CN100537845C - Metal finishing treatment solution and surface treatment method - Google Patents
Metal finishing treatment solution and surface treatment method Download PDFInfo
- Publication number
- CN100537845C CN100537845C CNB2003801059479A CN200380105947A CN100537845C CN 100537845 C CN100537845 C CN 100537845C CN B2003801059479 A CNB2003801059479 A CN B2003801059479A CN 200380105947 A CN200380105947 A CN 200380105947A CN 100537845 C CN100537845 C CN 100537845C
- Authority
- CN
- China
- Prior art keywords
- surface treatment
- compound
- treatment
- treatment solution
- solution
- 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
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- 238000004381 surface treatment Methods 0.000 title claims abstract description 186
- 238000011282 treatment Methods 0.000 title claims abstract description 141
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 82
- 238000000034 method Methods 0.000 title claims abstract description 53
- 239000002184 metal Substances 0.000 title claims abstract description 51
- 239000000463 material Substances 0.000 claims abstract description 119
- 239000007769 metal material Substances 0.000 claims abstract description 52
- 239000002775 capsule Substances 0.000 claims abstract description 45
- 150000001875 compounds Chemical class 0.000 claims abstract description 40
- 239000011777 magnesium Substances 0.000 claims abstract description 34
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 33
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 32
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000004411 aluminium Substances 0.000 claims abstract description 25
- 229920002521 macromolecule Polymers 0.000 claims abstract description 24
- 150000003751 zinc Chemical class 0.000 claims abstract description 21
- 239000002253 acid Substances 0.000 claims abstract description 18
- 150000003755 zirconium compounds Chemical class 0.000 claims abstract description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 17
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 16
- 239000011575 calcium Substances 0.000 claims abstract description 16
- 150000003609 titanium compounds Chemical class 0.000 claims abstract description 16
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 claims abstract description 15
- 150000002681 magnesium compounds Chemical class 0.000 claims abstract description 12
- 150000003438 strontium compounds Chemical class 0.000 claims abstract description 12
- 239000013543 active substance Substances 0.000 claims abstract description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 11
- 239000001301 oxygen Substances 0.000 claims abstract description 11
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 10
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 110
- 239000007864 aqueous solution Substances 0.000 claims description 31
- 238000005406 washing Methods 0.000 claims description 26
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 25
- 229910052726 zirconium Inorganic materials 0.000 claims description 25
- 239000010936 titanium Substances 0.000 claims description 22
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 20
- 229910052719 titanium Inorganic materials 0.000 claims description 20
- 238000005238 degreasing Methods 0.000 claims description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 14
- 239000011701 zinc Substances 0.000 claims description 14
- 229910052725 zinc Inorganic materials 0.000 claims description 14
- 239000010941 cobalt Substances 0.000 claims description 8
- 229910017052 cobalt Inorganic materials 0.000 claims description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 8
- 230000002378 acidificating effect Effects 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 229910052718 tin Inorganic materials 0.000 claims description 6
- 239000011135 tin Substances 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 4
- CUILPNURFADTPE-UHFFFAOYSA-N hypobromous acid Chemical compound BrO CUILPNURFADTPE-UHFFFAOYSA-N 0.000 claims description 3
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- 238000012360 testing method Methods 0.000 description 43
- 239000003153 chemical reaction reagent Substances 0.000 description 33
- 230000000052 comparative effect Effects 0.000 description 31
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 29
- 239000011737 fluorine Substances 0.000 description 29
- 229910052731 fluorine Inorganic materials 0.000 description 29
- 239000011248 coating agent Substances 0.000 description 25
- 238000000576 coating method Methods 0.000 description 25
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 20
- 230000003628 erosive effect Effects 0.000 description 19
- 230000000694 effects Effects 0.000 description 18
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- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
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- -1 iron ion Chemical class 0.000 description 10
- 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 10
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- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 8
- 229910000165 zinc phosphate Inorganic materials 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 description 6
- 239000012530 fluid Substances 0.000 description 6
- 239000008399 tap water Substances 0.000 description 6
- 235000020679 tap water Nutrition 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 229910000861 Mg alloy Inorganic materials 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 5
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- 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 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 238000004070 electrodeposition Methods 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 4
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical compound CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- 229910001335 Galvanized steel Inorganic materials 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
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- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
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- 229910052742 iron Inorganic materials 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 230000003381 solubilizing effect Effects 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 229910052712 strontium Inorganic materials 0.000 description 3
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 3
- 229910000348 titanium sulfate Inorganic materials 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 229910001018 Cast iron Inorganic materials 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
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- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
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- 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
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- KWCHQJSISLQWHH-UHFFFAOYSA-N phosphoric acid;trihydrate Chemical compound O.O.O.OP(O)(O)=O KWCHQJSISLQWHH-UHFFFAOYSA-N 0.000 description 1
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- 239000011780 sodium chloride Substances 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- BFXAWOHHDUIALU-UHFFFAOYSA-M sodium;hydron;difluoride Chemical compound F.[F-].[Na+] BFXAWOHHDUIALU-UHFFFAOYSA-M 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 235000018553 tannin Nutrition 0.000 description 1
- 229920001864 tannin Polymers 0.000 description 1
- 239000001648 tannin Substances 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Images
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- 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
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- 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
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- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
- C23C22/44—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates containing also fluorides or complex fluorides
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- 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
- C23C22/73—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 characterised by the process
- C23C22/76—Applying the liquid by spraying
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- 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
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- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
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Abstract
The invention provides and do not contain environmentally harmful composition, do not produce the sludge that becomes waste, the surface treatment of the surface treatment capsule of the excellent corrosion resistance after application can be separated out in the metallic surface treatment solution and surface treatment method.The invention provides the metal finishing treatment solution, this treatment solution is to be used for to the metallic substance of chosen from Fe based material, zinc series materials, aluminium based material and magnesium based material respectively separately or carry out surface-treated water system surface treatment liquid more than 2 kinds simultaneously, it contains the above-mentioned metallic element of compound more than a kind of 5～5000ppm selected among zirconium compound and titanium compound, also contain 0.1～100ppm free fluorine ion, and pH is 2～6.And then in this treatment solution, also can contain calcium cpd, magnesium compound or strontium compound, nitrate radical, oxygen acid and/or oxysalt, macromolecular compound, tensio-active agent.Metallic substance is contacted with above-mentioned treatment solution, or in above-mentioned treatment solution, carry out electrolysis treatment, form tunicle.
Description
Technical field
The present invention relates to surface treatment treatment solution and surface treatment method, its with the body of motor vehicle be representative contain ferrous material, zinc series materials, aluminium system and magnesium based material separately or the metal material surface of its structure of 2 kinds to 4 kinds, the surface treatment capsule that can make excellent corrosion resistance after the application respectively separately or its 2 kinds to 4 kinds separate out simultaneously.
Background technology
As the method that the surface treatment capsule of excellent corrosion resistance after making application in the metallic surface is separated out, general now Zinc Coslettising process or the chromating of using.Zinc Coslettising process can be separated out the tunicle of excellent corrosion resistance in steel such as cold-rolled steel sheet, steel plate galvanized and a part of aluminum alloy surface.But, carrying out zinc phosphate when handling, can not avoid the generation of byproduct of reaction sludge, and can not fully guarantee rust-preventing characteristic after the application different types of aluminium alloy.Can guarantee to have sufficient performance after the application by implementing chromate treating for aluminium alloy.But, the trend of avoiding containing the chromate treating that is harmful to 6 valency chromium in treatment solution is arranged in the environment regulations now.Therefore as the surface treatment method that does not contain objectionable constituent in the treatment solution invention shown below is disclosed.
