目視判別所製作試驗板的著色情況。
＜判別基準＞
Y・・・觀察到著色
N・・・未觀察到著色
(3)耐腐蝕性
各個試驗板的耐腐蝕性係根據JIS Z 2371：2015進行中性鹽水噴霧試驗，測量相對於具有化成皮膜的評價產生生鏽的面積達10%的所需時間。此外，具有化成皮膜的評價面當中的生鏽面積係以目視確認到部分的總面積來測量。
(4)耐酸性
將各個試驗板浸漬至調整為pH2的硝酸水溶液(25℃)中5分鐘，目視觀察化成皮膜是否有褪色，並根據以下的評價基準來評價耐酸性(硝酸水溶液)。
＜評價基準＞
Y・・・未褪色
N・・・有褪色
此外，將使用實施例4或15的化成處理劑以上述方式形成了化成皮膜的各個試驗板，浸漬至5%或是10%的乙酸水溶液；或是5%或是10%的檸檬酸水溶液(各25℃)，目視觀察化成皮膜是否褪色，並以相同的評價基準進行評價。其結果為於任何水溶液當中都沒有發生褪色。此外，使用乙酸及檸檬酸所作的耐酸性評價結果並未表示於表2中。
(5)耐鹼性
將各個試驗板浸漬至調整為pH12的氫氧化鈉水溶液(25℃)中5分鐘，並且以目視評價化成皮膜是否有褪色。
＜評價基準＞
Y・・・未褪色
N・・・有褪色
[表2]
| 評價 | ||||||
| 全部金屬合計附著量mg/m2 | 染料附著量mg/m2 | 著色性 | 耐腐蝕性 | 耐酸性 | 耐鹼性 | |
| 實施例1 | 31 | 24 | Y | 480h | Y | Y |
| 實施例2 | 43 | 35 | Y | 480h | Y | Y |
| 實施例3 | 35 | 26 | Y | 480h | Y | Y |
| 實施例4 | 66 | 51 | Y | 480h | Y | Y |
| 實施例5 | 52 | 43 | Y | 480h | Y | Y |
| 實施例6 | 50 | 41 | Y | 480h | Y | Y |
| 實施例7 | 31 | 22 | Y | 480h | Y | Y |
| 實施例8 | 59 | 46 | Y | 480h | Y | Y |
| 實施例9 | 62 | 49 | Y | 480h | Y | Y |
| 實施例10 | 58 | 45 | Y | 480h | Y | Y |
| 實施例11 | 61 | 56 | Y | 480h | Y | Y |
| 實施例12 | 54 | 46 | Y | 480h | Y | Y |
| 實施例13 | 60 | 57 | Y | 480h | Y | Y |
| 實施例14 | 51 | 52 | Y | 480h | Y | Y |
| 實施例15 | 53 | 78 | Y | 480h | Y | Y |
| 實施例16 | 62 | 58 | Y | 48h | Y | Y |
| 實施例17 | 67 | 57 | Y | 48h | Y | Y |
| 實施例18 | 63 | 54 | Y | 144h | Y | Y |
| 實施例19 | 64 | 61 | Y | 144h | Y | Y |
| 實施例20 | 33 | 31 | Y | 72h | Y | Y |
| 實施例21 | 32 | 32 | Y | 72h | Y | Y |
| 比較例1 | 60 | 0 | N | 360h | -- | -- |
| 比較例2 | 61 | 0 | N | 24h | -- | -- |
| 比較例3 | 5 | 4 | N | 360h | -- | -- |
| 比較例4 | 30 | 5 | N | 360h | -- | -- |
| 比較例5 | 7 | 3 | N | 360h | -- | -- |
| 比較例6 | 61 | 0 | N | 360h | -- | -- |
| 比較例7 | 66 | 0 | N | 360h | -- | -- |
| 比較例8 | 63 | 0 | N | 360h | -- | -- |
如表2所示，相較於比較例(比較例1～8)的化成處理劑時，使用實施例(實施例1～21)的化成處理劑時可於金屬材料之表面或表面上形成具有優異耐腐蝕性且經著色的化成皮膜。此外，所述化成皮膜具有優異的耐酸性及耐鹼性。此外，當使用本實施型態的化成處理劑時，化成皮膜的色調(形成化成皮膜之前的金屬材料的色調，與形成化成皮膜之後的金屬材料的色調之間的差：色差)係與所述化成皮膜的附著量呈現相關。也就是說，藉由以目視來確認化成皮膜的色調，可控制所述化成皮膜的附著量。此外，可於金屬材料的表面或是表面上形成無顏色落差且附著量均勻的化成皮膜。
此外，關於本發明已參考具體實施例進行詳細說明，但顯而易見地，在不脫離本發明主旨及範圍的情況下，本發明所屬技術領域中具通常知識者可進行各種的變更、改變。
無
無。
Claims (3)
- 一種化成處理劑，其包含：離子(A)，其包含選自鋯、鈦及鉿之金屬元素；離子(B)，其包含選自鉻、鐵、鈷、釩及銅之金屬元素；離子(C)，其包含氟；以及酸性染料(D)，其中，所述離子(C)的莫耳濃度係為相對於所述離子(A)的莫耳濃度的6倍以上，且所述酸性染料(D)係具有酸性基的水溶性染料及該酸性基反應而可形成鹽的水溶性染料。
- 一種具有化成皮膜的金屬材料的製造方法，其包含使如請求項1所述之化成處理劑接觸金屬材料之表面或是表面上。
- 一種具有化成皮膜的金屬材料，其係藉由如請求項2所述之製造方法而獲得。
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