CN100363537C - Metal surface treatment composite, metal surface treatment method and galvanized steel sheet obtained by it - Google Patents
Metal surface treatment composite, metal surface treatment method and galvanized steel sheet obtained by it Download PDFInfo
- Publication number
- CN100363537C CN100363537C CNB031500749A CN03150074A CN100363537C CN 100363537 C CN100363537 C CN 100363537C CN B031500749 A CNB031500749 A CN B031500749A CN 03150074 A CN03150074 A CN 03150074A CN 100363537 C CN100363537 C CN 100363537C
- Authority
- CN
- China
- Prior art keywords
- metal surface
- surface treating
- treating composition
- quality
- steel plate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 81
- 239000002184 metal Substances 0.000 title claims abstract description 81
- 238000000034 method Methods 0.000 title claims abstract description 39
- 238000004381 surface treatment Methods 0.000 title abstract description 10
- 229910001335 Galvanized steel Inorganic materials 0.000 title abstract 3
- 239000008397 galvanized steel Substances 0.000 title abstract 3
- 239000002131 composite material Substances 0.000 title 1
- 239000000203 mixture Substances 0.000 claims abstract description 76
- 229910000484 niobium oxide Inorganic materials 0.000 claims abstract description 41
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims abstract description 40
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 60
- 239000007787 solid Substances 0.000 claims description 55
- 229910000831 Steel Inorganic materials 0.000 claims description 44
- 239000010959 steel Substances 0.000 claims description 44
- 239000000377 silicon dioxide Substances 0.000 claims description 27
- 229920005989 resin Polymers 0.000 claims description 26
- 239000011347 resin Substances 0.000 claims description 26
- 229960001866 silicon dioxide Drugs 0.000 claims description 26
- 235000012239 silicon dioxide Nutrition 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 22
- 150000003755 zirconium compounds Chemical class 0.000 claims description 14
- 150000003609 titanium compounds Chemical class 0.000 claims description 13
- 150000003682 vanadium compounds Chemical class 0.000 claims description 13
- 239000000126 substance Substances 0.000 abstract description 25
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 239000002245 particle Substances 0.000 abstract description 11
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract 1
- 239000002585 base Substances 0.000 description 19
- 239000010955 niobium Substances 0.000 description 15
- 239000006087 Silane Coupling Agent Substances 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 11
- -1 vanadyl compound Chemical class 0.000 description 11
- 239000011651 chromium Substances 0.000 description 10
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 9
- 229910019142 PO4 Inorganic materials 0.000 description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 9
- 229910052804 chromium Inorganic materials 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 239000010452 phosphate Substances 0.000 description 9
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 8
- 229910004298 SiO 2 Inorganic materials 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 8
- 239000010936 titanium Substances 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 7
- 230000001070 adhesive effect Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000011701 zinc Substances 0.000 description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 6
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 6
- 229910052725 zinc Inorganic materials 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 238000005254 chromizing Methods 0.000 description 5
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000010808 liquid waste Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 4
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 3
- 241000406668 Loxodonta cyclotis Species 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 230000003628 erosive effect Effects 0.000 description 3
- IBKNSIPMTGYUNZ-UHFFFAOYSA-N ethenyl(methoxy)silane Chemical compound CO[SiH2]C=C IBKNSIPMTGYUNZ-UHFFFAOYSA-N 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 150000003016 phosphoric acids Chemical class 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- 229910002012 Aerosil® Inorganic materials 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 2
- 241000863032 Trieres Species 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- PKTOVQRKCNPVKY-UHFFFAOYSA-N dimethoxy(methyl)silicon Chemical compound CO[Si](C)OC PKTOVQRKCNPVKY-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- MASNVFNHVJIXLL-UHFFFAOYSA-N ethenyl(ethoxy)silicon Chemical compound CCO[Si]C=C MASNVFNHVJIXLL-UHFFFAOYSA-N 0.000 description 2
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- WPCMRGJTLPITMF-UHFFFAOYSA-I niobium(5+);pentahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[Nb+5] WPCMRGJTLPITMF-UHFFFAOYSA-I 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- QLNOVKKVHFRGMA-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical group [CH2]CC[Si](OC)(OC)OC QLNOVKKVHFRGMA-UHFFFAOYSA-N 0.000 description 2
- 229960004418 trolamine Drugs 0.000 description 2
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical compound O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 0.000 description 2
- 229910001935 vanadium oxide Inorganic materials 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 description 1
- DJSWDXUOSQTQCP-UHFFFAOYSA-N 2-ethylhexanoic acid;titanium Chemical compound [Ti].CCCCC(CC)C(O)=O DJSWDXUOSQTQCP-UHFFFAOYSA-N 0.000 description 1
- IAGCDJZAYOZMCS-UHFFFAOYSA-N 2-hydroxypropanoic acid;titanium Chemical compound [Ti].CC(O)C(O)=O IAGCDJZAYOZMCS-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 description 1
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 1
- PRKPGWQEKNEVEU-UHFFFAOYSA-N 4-methyl-n-(3-triethoxysilylpropyl)pentan-2-imine Chemical compound CCO[Si](OCC)(OCC)CCCN=C(C)CC(C)C PRKPGWQEKNEVEU-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- WRAGBEWQGHCDDU-UHFFFAOYSA-M C([O-])([O-])=O.[NH4+].[Zr+] Chemical compound C([O-])([O-])=O.[NH4+].[Zr+] WRAGBEWQGHCDDU-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229910001200 Ferrotitanium Inorganic materials 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910000617 Mangalloy Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- KYNKUCOQLYEJPH-UHFFFAOYSA-N [K][Ti] Chemical compound [K][Ti] KYNKUCOQLYEJPH-UHFFFAOYSA-N 0.000 description 1
- LOUBVQKDBZRZNQ-UHFFFAOYSA-M [O-2].[O-2].[OH-].O.[V+5] Chemical compound [O-2].[O-2].[OH-].O.[V+5] LOUBVQKDBZRZNQ-UHFFFAOYSA-M 0.000 description 1
- QKDGGEBMABOMMW-UHFFFAOYSA-I [OH-].[OH-].[OH-].[OH-].[OH-].[V+5] Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[V+5] QKDGGEBMABOMMW-UHFFFAOYSA-I 0.000 description 1
- DBPSXFFYFVICGW-UHFFFAOYSA-N [Si](=O)=O.[V] Chemical compound [Si](=O)=O.[V] DBPSXFFYFVICGW-UHFFFAOYSA-N 0.000 description 1
- DZOAJBFFBLATMV-UHFFFAOYSA-M [Ti]F Chemical compound [Ti]F DZOAJBFFBLATMV-UHFFFAOYSA-M 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 150000001553 barium compounds Chemical class 0.000 description 1