For example, proposed to contain the compound of nitrogenous source with lone-pair electron and contain above-claimed cpd and the metallic surface of zirconium compounds with non-chromiumcoating agent (opening the 2000-204485 communique) with reference to the spy.This method can not contained erosion resistance and the good surface treatment capsule of adaptation after objectionable constituent 6 valency chromium, the application by the coating above-mentioned composition.But, only limit to aluminium alloy as the object metallic substance, and make it form surface treatment capsule by being coated with drying, therefore be difficult to be coated with the complex structure thing that resembles body of motor vehicle and so on.
Therefore, the method (for example can reference: the spy opens clear 56-136978 communique, spy and opens that flat 8-176841 communique, spy are opened flat 9-25436 communique, the spy opens flat 9-31404 communique) of separating out the surface treatment capsule of adaptation and excellent corrosion resistance after the application by chemical reaction is disclosed a lot.But no matter which kind of method as the metallic substance of object, only limits to the aluminium alloy of material self excellent corrosion resistance, it is impossible separating out surface treatment capsule on ferrous material or zinc series materials surface.
In addition, disclose with the surface treating composition that contains metal acetylacetonates, water-soluble inorganic titanium compound or water-soluble inorganic zirconium compounds, can separate out the method (opening the 2000-199077 communique) of the surface treatment capsule that erosion resistance and adaptation are good after the application with reference to the spy.By using this method, suitable metallic substance expands magnesium, magnesium alloy, zinc and the galvanized alloy beyond the aluminium alloy to.But this method can not be separated out surface treatment capsule on ferrous material surfaces such as cold-rolled steel sheets, can not handle ferrous material simultaneously.
And then, propose to use the metal treatment method of Chrome-free application type acidic composition, for example, after the aqueous solution by film component that can form excellent corrosion resistance is coated the metallic surface, need not implement washing step, make the immobilized metal surface treating method of tunicle (opening flat 5-195244 communique) with reference to the spy by toasting drying.This method generates tunicle without chemical reaction, therefore can implement tunicle in metallic surfaces such as steel plate galvanized, cold-rolled steel sheet and aluminium alloys and handle.But with to open in the 2000-204485 communique invention disclosed above-mentioned spy identical, generate tunicle, be difficult to that therefore the complex structure thing of body of motor vehicle and so on is implemented uniform tunicle and handle by being coated with drying.
Therefore, adopt prior art can not implement following surface treatment: to use the treatment solution that does not contain environmentally harmful composition, do not produce the sludge of waste, zinc series materials such as ferrous material such as the cold-rolled steel sheet of body of motor vehicle and so on and steel plate galvanized and aluminium system and magnesium based material 2 kinds to 4 kinds are handled simultaneously, and implemented erosion resistance and the good surface treatment of adaptation.
Summary of the invention
The objective of the invention is: provide prior art irrealizable, do not contain environmentally harmful composition, do not produce the sludge of waste, the surface treatment treatment solution of the surface treatment capsule of excellent corrosion resistance after application can be separated out in ferrous material, zinc series materials, aluminium system and magnesium based material surface.Be provided at 2 kind the metallic surfaces to 4 kind structures of combination in addition as ferrous material, zinc series materials, aluminium system and the magnesium based material of body of motor vehicle and so on, under identical conditions, simultaneously the surface treatment of the surface treatment capsule of excellent corrosion resistance after the coating of same composition is gone out with the processing liquation, and provide and use the surface treatment method of this surface treatment with treatment solution.
The inventor is to solving the method process lucubrate of above-mentioned problem, and the result has finished unexistent surface treatment treatment solution and surface treatment method in the prior art.
Be metal finishing treatment solution of the present invention be used for to the metallic substance of chosen from Fe based material, zinc series materials, aluminium based material and magnesium based material respectively separately or its carry out surface-treated water system surface treatment liquid more than 2 kinds simultaneously, it is characterized by: the above-mentioned metallic element that contains the compound more than a kind of 5～5000ppm selected among zirconium compound and titanium compound, contain 0.1～100ppm free fluorine ion in addition, and pH is 2～6.
With in the treatment solution, also can and then contain the compound more than a kind that is selected from calcium cpd, magnesium compound and strontium compound in this surface treatment.This moment, these compound concentrations were preferred respectively to these metallic elements: calcium cpd is that 5～100ppm, magnesium compound or strontium compound are 10～5000ppm.Wherein, preferably contain 1000～50000ppm nitrate radical in this treatment solution.Preferably contain in addition and be selected from HClO
3, HBrO
3, HNO
2, HNO
3, HMnO
4, HVO
3, H
2O
2, H
2WO
4And H
2MoO
4And at least a kind of oxygen acid in its esters and/or oxysalt.These surface treatments are with in the treatment solution, also can and then contain at least a kind of macromolecular compound that is selected from water-soluble high-molecular compound and water dispersible macromolecular compound, also can contain at least a kind of tensio-active agent that is selected from nonionic surface active agent, aniorfic surfactant and the cationic surfactant.
Being characterized as of metal surface treating method of the present invention: the metallic substance that makes chosen from Fe based material, zinc series materials, aluminium based material and magnesium based material respectively separately or its contact above-mentioned surface treatment treatment solution more than 2 kinds simultaneously.In this surface treatment method, metallic substance is with after surface treatment contacts with treatment solution, wash or do not wash, and then can contact with the acidic aqueous solution of the compound that contains at least a kind of element that is selected from cobalt, nickel, tin, copper, titanium and zirconium, or also can with contain the treatment solution that is selected from water-soluble high-molecular compound and at least a kind of macromolecular compound of water dispersible macromolecular compound and contact.
Being characterized as of metal surface treating method of the present invention: the metallic substance that makes chosen from Fe based material, zinc series materials, aluminium based material and magnesium based material respectively separately or its more than 2 kinds simultaneously with this metallic substance as negative electrode, carry out electrolysis treatment in above-mentioned surface treatment in surface treatment liquid.In this surface treatment method, metallic substance is after above-mentioned surface treatment is carried out electrolysis treatment in treatment solution, wash or do not wash, and then its acidic aqueous solution with the compound that contains at least a kind of element that is selected from cobalt, nickel, tin, copper, titanium and zirconium is contacted, or also can make it and contain the treatment solution that is selected from water-soluble high-molecular compound and at least a kind of macromolecular compound of water dispersible macromolecular compound and contact.
In addition, method of the present invention be with chosen from Fe based material, zinc series materials, aluminium based material and magnesium based material without the metallic substance of degreasing purifying treatment respectively separately or they are more than 2 kinds, simultaneously with contain that to be selected from above-mentioned nonionic be that tensio-active agent, negatively charged ion be tensio-active agent with positively charged ion are that the surface treatment liquid of at least a kind of tensio-active agent of tensio-active agent contact, the skimming treatment and the tunicle that carry out the metallic surface simultaneously form processing.
In addition, being characterized as of metallic substance of the present invention: on the metallic surface of chosen from Fe based material, zinc series materials, aluminium based material and magnesium based material, has the surface treatment capsule that contains at least a kind the metallic element that is selected from titanium and zirconium that forms by above-mentioned surface treatment method, and the adhesion amount of this surface treatment capsule, convert with above-mentioned metallic element, the Ferrious material material surface is 30mg/m
2More than, zinc is that metal material surface is 20mg/m
2More than, the aluminum-based metal material surface is 10mg/m
2More than, magnesium is that metal material surface is 10mg/m
2More than.
The accompanying drawing summary
The orthographic plan for test plate (panel) of Fig. 1 for providing in embodiments of the invention and the comparative example.Fig. 2 supplies the front elevation of test plate (panel) for this reason.
Embodiment
The present invention relates to the metallic substance of chosen from Fe based material, zinc series materials, aluminium based material and magnesium based material respectively separately or its carry out surface treatment more than 2 kinds simultaneously, separate out the technology of the surface treatment capsule of excellent corrosion resistance after the application.Wherein, ferrous material is meant Ferrious materials such as steel plates such as cold-rolled steel sheet and hot-rolled steel sheet, cast iron and agglomerated material.In addition, zinc series materials is meant die case zinc or contains zinc coating.This contains zinc coating and refers to be plated to by the alloy and the unavoidable impurities of zinc or zinc and other metals (for example at least a kind of metal such as nickel, iron, aluminium, manganese, chromium, magnesium, cobalt, lead and antimony), and its method for plating is not limited only to for example molten plating, plating, evaporation etc.The aluminium based material represents as the aluminum alloy plate materials of 5000 line aluminium alloys or 6000 line aluminium alloys and so on or with ADC-12 to be aluminium diecast alloy of representative etc. in addition.The magnesium based material refers to adopt the sheet material of magnesium alloy or die-casting material etc.
The present invention is applicable to and contains a kind of structure of above-mentioned metallic substance separately or contain 2 kinds of structures to 4 kinds of above-mentioned metallic substance in structural member in structural member.In structural member, contain 2 kinds when to the structure of 4 kinds of above-mentioned metallic substance, using, can carry out surface treatment simultaneously 2 kinds to 4 kinds metal material surfaces.At this moment, when 2 kinds to 4 kinds metallic substance are carried out surface treatment simultaneously, can be discontiguous state between the metal not of the same race, also can be to make the contact condition that connects between the different metal by methods of attachment such as welding, bonding, riveteds.
Surface treatment treatment solution of the present invention is the above-mentioned metallic element that contains the compound more than a kind of 5～5000ppm selected among zirconium compound and titanium compound, contains free fluorine ion 0.1～100ppm, and pH is 2～6 treatment solution.Wherein, the zirconium compounds of the present invention's use can be enumerated ZrCl
4, ZrOCl
2, Zr (SO
4)
2, ZrOSO
4, Zr (NO
3)
4, ZrO (NO
3)
2, H
2ZrF
6, H
2ZrF
6Salt, ZrO
2, ZrOBr
2And ZrF
4Deng.Titanium compound can be enumerated TiCl in addition
4, Ti (SO
4)
2, TiOSO
4, Ti (NO3)
4, TiO (NO
3)
2, TiO
2OC
2O
4, H
2TiF
6, H
2TiF
6Salt, TiO
2And TiF
4Deng.The preferred zirconium compounds that uses among the present invention.
The selected among zirconium compound that uses among the present invention and the compound concentrations more than a kind of titanium compound are preferably 5～5000ppm, more preferably 10～3000ppm in above-mentioned metallic element (that is, in zirconium and/or titanium).Use surface treatment of the present invention to be zirconium or titanyl compound or oxyhydroxide with the tunicle that treatment solution and surface treatment method obtain, so the compound more than a kind that is selected from above-mentioned zirconium compounds and titanium compound is in the concentration of zirconium and/or titanium during less than 5ppm, because tunicle principal constituent concentration is little, in order to obtain erosion resistance, obtain sufficient adhesion amount in the treatment time when practicality and become difficult.In addition, concentration though can obtain sufficient adhesion amount, does not improve the effect of erosion resistance during greater than 5000ppm on this basis, and is just uneconomical.
Zirconium compounds or titanium compound be more easily dissolving in acidic solution, but unstable in basic solution, separates out with zirconium or titanyl compound or oxyhydroxide easily.Surface treatment of the present invention is 2～6 with the pH of treatment solution, and more preferably selecting pH is 3～6.Contact with treatment solution with surface treatment of the present invention at this pH metal to be treated material, cause the solubilizing reaction of metal to be treated material.Then, because the metal to be treated material dissolves causes the rising of metal to be treated material contact surface pH, zirconium and titanyl compound or oxyhydroxide are separated out at the metal to be treated material surface as tunicle.
Surface treatment of the present invention makes and wherein has the free fluorine ion with in the treatment solution.For the free fluorine ion is existed, add fluorochemical in treatment solution in surface treatment.As this free fluorine ionic supply source, can enumerate hydrofluoric acid, H
2ZrF
6, H
2ZrF
6Salt, H
2TiF
6, H
2TiF
6Salt, H
2SiF
6, H
2SiF
6Salt, H
2BF
4, H
2BF
4Salt, NaHF
2, KHF
2, NH
4HF
2, NaF, KF and NH
4F etc.The free fluorine ion has the effect of raising surface treatment with zirconium compounds in the treatment solution and titanium compound stability.And the free fluorine ion has the metallic substance of promotion as surface treatment object of the present invention: the effect of solubilizing reaction takes place in any one material of ferrous material, zinc series materials, aluminium based material and magnesium based material in acidic solution.Therefore, the free fluorine ion is existed, surface treatment of the present invention is improved with the stability of treatment solution, and also can improve metal to be treated material reactivity by adding fluorochemical.
The applicant at first discloses following invention: to surface treatment composition and the surface treatment treatment solution that is used to handle the metallic surface of containing a kind of iron or zinc at least, use titanium compound or zirconium compounds and fluorochemicals, surface treatment is specified range 0.06～0.18 (WO02/103080) with the ratio A/B of composition and the surface treatment molal weight B when in the total molal weight A of above-mentioned metallic element in the treatment solution and the fluorochemicals whole fluorine atoms being scaled HF.According to the present invention, metallic element concentration, pH, free fluorine ionic concn by regulation titanium compound or zirconium compounds, even outside above-mentioned specified range, also can to the metallic substance of chosen from Fe based material, zinc series materials, aluminium based material and magnesium based material respectively separately or its carry out surface treatment more than 2 kinds simultaneously.
The reactivity separately of ferrous material, zinc series materials, aluminium system and magnesium based material is different, so prior art can not be carried out surface treatment simultaneously to above-mentioned metallic substance more than 2 kinds.In the present invention, can freely change stability and the reactive balance of surface treatment by regulating free fluorine ionic concentration with treatment solution, thus can to reactivity different, chosen from Fe based material, zinc series materials, aluminium be and the magnesium based material implement surface treatment more than 2 kinds at the same time or separately separately.
Wherein, the free fluorine ionic concn of indication is meant the fluorinion concentration of measuring with commercially available ion electrode.The free fluorine ionic concn preferred 0.1～100ppm of surface treatment of the present invention in the treatment solution, more preferably 2～70ppm.When free fluorine ionic concentration is higher than 100ppm, though can promote the solubilizing reaction of metal to be treated, but surface treatment is highly stable with zirconium compounds and titanium compound in the treatment solution, is difficult to separate out as tunicle even therefore rise also to become at metal to be treated contact surface pH.In addition, during less than 0.1ppm, surface treatment is little to stability and the reactive effect that improves with treatment solution, has lost and has contained free fluorine ionic meaning.
Free fluorine ion of the present invention improves surface treatment with treatment solution stability and the reactive effect except bearing, and also bears dissolving by the metal to be treated material and stripping stable components ground is kept at surface treatment uses in the treatment solution.In the zinc phosphate of one of prior art is handled, for example produced sludge owing to being generated as the insoluble salt tertiary iron phosphate from the iron ion of Ferrious material material stripping and phosphoric acid.Even with in the treatment solution, also can in treatment solution, contain phosphate radical, but, can produce sludge if the concentration of phosphate radical surpasses 1.0g/L in surface treatment of the present invention.In addition the treatment capacity of metal to be treated material handle bath relatively capacity significantly for a long time, can dissolve in order to make the stripping composition, also can add for example mineral acid such as sulfuric acid, hydrochloric acid; Organic acids such as acetate, oxalic acid, tartrate, citric acid, succsinic acid, gluconic acid, phthalic acid; But more than a kind or 2 kinds of the sequestrant of chelating stripping composition etc.