- NUDBTPOFFXMXJM-UHFFFAOYSA-N boric acid zirconium Chemical compound [Zr].B(O)(O)O NUDBTPOFFXMXJM-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- NMGYKLMMQCTUGI-UHFFFAOYSA-J diazanium;titanium(4+);hexafluoride Chemical compound [NH4+].[NH4+].[F-].[F-].[F-].[F-].[F-].[F-].[Ti+4] NMGYKLMMQCTUGI-UHFFFAOYSA-J 0.000 description 1
- HLJCWGPUCQTHFY-UHFFFAOYSA-H disodium;hexafluorotitanium(2-) Chemical compound [F-].[F-].[Na+].[Na+].F[Ti](F)(F)F HLJCWGPUCQTHFY-UHFFFAOYSA-H 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229940040145 liniment Drugs 0.000 description 1
- 239000000865 liniment Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- ALTWGIIQPLQAAM-UHFFFAOYSA-N metavanadate Chemical compound [O-][V](=O)=O ALTWGIIQPLQAAM-UHFFFAOYSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- HRRDCWDFRIJIQZ-UHFFFAOYSA-N naphthalene-1,8-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=C2C(C(=O)O)=CC=CC2=C1 HRRDCWDFRIJIQZ-UHFFFAOYSA-N 0.000 description 1
- BPYXFMVJXTUYRV-UHFFFAOYSA-J octanoate;zirconium(4+) Chemical compound [Zr+4].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O.CCCCCCCC([O-])=O.CCCCCCCC([O-])=O BPYXFMVJXTUYRV-UHFFFAOYSA-J 0.000 description 1
- ZDYUUBIMAGBMPY-UHFFFAOYSA-N oxalic acid;hydrate Chemical class O.OC(=O)C(O)=O ZDYUUBIMAGBMPY-UHFFFAOYSA-N 0.000 description 1
- IJZKJRUCRGJGKO-UHFFFAOYSA-N oxalic acid;zirconium Chemical compound [Zr].OC(=O)C(O)=O IJZKJRUCRGJGKO-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- AHBPBADERZDJKT-UHFFFAOYSA-N pentane-2,3-dione zirconium Chemical compound [Zr].C(C)C(=O)C(=O)C AHBPBADERZDJKT-UHFFFAOYSA-N 0.000 description 1
- LYHRKKPIWZCMEW-UHFFFAOYSA-N pentane-2,3-dione zirconium(4+) Chemical compound C(C)C(=O)C(=O)C.[Zr+4] LYHRKKPIWZCMEW-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- BFDQRLXGNLZULX-UHFFFAOYSA-N titanium hydrofluoride Chemical compound F.[Ti] BFDQRLXGNLZULX-UHFFFAOYSA-N 0.000 description 1
- XROWMBWRMNHXMF-UHFFFAOYSA-J titanium tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[Ti+4] XROWMBWRMNHXMF-UHFFFAOYSA-J 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- KAHROJAJXYSFOD-UHFFFAOYSA-J triazanium;zirconium(4+);tricarbonate;hydroxide Chemical compound [NH4+].[NH4+].[NH4+].[OH-].[Zr+4].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O KAHROJAJXYSFOD-UHFFFAOYSA-J 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 125000005287 vanadyl group Chemical group 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- OMQSJNWFFJOIMO-UHFFFAOYSA-J zirconium tetrafluoride Chemical compound F[Zr](F)(F)F OMQSJNWFFJOIMO-UHFFFAOYSA-J 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
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 1
Abstract
Provided is a chemical conversion treatment agent and a chemical conversion treatment method by which a galvanized steel sheet can satisfactorily be subjected to chemical conversion treatment, and to provide a galvanized steel sheet which is obtained by the chemical conversion method, and has excellent rust preventability and excellent adhesion, and to provide a metal surface treatment composition comprising niobium oxide colloidal particles.
Description
Technical field
The steel plate galvanized that the present invention relates to metal surface treating composition, metal surface treating method and obtain thus.
Background technology
The steel plate galvanized that is coated with zinc or zinc alloy etc. is the steel of fine corrosion resistance.The zinc coating of this steel plate galvanized contacts with air to be understood oxidized and the generation white rust, so need come inhibited oxidation by surface treatment.In addition, according to the requirement of using, this steel plate galvanized is not coated with application layer sometimes after processing.At this moment, not the steel plate galvanized of band coating to have an antirust ability just very important.
Know that above-mentioned surface treatment method can be to adopt chromium cpd to carry out the method that chromising is handled.Chromising can prevent the generation of white rust, thereby can obtain very ideal steel plate galvanized.Yet the treatment cost of waste liquor that contains chromium cpd is very high, so have the people to study not adopt the non-chromising treatment process of chromium cpd, i.e. chemical conversion processing method.
Japanese kokai publication hei 9-241856, TOHKEMY 2001-172771 and TOHKEMY 2001-247977 have described the metal conditioner that contains metal-salt that is used for steel plate galvanized.Yet, adopt this treatment agent that steel plate galvanized is carried out surface treatment after, the rust-preventing characteristic of steel plate galvanized and the adhesive ability of filming etc. are not good.
TOHKEMY 2002-105659 discloses a kind of chemical conversion that is used for steel plate galvanized and has handled solution, and described solution contains oxygen acid, manganic compound, titanium compound and phosphoric acid or the phosphoric acid salt of metals such as being selected from molybdenum, vanadium, tungsten, niobium or tantalum.Yet this chemical conversion that is used for steel plate galvanized is handled solution and need be used manganic compound.Using of manganic compound must bring white elephant as liquid waste disposal, so, preferably do not use manganic compound.
In addition, the someone has adopted the silicon-dioxide that can the be scattered in water antirust component as metal surface treating composition.Yet when independent use can be scattered in the silicon-dioxide of water, rust-proof effect was not good, thereby can not obtain the good steel plate galvanized of rust-preventing characteristic.
Summary of the invention
In view of above-mentioned present situation, the present invention aims to provide a kind of chemical conversion treating agent, a kind ofly can carry out the method for effective chemical conversion processing and a kind ofly have the excellent rust-preventing characteristic and a steel plate galvanized of adhesive ability by what this method obtained steel plate galvanized.
The invention provides a kind of metal surface treating composition, wherein contain the niobium oxides colloidal solid.
Described metal surface treating composition preferably contains the silicon-dioxide that can be scattered in water.
Described metal surface treating composition preferably contains at least a compound that is selected from the group of being made up of vanadium compound, zirconium compounds and titanium compound.
Described metal surface treating composition preferably contains water-base resin.
The invention provides a kind of metal surface treating method, described method comprises with described metal surface treating composition handles steel plate galvanized, thereby forms the step of handling film.
The invention provides a kind of steel plate galvanized with the processing film that forms by described metal surface treating method.
To describe the present invention in detail below.