Surface treatment of the present invention is selected from calcium cpd, magnesium compound and strontium compound more than at least a kind with containing in the treatment solution.The present invention by will containing certain specific concentrations zirconium compounds and the free fluorine ionic concn in the aqueous solution of titanium compound be controlled at certain limit, can make 2 kinds to the 4 kinds whiles of chosen from Fe based material, zinc series materials, aluminium system and magnesium based material or carry out surface treatment respectively separately.Wherein, the metallic element that contains in above-mentioned calcium cpd, magnesium compound or the strontium compound (calcium, magnesium or strontium) has the effect that the free fluorine ionic concn that makes in the aqueous solution remains on certain value owing to generate the salt of fluorochemical with fluorine in the aqueous solution.Because this effect even simultaneously various metal to be treated materials are carried out surface treatment, is disobeyed its usage ratio, keeps certain free fluorine ionic concn usually, therefore can obtain best tunicle adhesion amount to different metal to be treated materials.
As the calcium cpd that can use in the present invention, magnesium compound or strontium compound, can enumerate oxide compound, oxyhydroxide, muriate, vitriol, nitrate and the carbonate etc. of these metals.In addition, except calcium cpd, magnesium compound or strontium compound,,, all can be able to use in the present invention no matter be inorganics, organism so long as have the compound that keeps free fluorinion concentration effect in the fluorinated water solution.
The magnesium compound that the present invention uses or the concentration of strontium compound, in above-mentioned metallic element, preferred 10～5000ppm, more preferably 100～3000ppm.For calcium cpd, because the solubleness of Calcium Fluoride (Fluorspan) is very little, in the preferred 5～100ppm of calcium, more preferably 5～50ppm.Wherein, when the concentration ratio higher limit of above-claimed cpd is big, may handle the stability of using treatment solution by failure surface, produce the obstacle in the operate continuously.In addition, the concentration ratio lower value of above-claimed cpd hour has the worry that reduces tunicle adhesion amount of the present invention especially on ferrous material.
In addition, surface treatment of the present invention is with the nitrate radical that can add 1000～50000ppm in the treatment solution, more preferably 1000～30000ppm.Nitrate radical works as oxygenant, has the effect that promotes the tunicle evolution reaction among the present invention and improves calcium cpd, magnesium compound or strontium compound in the effect of surface treatment with solubleness in the treatment solution.Therefore, even the concentration of nitrate radical during less than 1000ppm, also can be separated out the tunicle of excellent corrosion resistance, still, when above-mentioned calcium cpd, magnesium compound or strontium compound concentration are high, may failure surface handle and use treatment solution stability.In addition, the concentration of nitrate radical is that 50000ppm is enough, can only be uneconomic even add more nitrate radical.
In addition, can add in surface treatment of the present invention and be selected from HClO with treatment solution
3, HBrO
3, HNO
3, HNO
2, HMnO
4, HVO
3, H
2O
2, H
2WO
4And H
2MoO
4At least a kind of oxygen acid and/or the salt of these oxygen acid.Oxygen acid or its salt work to treated material as oxygenant, promote tunicle of the present invention to form reaction.Interpolation concentration to above-mentioned oxygen acid or these oxygen acid salts does not have particular determination, can give full play to as oxidant in effect under the addition of 10～5000ppm left and right sides.
And then, can add at least a kind of macromolecular compound that is selected from water-soluble high-molecular compound and water dispersible macromolecular compound in surface treatment of the present invention in treatment solution.Use surface treatment of the present invention to make the surface-treated metallic substance that sufficient erosion resistance be arranged, but when further requiring function such as oilness, select to add and the corresponding macromolecular compound of desired function, also can change the rerum natura of tunicle with treatment solution.Can use as acrylic acids such as multipolymer, ethene and (methyl) vinylformic acid of polyvinyl alcohol, poly-(methyl) vinylformic acid, vinylformic acid and methacrylic acid or (methyl) acrylate as above-mentioned water-soluble high-molecular compound and water dispersible macromolecular compound is monomeric multipolymer; The macromolecular compound of using always in the metal finishing such as the multipolymer of ethene and vinyl acetate, polyurethane(s), amino modified resol, vibrin, Resins, epoxy.
When using surface treatment of the present invention with treatment solution the metallic surface to be handled, well-established law has only the metal to be treated material that skimming treatment, purifying treatment are carried out in the surface to contact with treatment solution with surface treatment.Thus, separate out the oxide compound of the metallic element that contains selected among zirconium and titanium and/or the tunicle of oxyhydroxide, and form adaptation and the erosion resistance surface of good is handled by rete at metal material surface.This contact is handled and can be used arbitrary methods such as spraying plating processing, dip treating and flow coat processing, and this contact method does not influence performance.Above-mentioned metal hydroxides will obtain its pure oxyhydroxide, chemically is being difficult, usually the form of above-mentioned metal oxide band water of hydration is also brought into the category of oxyhydroxide.Therefore, above-mentioned metal hydroxides finally becomes oxide compound through heating.Think the structure of the surface treatment capsule layer among the present invention, implement after the surface treatment under normal temperature or low temperature when dry, be that oxide compound and oxyhydroxide mix the state that exists, and implement after the surface treatment when at high temperature dry, only become to acidulants or mostly be the state of oxide compound.
Surface treatment among the present invention does not have particular determination with the working conditions of treatment solution.The reactivity of surface treatment liquid of the present invention can freely be regulated and control with the concentration and the free fluorine ionic concn of zirconium compounds in the treatment solution or titanium compound by changing surface treatment.Therefore treatment temp and treatment time may change arbitrarily by making up with handling the reactivity of bathing.
In addition, to be selected from nonionic be that tensio-active agent, negatively charged ion are that tensio-active agent and positively charged ion are at least a kind of tensio-active agent of tensio-active agent and are used for surface treatment with adding in the treatment solution in above-mentioned surface treatment.When adopting this surface treatment with treatment solution metallic substance to be carried out surface treatment, the metal to be treated material also can form good tunicle without skimming treatment in advance, purification.That is to say that this surface treatment is used with the surface treatment agent that treatment solution can be used as the double as degreasingization.
In addition, when adopting surface treatment of the present invention to carry out metal finishing with treatment solution, also can adopt with the metal to be treated material is negative electrode, carries out electrolytic method in surface treatment in treatment solution.Wherein, if carry out electrolysis treatment with the metal to be treated material as negative electrode, hydrogen reduction reaction takes place and the pH rising on the negative electrode contact surface.Follow the rising of pH, the zirconium compounds on the negative electrode contact surface and/or the stability of titanium compound reduce, and separate out surface treatment capsule with oxide compound or aqueous hydroxide.
In addition, metal to be treated material and surface treatment contact the back with treatment solution or after surface treatment is carried out electrolysis treatment in treatment solution, wash or do not wash, by with the acidic aqueous solution of the compound that contains at least a kind of element that is selected from cobalt, nickel, tin, copper, titanium and zirconium, or contact, and then can improve effect of the present invention with containing the treatment solution that is selected from water-soluble high-molecular compound and at least a kind of macromolecular compound of water dispersible macromolecular compound.
The surface treatment capsule layer that obtains by the present invention is film and has shown good coating performance that still according to the condition of surface of metal to be treated material, the surface treatment capsule layer may have the minute defects part.Therefore, by making it and the acidic aqueous solution that contains the compound of at least a kind of element that is selected from cobalt, nickel, tin, copper, titanium and zirconium, or contact with containing the treatment solution that is selected from water-soluble high-molecular compound and at least a kind of macromolecular compound of water dispersible macromolecular compound, further improve erosion resistance thereby coat above-mentioned trickle defect part.
The above-mentioned compound that contains at least a kind of element that is selected from cobalt, nickel, tin, copper, titanium and zirconium does not have particular determination, can use oxide compound, oxyhydroxide, fluorochemical, fluorinated complex, muriate, nitrate, nitric acid oxonium salt, vitriol, sulfuric acid oxonium salt, carbonate, carbonic acid oxonium salt, phosphoric acid salt, phosphoric acid oxonium salt, oxalate, oxalic acid oxonium salt and the organometallic compound etc. of the above-mentioned metallic element that obtains easily.In addition, it is preferred 2～6 to contain the pH of acidic aqueous solution of above-mentioned metallic element, acid such as phosphoric acid, nitric acid, sulfuric acid, hydrofluoric acid, hydrochloric acid and organic acid, or alkali such as sodium hydroxide, potassium hydroxide, lithium hydroxide, an alkali metal salt, ammonium salt and amine are regulated.
In addition, as at least a kind of macromolecular compound that is selected from above-mentioned water-soluble high-molecular compound and water dispersible macromolecular compound, for example can using, acrylic acids such as polyvinyl alcohol, the multipolymer, ethene and (methyl) vinylformic acid that gather (methyl) vinylformic acid, vinylformic acid and methacrylic acid or (methyl) acrylate are monomeric multipolymer; The multipolymer of ethene and vinyl acetate, polyurethane(s), amino modified resol, vibrin, Resins, epoxy, tannin and Weibull and salt and phytinic acid etc.
The present invention is provided with the oxide compound of the metallic element that contains selected among zirconium or titanium and/or the surface treatment capsule layer of oxyhydroxide on the metal to be treated material surface, therefore can improve the erosion resistance of metallic substance tremendously.Wherein, the oxide compound of above-mentioned metallic element and oxyhydroxide have and are difficult to by acid or the chemically stable character of alkali erosive.In the environment of actual corroding metal, the pH that the anode portion of metal stripping takes place reduces, and causes that the pH of the negative pole part that reduction reaction takes place rises.Therefore, the surface treatment capsule of acid resistance and alkali resistance difference, dissolving under corrosive atmosphere and lose its effect.The principal constituent of the surface treatment capsule layer among the present invention is difficult to be corroded by acid or alkali, therefore also can keep good effect under corrosive atmosphere.
In addition, the oxide compound of above-mentioned metallic element and oxyhydroxide owing to formed the reticulated structure of being got involved by metal and oxygen, have formed very good barrier tunicle.The Corrosion of Metallic Materials situation according to environment for use and difference, but generally is to have aerobic-type corrosion under the situation at water and oxygen, and this corrosion speed is because the existence of compositions such as muriate and being promoted.Wherein, surface treatment capsule layer of the present invention has screen effect to water, oxygen and promotion corrosive composition, therefore can bring into play superior corrosion resistance.
At this, utilize above-mentioned screen effect, in order to improve the erosion resistance of ferrous materials such as cold-rolled steel sheet, hot-rolled steel sheet, cast iron and agglomerated material, with above-mentioned metallic element conversion 30mg/m
2Above adhesion amount is necessary, preferred 40mg/m
2Above adhesion amount, more preferably 50mg/m
2Above adhesion amount.In addition, in order to improve the erosion resistance of zinc systems such as zinc, steel plate galvanized, alloy galvanized steel plate, with above-mentioned metallic element conversion 20mg/m
2Above adhesion amount is necessary, preferred 30mg/m
2Above adhesion amount.And then, in order to improve the erosion resistance of aluminium based materials such as aluminium casting and aluminium alloy plate, with above-mentioned metallic element conversion 10mg/m
2Above adhesion amount is necessary, preferred 20mg/m
2Above adhesion amount.In addition, in order to improve the erosion resistance of magnesium systems such as magnesium alloy plate and magnesium foundry goods, with above-mentioned metallic element conversion 10mg/m
2Above adhesion amount is necessary, preferred 20mg/m
2Above adhesion amount.The upper limit to adhesion amount does not have particular determination, but if adhesion amount surpasses 1g/m
2, generating sludge on the surface treatment capsule easily, the operation that obtains uniform tunicle becomes difficult.Therefore, all preferred 800mg/m of the adhesion amount upper limit of ferrous material, zinc series materials and aluminium based material
2But not 1g/m
2
Embodiment
Enumerate embodiment and comparative example when as follows, specify the effect of surface treatment of the present invention with treatment solution and surface treatment method.And the treated material that uses among the embodiment, grease-removing agent and coating are selected arbitrarily in the commercially available material, and the non-limiting surface treatment of the present invention practical use of treatment solution and surface treatment method.
[for test plate (panel)]
Use cold-rolled steel sheet, hot-dip galvanized steel sheet, aluminium alloy and magnesium alloy plate the test plate (panel) that supplies as embodiment and comparative example.This brevity code and detail for test plate (panel) is expressed as follows.Adopt the confession test plate (panel) of the state that 3 kinds of metallic substance of SPC, GA and Al are connected with spot welding when estimating the outward appearance after the surface treatment.Adopt SPC, GA, Al, Mg for test plate (panel) respectively separately when estimating the adhesion amount of surface treatment capsule layer, with the test plate (panel) that supplies of the state that 3 kinds of metallic substance of SPC, GA and Al are connected with spot welding.When estimating coating performance, adopt state that SPC, GA and Al3 kind metallic substance are connected with spot welding for test plate (panel), implement a series of tests of surface treatment, coating, coating performance evaluation.Fig. 1 is the orthographic plan for test plate (panel) that 3 kinds of metallic substance of SPC, GA and Al are connected with spot welding, and Fig. 2 is its front elevation.1 expression spot welding position.
SPC (cold-rolled steel sheet: JIS-G-3141)
GA (two sides alloy galvanized steel plate: plating amount 45g/m
2)
Al (aluminium alloy plate: 6000 line aluminium alloys)
Mg (magnesium alloy plate: JIS-H-4201)
[treatment process]
The treatment process of embodiment, comparative example is as follows.
Embodiment 1-4, embodiment 7 and comparative example 1-4: alkali degreasing → washing → formation tunicle processing → washing → pure water is washed → drying
Embodiment 5: alkali degreasing → washing → formation electrolysis tunicle processing → washing → pure water is washed → drying
Embodiment 6: form tunicle processing (dual-purpose skimming treatment) → washing → pure water and wash → drying
Embodiment 8: alkali degreasing → washing → formation tunicle processing → washing → aftertreatment → pure water is washed → drying
Embodiment 9: form tunicle processing (dual-purpose skimming treatment) → washing → aftertreatment → pure water and wash → drying
Comparative example 5: alkali degreasing → washing → surface adjustment → zinc phosphate processing → washing → pure water is washed → drying
In above-mentioned, it all is with FINE CLEANERL4460 (registered trademark: Japanese パ-カ ラ イ ジ Application グ (strain) system) be diluted to 2%, 40 ℃ with tap water, sprayed 120 seconds to processed plate that embodiment, comparative example are carried out alkali degreasing.It all is at room temperature to spray 30 seconds to processed plate that embodiment, comparative example are carried out that washing after tunicle is handled and pure water wash.
Use Zircosol ZN reagent and nitric acid, preparation zirconium concentration is the aqueous solution of 200ppm.At 45 ℃ down after the heating, using sodium hydroxide reagent and hydrofluoric acid is 3.0 with pH regulator with this solution, will be with fluorion instrument (IM-55G; East Asia electric wave industry (strain) system) the free fluorine ionic concn of measuring is adjusted to 1ppm, with this as the surface treatment treatment solution.Regulating the surface treatment afterwards of free fluorine ionic concn is 50ppm with whole fluorinion concentrations in the treatment solution.
Impregnated in above-mentioned surface treatment with in the treatment solution 120 seconds with what implement washing after the degreasing for test plate (panel), carry out surface treatment.
Embodiment 2
Use Zircosol ZN reagent, magnesium nitrate reagent and strontium nitrate reagent, preparation zirconium concentration is that 100ppm, magnesium density are that 5000ppm, strontium concentration are that 2000ppm, nitrate radical are the aqueous solution of 28470ppm.After this solution was heated to 50 ℃, using ammoniacal liquor reagent and hydrofluoric acid to regulate pH was 4.0, will be with fluorion instrument (IM-55G; East Asia electric wave industry (strain) system) the free fluorine ionic concn of measuring is adjusted to 80ppm, with this as the surface treatment treatment solution.Regulating the surface treatment afterwards of free fluorine ionic concn is 2000ppm with whole fluorinion concentrations in the treatment solution.