Surface treating composition of the present invention contains the niobium oxides colloidal solid that is scattered in the aqueous medium.Because, if the median size of above-mentioned niobium oxides colloidal solid is more little, just can stably form fine and close niobium oxides more and handle film, this niobium oxides colloidal solid can be processed object and gives stable rust-preventing characteristic, so the less niobium oxides colloidal solid of preferable particle size.In addition, need not to add for example component such as chromium, manganese in the surface treating composition of the present invention, these components can be brought very big difficulty to liquid waste disposal.
The used niobium oxides colloidal solid of the present invention is the particulate niobium oxides that is scattered in the water, and or rather, described particle comprises for example unbodied particle and the midbody particle between niobium hydroxide and niobium oxides.
Can adopt niobium oxides colloidal sol to prepare metal surface treating composition of the present invention by the currently known methods preparation.Have no particular limits for above-mentioned niobium oxides colloidal sol, it can be the colloidal sol by the currently known methods preparation, for example, and by the colloidal sol of described method preparation such as Japanese kokai publication hei 6-321543, Japanese kokai publication hei 8-143314 and Japanese kokai publication hei 8-325018.Also can adopt from TakiChemical Co., the commodity niobium oxides colloidal sol of Ltd..
The currently known methods of above-mentioned preparation niobium oxides colloidal sol can be the method that can obtain the niobium oxides colloidal solid solution of homogeneous, said method comprising the steps of, for example, niobium oxides is dissolved in hydrofluoric acid, gained solution is added in the ammoniacal liquor, filter the slurry that gained solution and washing obtain niobium hydroxide, subsequently, successively add two oxalic acid hydrates and water, under stirring and reflux conditions, promote the reaction of gained slurry.Can determine the terminal point of reaction according to the color of described slurry, that is, determine whether to obtain the niobium oxides colloidal solid solution of homogeneous,, can determine that then this slurry is the homogeneous state if described slurry has become blueness.Above-mentioned niobium oxides colloidal sol can be diluted to desired concn or add other components as required, thereby make metal surface treating composition of the present invention.
The median size of the niobium oxides colloidal solid that metal surface treating composition of the present invention is contained is preferably 1000nm or littler.More preferably 2nm is to 600nm for described median size, and further preferred 2nm is to 100nm.Because if described median size is more little, then can stably form fine and close niobium oxides film more, and the niobium oxides particle can be processed object and gives stable rust-preventing characteristic, so preferred smaller particle size.Can adopt particle size analyzer to measure described median size.Described particle size analyzer can be the particle size analyzer that adopts dynamic scattering light, for example NICOMP 370 type particle size analyzers (PACIFIC SCIENTIFIC product).
In metal surface treating composition of the present invention, the Nb in the niobium oxides colloidal solid is being scaled Nb
2O
5Situation under, with respect to the solid matter total amount in the metal surface treating composition, the content of niobium oxides colloidal solid is preferably 1 quality % or higher.If above-mentioned content is lower than 1 quality %, then can not obtain enough rust-preventing characteristics, therefore preferred above-mentioned content is not less than 1 quality %.Additional disclosure once, above-mentioned numerical value is meant, the Nb in the niobium oxides colloidal solid is being scaled Nb
2O
5Situation under, with respect to the content of the solid matter total amount in the metal surface treating composition.Above-mentioned content more preferably 2 quality % to 30 quality %.
Metal surface treating composition of the present invention preferably further contains the silicon-dioxide that can be scattered in water, so that improve the rust-preventing characteristic of surface treatment film.Although separately the use silicon-dioxide that can be scattered in water can not obtain good rust-preventing characteristic, silicon-dioxide and described niobium oxides colloidal solid be used in combination then can improve rust-preventing characteristic synergistically.
Have no particular limits for the described silicon-dioxide that is scattered in water, it for example can comprise, has the silicon-dioxide etc. of spherical silicon dioxide, chain silicon-dioxide and the aluminium modification of small amount of impurities such as sodium etc.
Have no particular limits for described spherical silicon dioxide, it for example can comprise that " SnowtexN ", " Snowtex O ", " Snowtex OXS " and " Snowtex UP " (are Nissan ChemicalIndustries, Ltd. produce) isocolloid silicon-dioxide, and " Aerosil " pyrogenic silicas such as (Nippon Aerosil Co., Ltd. produces).Have no particular limits for described chain silicon-dioxide, it for example can comprise " Snowtex PS-M " and " Snowtex PS-MO " silica gel such as (be NissanChemical Industries, Ltd. produce).The silicon-dioxide of described aluminium modification for example can comprise " Adelite AT-20A " commercially available silica gels such as (Asahi Denka Co., Ltd. produces).
Contain the described silicon-dioxide that is scattered in water if be used for the metal surface treating composition of metal surface treating method of the present invention, then with respect to the solid matter total amount in the described metal surface treating composition, the dioxide-containing silica in the described metal surface treating composition is preferably 80 quality % or lower.If greater than 80 quality %, then can producing, this content handles the problem that film becomes fragile, so rust-preventing characteristic can suffer damage.The upper limit of described content is 60 quality % more preferably, and then preferred 30 quality %.
When metal surface treating composition of the present invention contains the above-mentioned silicon-dioxide that is scattered in water, with respect to the solid matter total amount in the described metal surface treating composition, Nb
2O
5/ SiO
2Ratio be preferably 1/99 to 99/1.If Nb
2O
5Content make described ratio be lower than 1/99, then preferred this content is because Nb at this moment
2O
5Can not produce good rust-preventing characteristic.Described ratio more preferably 2/98 to 30/70.
In order to improve the rust-preventing characteristic of surface treatment film, metal surface treating composition of the present invention preferably further contains at least a compound that is selected from the group of being made up of vanadium compound, zirconium compounds and titanium compound.Be selected from being used in combination of at least a compound and niobium oxides colloidal solid in the group of forming by vanadium compound, zirconium compounds and titanium compound, can further improve rust-preventing characteristic.More preferably adopt three kinds, four kinds or five kinds of components, described component comprises the niobium oxides colloidal solid, describedly is scattered in the silicon-dioxide of water and is selected from least a compound in the group of being made up of vanadium compound, zirconium compounds and titanium compound.
Have no particular limits for described vanadium compound, it for example can comprise, the roasting enriched material of vanadyl compound, Vanadium Pentoxide in FLAKES, vanadate, vanadic acid, assorted enriched material of vanadic acid and composition thereof.Real example has: V (II) compound such as vanadium oxide and vanadium hydroxide; V (III) compound such as vanadous oxide (V
2O
3); V (IV) compound such as vanadium tetraoxide (V
2O
4) and dihalide vanadyl (VOX
2); V (V) compound such as Vanadium Pentoxide in FLAKES (V
2O
5); Various vanadate such as ortho-vanadate, metavanadate and pyrovanadate and three halo vanadyl (VOX
3), and the mixture of above-mentioned substance.To described vanadate without limits, it can comprise for example ammonium salt, an alkali metal salt, alkaline earth salt (for example magnesium, calcium), other typical metal-salts (for example aluminium, tin etc.) and transition metal salt (for example manganese, cobalt, iron and nickel) or the like.At first preferred bases earth metal salt, zinc salt, manganese salt and cobalt salt.Can be by obtaining above-claimed cpd at 600 ℃ or higher roasting temperature vanadium oxide and oxide compound, oxyhydroxide and the carbonate etc. of various metals.