Impregnated in above-mentioned surface treatment with in the treatment solution 60 seconds with what implement washing after the degreasing for test plate (panel), carry out surface treatment.
Embodiment 3
Use hexafluoro zirconate (IV) aqueous solution, titanium sulfate (IV) aqueous solution, calcium sulfate reagent and nitric acid, preparation zirconium concentration is that 1000ppm, titanium concentration are that 2000ppm, calcium concn are that 5ppm, nitrate radical are the aqueous solution of 1000ppm.After this solution was heated to 40 ℃, using potassium hydroxide reagent and hydrofluoric acid to regulate pH was 5.0, will be with fluorion instrument (IM-55G; East Asia electric wave industry (strain) system) the free fluorine ionic concn of measuring is adjusted to 25ppm, with this as the surface treatment treatment solution.Regulating the surface treatment afterwards of free fluorine ionic concn is 2250ppm with whole fluorinion concentrations in the treatment solution.
Impregnated in above-mentioned surface treatment with in the treatment solution 90 seconds with what implement washing after the degreasing for test plate (panel), carry out surface treatment.
Embodiment 4
Use hexafluoro metatitanic acid (IV) aqueous solution, strontium nitrate reagent and Sodium Nitrite reagent, preparation titanium concentration is that 5000ppm, strontium concentration are that 5000ppm, nitrate radical are that 7080ppm, nitrite anions concentration are the aqueous solution of 40ppm.After this solution was heated to 35 ℃, using trolamine reagent and hydrofluoric acid to regulate pH was 4.0, will be with fluorion instrument (IM-55G; East Asia electric wave industry (strain) system) the free fluorine ionic concn of measuring is adjusted to 10ppm, with this as the surface treatment treatment solution.Regulating the surface treatment afterwards of free fluorine ionic concn is 11900ppm with whole fluorinion concentrations in the treatment solution.
By nozzle above-mentioned surface treatment is sprayed to last 120 second of confession test plate (panel) of implementing washing after the degreasing with treatment solution, carries out surface treatment.
Embodiment 5
Use Zircosol ZN reagent, hexafluoro metatitanic acid (IV) aqueous solution, magnesium nitrate reagent and sodium chlorate reagent, preparation zirconium concentration is that 5ppm, titanium concentration are that 5ppm, magnesium density are that 100ppm, nitrate radical are that 30520ppm, chlorate anions are the aqueous solution of 100ppm.After this solution was heated to 30 ℃, using ammoniacal liquor reagent and hydrofluoric acid to regulate pH was 6.0, will be with fluorion instrument (IM-55G; East Asia electric wave industry (strain) system) the free fluorine ionic concn of measuring is adjusted to 0.5ppm, with this as the surface treatment treatment solution.Regulating the surface treatment afterwards of free fluorine ionic concn is 12ppm with whole fluorinion concentrations in the treatment solution.
Supply test plate (panel) as negative electrode with what implement after the degreasing to wash, anode uses carbon dioxide process carbon electrode, at above-mentioned surface treatment 5A/dm in the treatment solution
2Electrolytic condition under, surface treatment is carried out in electrolysis 5 seconds.
Embodiment 6
Use Zircosol ZN reagent, magnesium oxide reagent, nitric acid and aquae hydrogenii dioxidi reagent, preparation zirconium concentration is that 150ppm, magnesium density are that 10ppm, nitrate radical are that 5200ppm, hydrogen peroxide are the aqueous solution of 10ppm.After this solution was heated to 50 ℃, using ammoniacal liquor reagent and hydrofluoric acid to regulate pH was 5.0, will be with fluorion instrument (IM-55G; East Asia electric wave industry (strain) system) the free fluorine ionic concn of measuring is adjusted to 50ppm, and then adds the non-ionic surfactant polyoxyethylene nonylplenyl ether (oxyethane addition mole number: 12 moles) of 2g/L, with this as the surface treatment treatment solution.Regulating the surface treatment afterwards of free fluorine ionic concn is 170ppm with whole fluorinion concentrations in the treatment solution.
Do not carry out skimming treatment, above-mentioned surface treatment is sprayed to last 90 second of confession test plate (panel) that is coated with oil condition with treatment solution, carry out surface treatment in the time of degreasing by nozzle.
Embodiment 7
Use titanium sulfate (IV) aqueous solution, nitrocalcite reagent, magnesium nitrate reagent and potassium permanganate, preparation titanium concentration is that 100ppm, calcium concn are that 50ppm, magnesium density are that 5000ppm, nitrate radical are that 25660ppm, permanganic acid are the aqueous solution of 10ppm.And then in this aqueous solution, add the water-soluble propenoic-acids macromolecular compound (ジ ユ リ マ-AC-10L: Japanese pure medicine company limited system) make solid shape branch concentration be 1% and be heated to 50 ℃ after, using sodium hydroxide reagent and hydrofluoric acid to regulate pH is 3.0, will be with fluorion instrument (IM-55G; East Asia electric wave industry (strain) system) the free fluorine ionic concn of measuring is adjusted to 95ppm, with this as the surface treatment treatment solution.Regulating the surface treatment afterwards of free fluorine ionic concn is 2000ppm with whole fluorinion concentrations in the treatment solution.
Impregnated in above-mentioned surface treatment with in the treatment solution 60 seconds with what implement washing after the skimming treatment for test plate (panel), carry out surface treatment.
Embodiment 8
Preparation divides densitometer water-soluble propenoic-acids macromolecular compound (ジ ユ リ マ-AC-10L: the aqueous solution of Japanese pure medicine company limited system) be 1%, phosphoric acid reagent being counted 2g/L with phosphate radical with solid shape.After this solution was heated to 40 ℃, using ammoniacal liquor reagent to regulate pH was 4.5, the preparation aftertreatment fluid.To impregnated in the above-mentioned aftertreatment fluid 30 seconds for test plate (panel) by what embodiment 5 surface treatments had implemented to form tunicle and washing, carry out aftertreatment.
Embodiment 9
Use hexafluoro zirconate (IV) aqueous solution and Xiao Suangu reagent, preparation zirconium concentration is that 50ppm, cobalt concentration are the aqueous solution of 50ppm, and then after the above-mentioned aqueous solution was heated to 40 ℃, using ammoniacal liquor reagent to regulate pH was 5.0, the preparation aftertreatment fluid.To impregnated in the above-mentioned aftertreatment fluid 30 seconds for test plate (panel) by what embodiment 6 surface treatments had implemented to form tunicle and washing, carry out aftertreatment.
Comparative example 1
Use Zircosol ZN reagent, magnesium nitrate reagent and nitric acid, preparation zirconium concentration is that 500ppm, magnesium density are that 1000ppm, nitrate radical are the aqueous solution of 6780ppm.After this solution was heated to 45 ℃, using sodium hydroxide reagent to regulate pH was 4.0, with this as the surface treatment treatment solution.With commercially available fluorion instrument (IM-55G; East Asia electric wave industry (strain) system) the free fluorine ionic concn of the above-mentioned surface treatment of mensuration in the treatment solution, consequently 0ppm.
Impregnated in above-mentioned surface treatment with in the treatment solution 120 seconds with what implement washing after the degreasing for test plate (panel), carry out surface treatment.
Comparative example 2
Use titanium sulfate (IV) aqueous solution, preparation titanium concentration is the aqueous solution of 2000ppm.After this solution was heated to 50 ℃, using ammoniacal liquor reagent and hydrofluoric acid was 3.5 with pH regulator, will be with fluorion instrument (IM-55G; East Asia electric wave industry (strain) system) the free fluorine ionic concn of measuring is adjusted to 400ppm, with this as the surface treatment treatment solution.
Impregnated in above-mentioned surface treatment with in treatment solution 90 second for test plate (panel) with implementing after the degreasing after the washing, carry out surface treatment.
Comparative example 3
With commercially available chromium-chromic salt (the reagent treatment ア Le Network ロ system 713 of Network ロ ミ Star Network Network ロ メ-ト) (registered trademark: Japanese パ-カ ラ イ ジ Application グ (strain) system) be diluted to 3.6%, and then be the full acidity of centering control, free acidity with the goods catalogue value with tap water.
Impregnated in the above-mentioned chromate treating liquid that is heated to 35 ℃ 60 seconds with what implement washing after the degreasing for test plate (panel), carry out chromate treating.
Comparative example 4
With commercially available non-chromate reagent treatment パ Le コ-ト 3756 (registered trademark: Japanese パ-カ ラ イ ジ Application グ (strain) system) be diluted to 2%, and then be the full acidity of centering control, free acidity with the goods catalogue value with tap water.Impregnated in the above-mentioned non-chromate treatment solution that is heated to 40 ℃ 60 seconds with what implement washing after the degreasing for test plate (panel), carry out non-chromate and handle.
Comparative example 5
Under the room temperature, by nozzle with the surface adjust treatment agent プ レ パ レ Application ZN (registered trademark: Japanese パ-カ ラ イ ジ Application グ (strain) system) be diluted to tap water 0.1% liquid spray implement after the degreasing washing for test plate (panel) after last 30 second, be impregnated in the zinc phosphate tunicle is separated out, wherein, this treatment solution is prepared as follows: with パ Le ボ Application De L3020 (registered trademark: Japanese パ-カ ラ イ ジ Application グ (strain) system) be diluted to 4.8% with tap water, and then interpolation is in the sodium hydrogen fluoride reagent of fluorine 200ppm, be the full acidity of centering control with the goods catalogue value then, free acidity is made 42 ℃ zinc phosphate chemical synthesis treatment liquid.
[evaluation of surface treatment capsule]
Outward appearance after visual assessment embodiment and the comparative example surface treatment for test plate (panel).Its result is as shown in table 1.(System 3270 to use fluorescent x-ray analyzer; Electrical industry of science (strain) system) adhesion amount of mensuration surface treatment capsule layer.Its result is shown in table 2 and table 3.In addition, the adhesion amount of surface treatment capsule layer is that each metallic substance is not engaged and the situation (do not have and engage) handled respectively and merge the situation of handling (joint is arranged) with spot weld and measure.
Table 1
The ocular estimate result of the surface treatment capsule that obtains in table 1 expression embodiment and the comparative example.For whole metallic substance kinds of test plate (panel), embodiment can both obtain uniform tunicle for all.And the spot welding part for test plate (panel) that uses is in an embodiment also observed the situation that surface treatment capsule is separated out.To this, in comparative example,, all do not separate out uniform tunicle for whole test plate (panel)s that supplies.Particularly comparative example 3,4 and 5, do not separate out tunicle fully at spot welding part.In addition, though comparative example 5 is the zinc phosphate treatment solutions when handling cold-rolled steel sheet, steel plate galvanized and aluminium alloy simultaneously, but as this test, by welding under the condition that each testing plate engages, the exposed portions serve of the metallic substance base substrate of open country (ス ケ) has appearred on the cold-rolled steel sheet being called as.
Table 2
Table 3
The measurement result of the surface treatment capsule adhesion amount that obtains in table 2 and table 3 expression embodiment and the comparative example.In an embodiment, for whole metallic substance kinds of test plate (panel), can obtain the adhesion amount of target for all.In addition, the surface treatment capsule adhesion amount among the embodiment is certain, does not rely on for having or not that test plate (panel) engages.Yet in comparative example, the result shows by the tunicle ocular estimate, for whole test plate (panel)s that supplies, all can not separate out uniform tunicle.
[evaluation of coating performance]
(coating performance is estimated the making of plate)
In order to estimate the coating performance of embodiment and comparative example surface treatment plate, being coated with according to following operation: cation electrodeposition electrophoresis painting dressing → pure water washes → cures → the middle level application → cure → the top layer application → cure.Cation electrodeposition electrophoresis painting dressing, middle level application, top layer application are as follows.
The cation electrodeposition electrophoresis painting dressing: the epoxy resin cation electrophoretic coating (エ レ Network ロ Application 9400: Northwest pigment (strain) system), voltage 200V, thickness 20 μ m cured 20 minutes at 175 ℃.
The middle level application: alkyd amino is that (ア ミ ラ Star Network TP-37 ash: Northwest pigment (strain) system), spray, thickness 35 μ m cured 20 minutes at 140 ℃ coating.
The top layer application: alkyd amino is that (TM-13 is white for ア ミ ラ Star Network: Northwest pigment (strain) system), spray, thickness 35 μ m cured 20 minutes at 140 ℃ coating.
(coating performance evaluation)
Carry out the evaluation of embodiment and comparative example coating performance.Its result is shown in table 4 and table 5.Assessment item and mark are as follows.Filming when in addition, electrophoretic painting finishes is called that electrophoresis is filmed, filming when the top layer application finishes is called 3 and is coated with coating film.
1. SST: salt spray testing (electrophoresis is filmed)
2. SDT: salt warm water test (electrophoresis is filmed)
3. ADH:1 adaptation of 1st (3 are coated with coating film)
4. 2nd ADH: water-fast 2 adaptations (3 are coated with coating film)
SST: with sharp cutting knife with the crosscut of electrophoretic painting plate, to this electrophoretic painting plate 5% salt solution 840 hours (is standard with JIS-Z-2371) of spraying.After spraying finishes, measure the maximum swelling amplitude of crosscut portion both sides.
SDT: the electrophoretic painting plate be impregnated in the NaCl aqueous solution of the 5wt% that is warming up to 50 ℃ 840 hours.After dipping finishes, peel off with adhesive tape with whole faces of the testing plate of tap water washing → Air drying, that films on each metallic substance of range estimation judgement peels off area.
1st ADH: be coated with the checker that cuts out 100 2mm intervals on the coating film 3 with sharp cutting knife.The checker part is peeled off with fiber band, and number goes out the tessellated number of peeling off.
2nd ADH: be coated with in the deionized water that the coating film plate impregnated in 40 ℃ 240 hours with 3.The dipping back cuts out 100 2mm checker at interval with sharp cutting knife.The checker part is peeled off with fiber band, and number goes out the tessellated number of peeling off.
Table 4
The coating performance evaluation result that table 4 expression electrophoresis is filmed.The test plate (panel)s that supply whole among the embodiment show good anti-corrosion.Yet in the comparative example 1, owing to do not contain the free fluorion fully in treatment solution in surface treatment, so can not fully separate out surface treatment capsule, corrosion-resistant.In addition, in the comparative example 2, because at surface treatment free fluorinion concentration height in the treatment solution, so the tunicle adhesion amount on the SPC is especially little, the result is a corrosion-resistant.Though embodiment 5 and 6 shows the coating performance good than comparative example, compares with other embodiment, the erosion resistance behind the electrophoretic painting is slightly poor.But, shown in embodiment 8 and 9,, further improve erosion resistance by implementing aftertreatment.
Comparative example 3 is that aluminium alloy is aluminium alloy non-chromate treatment agents with chromate treating agent, comparative example 4, so the excellent corrosion resistance of Al, but other the erosion resistance that supplies test plate (panel) is obviously than embodiment difference.Comparative example 5 is that normally used zinc phosphate is handled now as cation electrodeposition electrophoresis painting dressing undercoat.But, as this test,,, comparing with embodiment by welding under the condition that each testing plate engages even in comparative example 5, its result also is poor.
Table 5
Table 5 expression 3 is coated with the adaptation evaluation result of coating film plate.The test plate (panel)s that supply whole among the embodiment show good adaptation.Even 1st ADH also shows good result in comparative example, and for 2nd ADH, the erosion resistance of filming with electrophoresis is identical, the test plate (panel) that supplies for whole does not reach the standard that shows good adaptation.In addition, in comparative example 5, during the processing after the surface treatment is bathed, the by product sludge when producing the zinc phosphate processing.But, in an embodiment, in any standard, all do not find to produce sludge.