Have no particular limits for described zirconium compounds, it for example can comprise, hexafluoro zirconate (H
2ZrF
6); The fluorozirconate of ammonium, lithium, sodium, potassium etc.; Ammonium zirconyl carbonate ((NH
4)
2(ZrO (CO
3)
2); Zirconates compound such as zirconium hydroxide, zirconium carbonate, boric acid zirconium, oxalic acid zirconium, zirconium sulfate, zirconium nitrate, Zircosol ZN and Zirconium tetrafluoride; Organic zirconate is as two lauric acid, two fourth zirconiums, two sad two fourth zirconiums, naphthalic acid zirconium, zirconium caprylate and methyl ethyl diketone zirconium; And the mixture of above-mentioned substance.
Have no particular limits for described titanium compound, it for example can comprise, fluoro-titanium compound such as hydrofluoric acid titanium, ammonium titanium fluoride, titanium sodium fluoride, potassium fluotitanate, hydrofluotitanic acid, alkali metal fluosilicate titanate and titanium fluoride; Organic titanic compound such as titanium potassium oxalate(T.P.O.), titanium isopropylate, isopropyl titanate, titanium ethanolate, 2 ethyl hexanoic acid titanium, titanium isopropylate, tetra-n-butyl titanate, butyl (tetra) titanate dimer, lactic acid titanium, trolamine titanium; And the mixture of above-mentioned substance.
When metal surface treating composition of the present invention contains at least a compound that is selected from the group of being made up of vanadium compound, zirconium compounds and titanium compound, with respect to the solid matter total amount of described metal surface treating composition, described at least a compound preferably is not more than 30 quality % in the content of V, Zr and Ti.If described content is greater than 30 quality %, then its add-on reaches capacity, and this is uneconomic, thereby not preferred this situation.With respect to the solid matter total amount of described metal surface treating composition, described at least a compound is in the content of V, Zr and the Ti 0.5 quality % or higher that preferably respectively does for oneself.If the content of described at least a compound is lower than 0.5 quality %, then damage rust-preventing characteristic sometimes, thereby not preferred this situation.Its lower limit is 1 quality % more preferably, and then preferred 2.5 quality %.Its upper limit is 15 quality % more preferably, and then preferred 7.5 quality %.
In addition, metal surface treating composition of the present invention preferably contains water-base resin.Term used herein " water-base resin " comprises water soluble resin and can be scattered in the resin of water.Have no particular limits for described water-base resin, its for example can comprise acrylic resin, polyolefin resin, polyurethanes resin, redix, ethylene-acrylic acid copolymer resin, phenolic resin, polyester resin, alkyd based resin, trimeric cyanamide resinoid, polycarbonate resin, polyacrylic acid, other heat cross-linking resin and thermoplastic resins.
These water-base resins can use separately, also can be used in combination its two or more, perhaps use the multipolymer that forms each other by its two or more.When using water-base resin, so that form more even and slick processing film, can use levelling agent, moistening agent and defoamer in order to improve its film-forming properties.
When metal surface treating composition of the present invention contained described water-base resin, with respect to the solid matter total amount of described metal surface treating composition, the content of the described water-base resin that is added was preferably 90 quality % or lower.If this content is greater than 90 quality %, then its add-on reaches capacity, and this is uneconomic, thereby not preferred this situation.With respect to the solid matter total amount of described metal surface treating composition, the content of the described water-base resin that is added is preferably 5 quality % or higher.If the content of described water-base resin is lower than 5 quality %, then damage rust-preventing characteristic sometimes, thereby not preferred this situation.Its lower limit is 10 quality % more preferably, and then preferred 20 quality %.Its upper limit is 80 quality % more preferably, and then preferred 70 quality %.
Metal surface treating composition of the present invention preferably contains phosphate cpd.Add described phosphate cpd in the metal surface treating composition of the present invention can wash-out as the metal of pending object material, thereby the surface at this object material forms metal phosphate, so can further improve the rust-preventing characteristic of this surface treatment film.
Can use any above-mentioned phosphate cpd that can form phosphate anion in water, for example, that can mention has phosphoric acid, phosphoric acid salt such as a Na
3PO
4, Na
2HPO
4And NaH
2PO
4Condensed phosphoric acid class such as condensed phosphoric acid, Tripyrophosphoric acid, metaphosphoric acid, tetra-sodium, super phosphoric acid etc. and salt thereof.
When metal surface treating composition of the present invention contains described phosphate cpd, solid matter total amount with respect to described metal surface treating composition, the content of described phosphoric acid in this metal surface treating composition is preferably, from the following upper limit that is limited to 20 quality % of 0.1 quality %.If this content is lower than 0.1 quality %, then its rust-preventing characteristic is not good sometimes, and if this content surpasses 20 quality %, excessive corrosion steel plate galvanized sometimes then, and also can make the composition that contains water-base resin form gel sometimes, thereby not preferred this situation.Described lower limit is 0.5 quality % more preferably, and the further preferred 10 quality % of the described upper limit.
Metal surface treating composition of the present invention preferably further contains silane coupling agent.The adding of silane coupling agent can improve the adhesive ability of handling between film and the described metallic surface, and the water-base resin that can be as linking agent provides functional group, thereby improves rust-preventing characteristic, so this situation is preferred.Have no particular limits for above-mentioned silane coupling agent, it for example can comprise, the vinyl methoxy silane, vinyltrimethoxy silane, the vinyl Ethoxysilane, vinyltriethoxysilane, the 3-aminopropyltriethoxywerene werene, the 3-glycidoxypropyltrime,hoxysilane, the 3-methacryloxypropyl trimethoxy silane, 3-sulfydryl propyl trimethoxy silicane, N-(1,3-dimethyl butylidene)-3-(triethoxysilyl)-1-propylamine, N, N '-two [3-(trimethoxysilyl) propyl group] quadrol, N-(beta-aminoethyl)-gamma-amino propyl group methyl dimethoxysilane, N-(beta-aminoethyl)-gamma-amino propyl trimethoxy silicane, the gamma-amino propyl trimethoxy silicane, γ-An Jibingjisanyiyangjiguiwan, γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxy propyl-triethoxysilicane, γ-glycidoxy propyl group methyl dimethoxysilane, 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, γ-methacryloxypropyl trimethoxy silane, γ-methacryloxypropyl triethoxyl silane, γ-Qiu Jibingjisanjiayangjiguiwan, γ-sulfydryl propyl-triethoxysilicane, N-[2-(vinyl benzyl amino) ethyl]-the 3-TSL 8330 etc.