Above result shows, the surface treatment of the application of the invention product need not change to handle and bathe and treatment condition with treatment solution and surface treatment method, and treatment S PC, GA and Al simultaneously can separate out the surface treatment capsule of adaptation and excellent corrosion resistance.And then the application of the invention, on weld part, can separate out the surface treatment capsule of excellent corrosion resistance.In addition, surface treatment method of the present invention only makes the metal to be treated material contact with treatment solution with surface treatment and gets final product, and therefore as in bag constructions inside, at the position of not wishing to have mixing effect, surface treatment capsule is separated out seek to improve erosion resistance.
Industrial applicibility
Surface treatment according to the present invention is with treatment fluid and the surface treatment of using this treatment fluid Method, can not realize in prior art, do not contain environmentally harmful composition In process bathing, do not produce sludge, simultaneously or contain separately ferrous material separately, zinc is material On 2 kinds to 4 kinds the metal surface of material, aluminium system and magnesium based material, separate out after the application anti-The surface treatment capsule that corrosivity is good. In addition, even do not carry out the metal to be treated material Operation is adjusted on the surface, also can separate out surface treatment capsule, in this case, can shorten Treatment process is saved the space.
Claims (10)
1. metal surface treating method, it is characterized by: with the metallic substance of chosen from Fe based material, zinc series materials, aluminium based material and magnesium based material respectively separately or its more than 2 kinds simultaneously with this metallic substance as negative electrode, carry out electrolysis treatment in metal finishing in treatment solution, described metal finishing is characterized as with treatment solution:
(1) contain the compound more than a kind of 5～5000ppm selected among zirconium compound and titanium compound as above-mentioned metallic element,
(2) contain 0.1～100ppm free fluorine ion,
(3) contain the compound more than a kind that is selected from calcium cpd, magnesium compound and strontium compound, above-claimed cpd concentration, in above-mentioned metallic element, calcium cpd is that 5～50ppm, magnesium compound or strontium compound are 10～5000ppm,
(4) contain 1000～50000ppm nitrate radical,
(5) contain and be selected from HBrO
3, HNO
2And H
2O
2And at least a kind of oxygen acid in its esters and/or oxysalt,
(6) pH is 3～6.
2. metal surface treating method as claimed in claim 1, described metal finishing are with treatment solution and then contain at least a kind of macromolecular compound that is selected from water-soluble high-molecular compound and water dispersible macromolecular compound.
3. metal surface treating method as claimed in claim 1, described metal finishing are with treatment solution and then contain at least a kind of tensio-active agent that is selected from nonionic surface active agent, aniorfic surfactant and the cationic surfactant.
4. metal surface treating method as claimed in claim 1, it is characterized by: metallic substance is after surface treatment is carried out electrolysis treatment in treatment solution, wash or do not wash, and then its acidic aqueous solution with the compound that contains at least a kind of element that is selected from cobalt, nickel, tin, copper, titanium and zirconium is contacted.
5. metal surface treating method as claimed in claim 1, it is characterized by: metallic substance is after surface treatment is carried out electrolysis treatment in treatment solution, washing or do not wash, and then make it and contain the treatment solution that is selected from water-soluble high-molecular compound and at least a kind of macromolecular compound of water dispersible macromolecular compound and contact.
6. metal surface treating method is characterized by: make chosen from Fe based material, zinc series materials, aluminium based material and magnesium based material, without the metallic substance of degreasing purifying treatment respectively separately or its contact with treatment solution with the described surface treatment of claim 3 simultaneously more than 2 kinds.
7. metallic substance, it is characterized by: on the Ferrious material material surface, have the surface treatment capsule that is selected from the metallic element of at least a kind of titanium and zirconium by any described surface treatment method of claim 1～6 containing of forming, and the adhesion amount of this surface treatment capsule is scaled 30mg/m with above-mentioned metallic element
2More than.
8. metallic substance, it is characterized by: at zinc is to have the surface treatment capsule that is selected from the metallic element of at least a kind of titanium and zirconium by any described surface treatment method of claim 1～6 containing of forming on the metal material surface, and the adhesion amount of this surface treatment capsule is scaled 20mg/m with above-mentioned metallic element
2More than.
9. metallic substance, it is characterized by: on the aluminum-based metal material surface, have the surface treatment capsule layer that is selected from the metallic element of at least a kind of titanium and zirconium by any described surface treatment method of claim 1～6 containing of forming, and the adhesion amount of this surface treatment capsule is scaled 10mg/m with above-mentioned metallic element
2More than.
10. metallic substance, it is characterized by: at magnesium is to have the surface treatment capsule layer that is selected from the metallic element of at least a kind of titanium and zirconium by any described surface treatment method of claim 1～6 containing of forming on the metal material surface, and the adhesion amount of this surface treatment capsule is scaled 10mg/m with above-mentioned metallic element
2More than.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002362640A JP4205939B2 (en) | 2002-12-13 | 2002-12-13 | Metal surface treatment method |
| JP362640/2002 | 2002-12-13 |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008101849496A Division CN101487115B (en) | 2002-12-13 | 2003-12-11 | Treating fluid for surface treatment of metal and method for surface treatment |
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| CN1726304A CN1726304A (en) | 2006-01-25 |
| CN100537845C true CN100537845C (en) | 2009-09-09 |
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| CNB2003801059479A Expired - Lifetime CN100537845C (en) | 2002-12-13 | 2003-12-11 | Metal finishing treatment solution and surface treatment method |
| CN2008101849496A Expired - Lifetime CN101487115B (en) | 2002-12-13 | 2003-12-11 | Treating fluid for surface treatment of metal and method for surface treatment |
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| CN2008101849496A Expired - Lifetime CN101487115B (en) | 2002-12-13 | 2003-12-11 | Treating fluid for surface treatment of metal and method for surface treatment |
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| US (1) | US20060185769A1 (en) |
| EP (1) | EP1571237B1 (en) |
| JP (1) | JP4205939B2 (en) |
| KR (1) | KR100674778B1 (en) |
| CN (2) | CN100537845C (en) |
| AU (1) | AU2003289323A1 (en) |
| CA (1) | CA2509772A1 (en) |
| ES (1) | ES2730576T3 (en) |
| MX (1) | MXPA05006156A (en) |
| TW (1) | TW200416300A (en) |
| WO (1) | WO2004055237A1 (en) |
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| CN101487115B (en) * | 2002-12-13 | 2013-05-22 | 日本帕卡濑精株式会社 | Treating fluid for surface treatment of metal and method for surface treatment |
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- 2003-12-11 MX MXPA05006156A patent/MXPA05006156A/en active IP Right Grant
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101487115B (en) * | 2002-12-13 | 2013-05-22 | 日本帕卡濑精株式会社 | Treating fluid for surface treatment of metal and method for surface treatment |
| TWI409363B (en) * | 2010-05-13 | 2013-09-21 |
Also Published As
| Publication number | Publication date |
|---|---|
| US20060185769A1 (en) | 2006-08-24 |
| MXPA05006156A (en) | 2005-12-05 |
| KR20050097916A (en) | 2005-10-10 |
| CN101487115A (en) | 2009-07-22 |
| EP1571237A4 (en) | 2007-11-21 |
| CN1726304A (en) | 2006-01-25 |
| WO2004055237A1 (en) | 2004-07-01 |
| EP1571237B1 (en) | 2019-03-20 |
| EP1571237A1 (en) | 2005-09-07 |
| JP4205939B2 (en) | 2009-01-07 |
| TW200416300A (en) | 2004-09-01 |
| CN101487115B (en) | 2013-05-22 |
| JP2004190121A (en) | 2004-07-08 |
| KR100674778B1 (en) | 2007-01-25 |
| AU2003289323A8 (en) | 2004-07-09 |
| ES2730576T3 (en) | 2019-11-12 |
| AU2003289323A1 (en) | 2004-07-09 |
| CA2509772A1 (en) | 2004-07-01 |
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