Wherein, particularly preferred silane coupling agent is vinyl methoxy silane, vinyl Ethoxysilane, 3-aminopropyltriethoxywerene werene, 3-glycidoxypropyltrime,hoxysilane, 3-methacryloxypropyl trimethoxy silane, 3-sulfydryl propyl trimethoxy silicane, N-(1,3-dimethyl butylidene)-and 3-(triethoxysilyl)-1-propylamine, N, N '-two [3-(trimethoxysilyl) propyl group] quadrol.Described silane coupling agent can use separately, perhaps is used in combination its two or more.
When metal surface treating composition of the present invention contained described silane coupling agent, with respect to the solid matter total amount of described metal surface treating composition, the content of described silane coupling agent was preferably the following upper limit that is limited to 30 quality % from 0.5 quality %.If the content of described silane coupling agent is lower than 0.5 quality %, then its improve rust-preventing characteristic and improve it and the adhesive ability of the antirust Liniment of non-chromium aspect effect not good sometimes, if and this content surpasses 30 quality %, then its add-on reaches capacity, and this is uneconomic.Described lower limit is 1 quality % more preferably, and more preferably 20 quality % of the described upper limit.
In metal surface treating composition of the present invention, in the quality of solid matter, the total amount of described solid matter is preferably the following upper limit that is limited to 50 quality % from 3 quality %.If the content of described solid matter is lower than 3 quality %, then after using this metal surface treating composition, sometimes can not obtain being enough to keep the processing film thickness of rust-preventing characteristic, if and this content surpasses 50 quality %, then produce the gel of said composition sometimes, thereby this situation not preferred.Described lower limit is 10 quality % more preferably, and the described upper limit is 30 quality % more preferably.
The metal surface treating composition of the present invention that contains above-mentioned each component is highly stable, thereby is fit to be used for stably handling the surface of steel plate galvanized.
Preparation method for metal surface treating composition of the present invention has no particular limits, can prepare described metal surface treating composition as follows, for example, in a container, be sequentially added into the niobium oxides colloidal solid, can be scattered in water silicon-dioxide, be selected from least a compound and water-base resin in the group of forming by vanadium compound, zirconium compounds and titanium compound, this mixture is stirred.
Metal surface treating method of the present invention is to adopt described metal surface treating composition to handle the method for steel plate galvanized.For having no particular limits with the handled steel plate galvanized of metal surface treating method of the present invention, it for example can be, being coated with the steel plate of zinc or Zn based alloy such as zinc and being electroplating steel plate, the molten steel plating plate of zinc system, zinc is evaporation steel plate etc., comprising steel plate galvanized, zinc-plated-the nickel steel plate, zinc-plated-the iron steel plate, zinc-plated-the chromium steel plate, zinc-plated-the aluminum steel plate, zinc-plated-titanium steel plate, zinc-plated-the magnesium steel plate, zinc-plated-manganese steel plate etc.
Described metal surface treating method comprises the step that described steel plate galvanized is handled, and according to the needs of described metal surface treating composition, described steel plate galvanized has passed through removes the oily processing.Have no particular limits for the treatment process that adopts described metal surface treating composition, it for example can comprise, traditionally method that is adopted such as rolling method, shower coat method, air spray finishing, airless spraying process, curtain coating method, spread coating, pickling process etc.
After the described metal surface treating composition of employing is handled, preferably carry out heat drying.The exsiccant temperature is preferably the following upper limit that is limited to 250 ℃ from 50 ℃.If be lower than 50 ℃, then the velocity of evaporation of moisture is slower, thereby causes drying efficiency not high sometimes.If be higher than 250 ℃, some component in the then formed processing film is at high temperature decomposed sometimes.More preferably 60 ℃ of described lower limits, more preferably 150 ℃ of the described upper limits.Be preferably the following upper limit that is limited to 300 seconds time of drying, more preferably from 3 seconds the following upper limit that is limited to 60 seconds from 1 second.
During metal surface treating composition of the present invention, gained is handled the quality of the coating amount of film in its solid matter in coating, for from 0.1g/m
2The following 10.0g/m that is limited to
2The upper limit.If described coating amount is lower than 0.1g/m
2, then can damage its processibility, perhaps the thickness low LCL because of gained processing film causes rust-preventing characteristic not good sometimes.If described coating amount surpasses 10.0g/m
2, then can not improve antirust ability because of the increase of handling film thickness, this is disadvantageous economically, and makes roller coat become difficult because of the thickness of handling film increases sometimes.Described lower limit is 0.2g/m more preferably
2, further preferred 0.3g/m
2The described upper limit is 5.0g/m more preferably
2, further preferred 3.0g/m
2
It is a kind of by the resulting steel plate galvanized of described metal surface treating method that the present invention also provides.Because with excellent surface treatment film, thereby this steel plate galvanized has excellent rust-preventing characteristic on the steel plate galvanized of the present invention, and can not produce white rust.
Metal surface treating composition of the present invention is a kind of chemical conversion treating agent that contains the niobium oxides colloidal solid, wherein component utilized can not brought white elephant for liquid waste disposal, therefore compare with the steel plate galvanized of chromising, said composition has the rust-preventing characteristic and the adhesive ability of same excellence.So the present invention can provide a kind of treatment process of metallic surface, described method can be carried out the ideal metal finishing to steel plate galvanized.In addition, can obtain the steel plate galvanized of rust-preventing characteristic and adhesive ability excellence by metal surface treating method of the present invention.
Because metal surface treating composition of the present invention contains described niobium oxides colloidal solid,, and can suppress the generation of white rust effectively so said composition has excellent rust-preventing characteristic and adhesive ability.In addition, because composition of the present invention does not contain as the chromium cpd of necessary composition or manganic compound etc., so it can not bring white elephant to liquid waste disposal.
Embodiment
Embodiment
To describe the present invention more practically below, but should be appreciated that the present invention is not limited to following embodiment.
Embodiment 1 to 8 and Comparative Examples 1 to 3
Under agitation condition, in a container, be sequentially added into niobium oxides colloidal solid, the silicon-dioxide that can be scattered in water, vanadium compound and zirconium compounds, add concentration to 10% that entry regulates solid matter to 15%, thereby obtain surface treating composition as shown in table 1.
Embodiment 9 to 21 and Comparative Examples 4 and 5
Under agitation condition, in a container, be sequentially added into niobium oxides colloidal solid, the silicon-dioxide that can be scattered in water, vanadium compound, zirconium compounds, titanium compound, water-base resin, phosphate cpd and silane coupling agent, add entry and regulate the concentration to 15% of solid matter, thereby obtain surface treating composition as shown in table 2.
Comparative Examples 6
Use commercial chromium treatment agent (Surf coat S-100, Nippon Paint Co., Ltd produces), the amount of regulating the chromium deposition thing is 20mg/m
2
Adopt commercially available alkaline degreasing fat agent Surf cleaner 53S (Nippon Paint Co., Ltd's product) under 60 ℃ to commodity steel plate galvanized (Nippon Testpanel Co., Ltd., produce, 70mm * 150mm * 0.4mm) sprayed 2 minutes, wash with water and drying, so that remove greasy processing, adopt the wire bar applicator coating by embodiment 1 to 21 and Comparative Examples 1 to 5 resulting metal conditioner subsequently, dry under 80 ℃ then, be 0.2g/m so that form the sedimental amount of exsiccant
2To 1.0g/m
2The sample bar.Adopt the applied chromising treatment agent of wire bar applicator coating Comparative Examples 6, the amount of regulating the chromium deposition thing is 20mg/m
2, dry under 80 ℃ metallic surface temperature in the same way then, thus the sample bar obtained.As follows the said sample bar is assessed.The result is shown in following table 1 and 2.
Used niobium oxides colloidal solid, the silicon-dioxide that can be scattered in water, vanadium compound, zirconium compounds, titanium compound, water-base resin, phosphate cpd and silane coupling agent is described as follows in the following table 1 and 2.
[niobium oxides colloidal solid]
A: niobium oxides colloidal sol (Nb
2O
5: 10%, median size: 5nm, Taki Chemical Co., Ltd. produces)
B: the niobium oxides colloidal solid (Nb that is scattered in water
2O
5: 10%, median size: 2,000nm)
[can be scattered in the silicon-dioxide of water]
A:Snowtex O (SiO
2: 20%, Nissan Chemical Industries, Ltd. produces)
B:Adelite AT-20A (SiO
2: 20%, Asahi Denka Co., Ltd. produces)
C:Snowtex N (SiO
2: 20%, Nissan Chemical Industries, Ltd. produces)
[vanadium compound]
A: ammonium meta-vanadate (V:43.6%, reagent)
B: Vanadium Pentoxide in FLAKES (V:56.0%, reagent)
C:Vanadil sulfate (vanadylic sulfate, V:22.6%, Shinko Kagaku Kogyo Co., Ltd. produces)
[zirconium compounds]
A:Zircosol AC-7 (zirconium carbonate ammonium, Zr: count 74.0% with solid matter content, DaiichiKigenso Kagaku Kogyo Co., Ltd. produces)
B: methyl ethyl diketone zirconium (IV) (Zr:18.7%, reagent)
C: two nitric hydrate zirconiums (Zr:33.0%, reagent)
[titanium compound]
A:Orgatix TC-400 (the trolamine titanium, Ti: count 10.4% with solid matter content, Matsumoto Chemical Industry Co., Ltd. produces)
[water-base resin]
A:PC 2200 (the ethylene-acrylic acid copolymer resin, solid substance concentration: 30%, ShoeiChemical Co., Ltd. produces)
B:Superflex 420 (urethane, solid substance concentration: 32%, Dai-ichi KogyoSeiyaku Co., Ltd. produces)
C:Jurymer AC-10L (polyacrylic acid, solid substance concentration: 40%, Nihon JunyakuCo., Ltd. produces)
[phosphate cpd]
A: Secondary ammonium phosphate (solid substance concentration: 100%, reagent)
[silane coupling agent]
A:Sila-Ace S-510 (γ-glycidoxypropyltrime,hoxysilane, solid substance concentration: 100%, Chisso Corporation produces)
B:Sila-Ace S-210 (the vinyl methoxy silane, solid substance concentration: 100%, ChissoCorporation produces)
(appraisal procedure)
＜erosion resistance 〉
End face area and position, the back side rubber belt sealing of the 8mm that extrudes with the position, plane of sample bar and with the Erichsen trier through processing, under 35 ℃, the salt solution that has spraying 5% on the surface of handling film at each sample bar, assess through after 24 or 72 hours according to following standard, produce the ratio of the surface-area of white rust.
◎: do not produce white rust
Zero: the ratio that produces the surface-area of white rust is lower than 10%
Zero △: described ratio is not less than 10%, but is lower than 30%
△: described ratio is not less than 30%, but is lower than 50%
*: described ratio is not less than 50%
Table 1
| Numbering | The composition of metal conditioner (with respect to the quality % of solid matter total amount) | Nb 2O 5/ SiO 2Ratio | The solid substance concentration of treatment agent (%) | Sedimental amount (g/m 2) | Erosion resistance (SST24 hour) | |||||||||
| The niobium oxides colloidal solid | Water-soluble silicon-dioxide | Vanadium compound | Zirconium compounds | |||||||||||
| Type | Quality % *1 | Type | Quality % *2 | Type | Quality % | Type | Quality % | The position, plane | Erichsen trier working position | |||||
| Embodiment | 1 | A | 100 | - | - | - | - | - | - | - | 10 | 1.0 | ○ | ○- |
| 2 | A | 30 | A | 70 | - | - | - | - | 30/70 | 15 | 1.0 | ◎ | ○ | |
| 3 | A | 1 | A | 99 | - | - | - | - | 1/99 | 15 | 1.0 | ○ | ○△ | |
| 4 | A | 90 | - | - | A | 10(V：4.4) | - | - | - | 10 | 1.0 | ◎ | ○ | |
| 5 | A | 25 | A | 70 | B | 5(V：2.8) | - | - | 26/74 | 15 | 0.7 | ◎ | ◎ | |
| 6 | B | 25 | A | 70 | B | 5(V：2.8) | - | - | 26/74 | 15 | 0.7 | ○ | ○△ | |
| 7 | A | 20 | A | 50 | - | - | A | 30(Zr：22.2) | 29/71 | 15 | 0.5 | ◎ | ◎ | |
| 8 | A | 20 | B | 70 | A | 5(V：2.2) | B | 5(Zr：0.9) | 22/78 | 15 | 0.5 | ◎ | ◎ | |
| Comparative Examples | 1 | - | - | A | 100 | - | - | - | - | - | 15 | 1.0 | × | × |
| 2 | - | - | A | 90 | A | 10(V：4.4) | - | - | - | 15 | 1.0 | △ | × | |
| 3 | - | - | A | - | A | 5(V：2.2) | B | 5(Zr：0.9) | - | 15 | 1.0 | △ | × | |
*1：Nb
2O
5
*2：SiO
2
Table 2
| Numbering | The composition of metal conditioner (with respect to the quality % of solid matter total amount) | Nb 2O 6/ SiO 2Ratio | The solid substance concentration of treatment agent (%) | Sedimental amount (g/m 2) position | Erosion resistance (SST24 hour) | |||||||||||||||||
| The niobium oxides colloidal solid | Can be scattered in the silicon-dioxide of water | Barium compound | Zirconium compounds | Titanium compound | Water-base resin | Phosphate cpd | Silane coupling agent | |||||||||||||||
| Type | Quality %*1 | Type | Quality %*2 | Type | Quality % | Type | Quality % | Type | Quality % | Type | Quality % | Type | Quality % | Type | Quality % | Machining is tested on the plane | Erichsen tries the position | |||||
| Embodiment | 9 | A | 10 | A | 50 | A | 10 (V：4.4) | - | - | - | - | A | 30 | - | - | - | - | 17/83 | 15 | 0.4 | ◎ | ◎ |
| 10 | A | 10 | A | 55 | - | - | A | 1 (Zr：0.7) | - | - | A | 34 | - | - | - | - | 15/85 | 15 | 0.6 | ◎ | ○ | |
| 11 | A | 10 | B | 40 | - | - | B | 20 (Zr：3.7) | - | - | B | 30 | - | - | - | - | 20/80 | 15 | 0.4 | ◎ | ◎ | |
| 12 | A | 1 | A | 8 | B | 1 (V：0.6) | - | - | - | - | A | 90 | - | - | - | - | 11/89 | 15 | 0.6 | ○ | ○ | |
| 13 | A | 40 | A | 1 | B | 50 (V：28.0) | - | - | - | - | C | 9 | - | - | - | - | 98/2 | 15 | 0.6 | ◎ | ○ | |
| 14 | A | 15 | C | 25 | - | - | C | 10 (Zr：3.3) | - | - | A | 50 | - | - | - | - | 38/62 | 15 | 0.5 | ◎ | ◎ | |
| 15 | A | 25 | A | 50 | A | 5 (V2.2) | - | - | - | - | A | 20 | - | - | - | - | 33/67 | 15 | 0.5 | ◎ | ◎ | |
| 16 | A | 10 | A | 80 | C | 5 (V：1.1) | - | - | - | - | C | 5 | - | - | - | - | 11/89 | 15 | 0.6 | ◎ | ○ | |
| 17 | A | 5 | A | 20 | A | 10 (V：4.4) | - | - | - | - | A | 65 | - | - | - | - | 20/80 | 15 | 0.2 | ◎ | ◎ | |
| 18 | A | 10 | A | 49 | A | 10 (V4.4) | - | - | - | - | A | 30 | A | 1 | - | - | 17/83 | 15 | 0.4 | ◎ | ◎ | |
| 19 | A | 10 | A | 48 | A | 10 (V：4.4) | - | - | - | - | A | 30 | A | 0.5 | A | 1.5 | 17/83 | 15 | 0.3 | ◎ | ◎ | |
| 20 | A | 10 | A | 44 | A | 10 (V：4.4) | - | - | A | 10 (Ti：1.0) | A | 22 | A | 2.5 | B | 1.5 | 19/81 | 15 | 0.4 | ◎ | ◎ | |
| 21 | A | 10 | A | 49 | A | 4 (V：1.7) | C | 3 (Zr：1.0) | A | 7 (Ti：0.7) | A | 24 | A | 1.5 | A | 1.5 | 17/83 | 15 | 0.4 | ◎ | ◎ | |
| Comparative Examples | 4 | - | - | A | 60 | A | 10 (V：4.4) | - | - | - | - | A | 30 | - | - | - | - | - | 15 | 0.6 | △ | × |
| 5 | - | - | A | 54 | A | 10 (V：4.4) | - | - | A | 10 (Ti：1.0) | A | 22 | A | 2.5 | A | 1.5 | - | 15 | 0.6 | △ | △ | |
| 6 | Surf coat S-100(Cr：20mg/m 2) | ◎ | ○ | |||||||||||||||||||
*1：Nb
2O
5
*2：SiO
2
Last table 1 and table 2 clearly illustrate that the metal surface treating composition that contains the niobium oxides colloidal solid of the present invention shows excellent rust-preventing characteristic, and can suppress the generation of white rust.In addition, when in the metal surface treating composition except that containing the niobium oxides colloidal solid, when also containing silicon-dioxide, water-base resin and the vanadium compound that can be scattered in water etc., because being used in combination of these components, the rust-preventing characteristic of this metal surface treating composition is significantly improved.On the other hand, the metal surface treating composition of oxygen-free niobium colloidal solid then can not form any chemical conversion film with excellent rust-preventing characteristic, thereby can not form the ideal steel plate galvanized by this based composition.Metal surface treating composition of the present invention also has excellent rust-preventing characteristic after through processing.
Claims (5)
1. a metal surface treating composition wherein contains niobium oxides colloidal solid and at least a compound that is selected from the group of being made up of vanadium compound, zirconium compounds and titanium compound.
2. metal surface treating composition according to claim 1 wherein also contains the silicon-dioxide that can be scattered in water.
3. metal surface treating composition according to claim 1 and 2 wherein also contains water-base resin.
4. metal surface treating method, this method comprise that employing carries out the surface-treated step according to each described metal surface treating composition of claim 1 to 3 to steel plate galvanized.
5. a steel plate galvanized has on the described steel plate galvanized with the formed processing film of the described metal surface treating method of claim 4.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002225178 | 2002-08-01 | ||
| JP2002225178 | 2002-08-01 | ||
| JP2003200654A JP3952198B2 (en) | 2002-08-01 | 2003-07-23 | Metal surface treatment method and galvanized steel sheet |
| JP2003200654 | 2003-07-23 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1478921A CN1478921A (en) | 2004-03-03 |
| CN100363537C true CN100363537C (en) | 2008-01-23 |
Family
ID=32032810
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB031500749A Expired - Lifetime CN100363537C (en) | 2002-08-01 | 2003-07-31 | Metal surface treatment composite, metal surface treatment method and galvanized steel sheet obtained by it |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP3952198B2 (en) |
| CN (1) | CN100363537C (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007002330A (en) * | 2005-06-27 | 2007-01-11 | Baoshan Iron & Steel Co Ltd | Surface treatment agent for zinc or zinc alloy galvanized steel sheet, and surface treated zinc or zinc alloy galvanized steel sheet |
| JP4719662B2 (en) * | 2006-11-21 | 2011-07-06 | 日本パーカライジング株式会社 | Water-based surface treatment agent for environment-friendly precoat metal material, surface treatment metal material, and environment-friendly precoat metal material |
| JP5188090B2 (en) * | 2006-12-27 | 2013-04-24 | 朝日化学工業株式会社 | Coating liquid and clear coated steel plate |
| TWI394864B (en) * | 2007-12-27 | 2013-05-01 | Kansai Paint Co Ltd | Metal surface treatment composition, and surface-treated metal material with metal surface treatment film obtained from the metal surface treatment composition |
| CN101747841A (en) * | 2008-12-05 | 2010-06-23 | 安集微电子（上海）有限公司 | Chemical-mechanical polishing solution |
| CN101659175B (en) * | 2009-09-02 | 2012-11-21 | 苏州扬子江新型材料股份有限公司 | Scratching-resistant and wear-resistant color-coated steel sheet |
| JP2010031297A (en) * | 2009-11-16 | 2010-02-12 | Kansai Paint Co Ltd | Paint composition with excellent corrosion resistance |
| JP5528925B2 (en) * | 2010-07-09 | 2014-06-25 | 日本パーカライジング株式会社 | Metal surface treatment agent, surface treatment metal material, and metal surface treatment method |
| CN102746778B (en) * | 2012-06-29 | 2014-12-03 | 宝山钢铁股份有限公司 | Galvanizing steel strip with good conductivity, high corrosion resistance and fingerprint resistance, surface treatment agent and treatment method |
| JP6044748B1 (en) | 2015-02-03 | 2016-12-14 | 新日鐵住金株式会社 | Steel plate for fuel tank |
| WO2016140146A1 (en) * | 2015-03-03 | 2016-09-09 | 株式会社スリーボンド | Anti-fogging agent composition |
| JP6674081B2 (en) * | 2016-07-14 | 2020-04-01 | ユケン工業株式会社 | Rust prevention coating solution |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1063129A (en) * | 1992-03-07 | 1992-07-29 | 冶金工业部钢铁研究总院 | The metallic surface treatment solution |
| CN1074716A (en) * | 1992-11-18 | 1993-07-28 | 冶金工业部钢铁研究总院 | Metal surface treating liquid |
| WO2001026895A1 (en) * | 1999-10-08 | 2001-04-19 | Kawasaki Steel Corporation | Surface treated zinc-based metal plated steel sheet |
| JP2001214283A (en) * | 1999-11-15 | 2001-08-07 | Kawasaki Steel Corp | Surface treated galvanized steel sheet |
| CN1354370A (en) * | 2000-11-13 | 2002-06-19 | 保谷株式会社 | Composition for vapour-phase deposition, method for forming anti-reflecting film using the same and its optical element |
-
2003
- 2003-07-23 JP JP2003200654A patent/JP3952198B2/en not_active Expired - Fee Related
- 2003-07-31 CN CNB031500749A patent/CN100363537C/en not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1063129A (en) * | 1992-03-07 | 1992-07-29 | 冶金工业部钢铁研究总院 | The metallic surface treatment solution |
| CN1074716A (en) * | 1992-11-18 | 1993-07-28 | 冶金工业部钢铁研究总院 | Metal surface treating liquid |
| WO2001026895A1 (en) * | 1999-10-08 | 2001-04-19 | Kawasaki Steel Corporation | Surface treated zinc-based metal plated steel sheet |
| JP2001214283A (en) * | 1999-11-15 | 2001-08-07 | Kawasaki Steel Corp | Surface treated galvanized steel sheet |
| CN1354370A (en) * | 2000-11-13 | 2002-06-19 | 保谷株式会社 | Composition for vapour-phase deposition, method for forming anti-reflecting film using the same and its optical element |
Non-Patent Citations (1)
| Title |
|---|
| Nb2O5薄膜的溶胶-凝胶法制备. 吴云等.硅酸盐学报，第25卷第3期. 1997 * |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3952198B2 (en) | 2007-08-01 |
| JP2004124254A (en) | 2004-04-22 |
| CN1478921A (en) | 2004-03-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100537846C (en) | Metal surface treating composition, metal surface treating method and steel plate galvanized | |
| JP4105765B2 (en) | Corrosion-resistant surface-treated metal material and surface treatment agent therefor | |
| CA2632720C (en) | Wet on wet method and chrome-free acidic solution for the corrosion control treatment of steel surfaces | |
| AU2006260006B2 (en) | Chrome-free composition of low temperature curing for treating a metal surface and a metal sheet using the same | |
| CN100374619C (en) | Treating liquid for surface treatment of aluminum or magnesium based metal and method of surface treatment | |
| US5938861A (en) | Method for forming a rust proof film | |
| KR100250366B1 (en) | Acid aqueous compositions and concentration in order to make zinc phosphate coating on the meal plate | |
| JP5446057B2 (en) | Zinc-based galvanized steel sheet for chemical conversion treatment, method for producing the same, and chemical conversion treated steel sheet | |
| CN100363537C (en) | Metal surface treatment composite, metal surface treatment method and galvanized steel sheet obtained by it | |
| US6193815B1 (en) | Composition and process for treating the surface of aluminiferous metals | |
| JP3844643B2 (en) | Ground treatment agent and ground treatment method | |
| JP3992173B2 (en) | Metal surface treatment composition, surface treatment liquid, and surface treatment method | |
| JP3623015B2 (en) | Surface treatment liquid for aluminum-containing metal material and surface treatment method | |
| WO2002061174A1 (en) | Rustproofing agent for zinc plated steel sheet | |
| US5391240A (en) | Process for the passivating post-treatment of phosphatized metal surfaces | |
| US20040173289A1 (en) | Rustproofing agent for zinc plated steel sheet | |
| JP3903594B2 (en) | Manufacturing method of surface-treated steel sheet with excellent corrosion resistance | |
| JPH11335864A (en) | Production of surface treated steel plate having excellent corrosion resistance | |
| KR100987588B1 (en) | Metallic surface-treating composition, metallic surface-treating method and galvanized steel sheet | |
| EP1205579B1 (en) | A chemically processed steel sheet excellent in corrosion resistance | |
| JPH11335862A (en) | Production of surface treated steel plate having excellent corrosion resistance | |
| JP4349712B2 (en) | Surface-treated galvanized steel without chromium | |
| JPH1136082A (en) | Surface treating solution for light metal or light alloy material | |
| JP2000248374A (en) | Rust preventing treated steel | |
| JP2000256870A (en) | Non-chromium type surface treated steel sheet excellent in corrosion resistance |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| C56 | Change in the name or address of the patentee | ||
| CP03 | Change of name, title or address |
Address after: Osaka Japan Patentee after: NIPPON PAINT HOLDINGS CO.,LTD. Address before: Osaka Patentee before: NIPPON PAINT Co.,Ltd. |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20160113 Address after: Tokyo, Japan Patentee after: NIPPON PAINT SURF CHEMICALS CO.,LTD. Address before: Osaka Japan Patentee before: NIPPON PAINT HOLDINGS CO.,LTD. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20171229 Address after: Shanghai City, Pudong New Area Zhuqiao gold smell Road No. 2 10 Patentee after: NIPPON (SHANGHAI) CHEMICAL CO.,LTD. Address before: Tokyo, Japan Patentee before: NIPPON PAINT SURF CHEMICALS CO.,LTD. |
|
| CX01 | Expiry of patent term |
Granted publication date: 20080123 |
|
| CX01 | Expiry of patent term |