EP1571237A1 - Treating fluid for surface treatment of metal and method for surface treatment - Google Patents
Treating fluid for surface treatment of metal and method for surface treatment Download PDFInfo
- Publication number
- EP1571237A1 EP1571237A1 EP03780727A EP03780727A EP1571237A1 EP 1571237 A1 EP1571237 A1 EP 1571237A1 EP 03780727 A EP03780727 A EP 03780727A EP 03780727 A EP03780727 A EP 03780727A EP 1571237 A1 EP1571237 A1 EP 1571237A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- metal
- surface treatment
- treating solution
- compound
- group
- 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.)
- Granted
Links
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- 238000004381 surface treatment Methods 0.000 title claims abstract description 154
- 239000002184 metal Substances 0.000 title claims abstract description 149
- 238000000034 method Methods 0.000 title claims description 56
- 239000012530 fluid Substances 0.000 title 1
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- 239000007769 metal material Substances 0.000 claims abstract description 106
- 150000001875 compounds Chemical class 0.000 claims abstract description 61
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- 229920000642 polymer Polymers 0.000 claims abstract description 24
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical group O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002253 acid Substances 0.000 claims abstract description 20
- 150000003839 salts Chemical class 0.000 claims abstract description 20
- 239000004094 surface-active agent Substances 0.000 claims abstract description 18
- 150000003755 zirconium compounds Chemical class 0.000 claims abstract description 18
- 150000003609 titanium compounds Chemical class 0.000 claims abstract description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 12
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- 150000001674 calcium compounds Chemical class 0.000 claims abstract description 12
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- 229910052804 chromium Inorganic materials 0.000 description 1
- ABXXWVKOBZHNNF-UHFFFAOYSA-N chromium(3+);dioxido(dioxo)chromium Chemical compound [Cr+3].[Cr+3].[O-][Cr]([O-])(=O)=O.[O-][Cr]([O-])(=O)=O.[O-][Cr]([O-])(=O)=O ABXXWVKOBZHNNF-UHFFFAOYSA-N 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 238000004512 die casting Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000005246 galvanizing Methods 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 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
- 238000005259 measurement Methods 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- YOYLLRBMGQRFTN-SMCOLXIQSA-N norbuprenorphine Chemical compound C([C@@H](NCC1)[C@]23CC[C@]4([C@H](C3)C(C)(O)C(C)(C)C)OC)C3=CC=C(O)C5=C3[C@@]21[C@H]4O5 YOYLLRBMGQRFTN-SMCOLXIQSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- KADRTWZQWGIUGO-UHFFFAOYSA-L oxotitanium(2+);sulfate Chemical compound [Ti+2]=O.[O-]S([O-])(=O)=O KADRTWZQWGIUGO-UHFFFAOYSA-L 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000000467 phytic acid Substances 0.000 description 1
- 235000002949 phytic acid Nutrition 0.000 description 1
- 229940068041 phytic acid Drugs 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- VBKNTGMWIPUCRF-UHFFFAOYSA-M potassium;fluoride;hydrofluoride Chemical compound F.[F-].[K+] VBKNTGMWIPUCRF-UHFFFAOYSA-M 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000007420 reactivation Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 229920002258 tannic acid Polymers 0.000 description 1
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 description 1
- 229940033123 tannic acid Drugs 0.000 description 1
- 235000015523 tannic acid Nutrition 0.000 description 1
- 229920001864 tannin Polymers 0.000 description 1
- 239000001648 tannin Substances 0.000 description 1
- 235000018553 tannin Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Inorganic materials [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- XROWMBWRMNHXMF-UHFFFAOYSA-J titanium tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[Ti+4] XROWMBWRMNHXMF-UHFFFAOYSA-J 0.000 description 1
- HDUMBHAAKGUHAR-UHFFFAOYSA-J titanium(4+);disulfate Chemical compound [Ti+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O HDUMBHAAKGUHAR-UHFFFAOYSA-J 0.000 description 1
- CENHPXAQKISCGD-UHFFFAOYSA-N trioxathietane 4,4-dioxide Chemical compound O=S1(=O)OOO1 CENHPXAQKISCGD-UHFFFAOYSA-N 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000010930 yellow gold Substances 0.000 description 1
- 229910001097 yellow gold Inorganic materials 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Inorganic materials [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
- OMQSJNWFFJOIMO-UHFFFAOYSA-J zirconium tetrafluoride Chemical compound F[Zr](F)(F)F OMQSJNWFFJOIMO-UHFFFAOYSA-J 0.000 description 1
- LBVWQMVSUSYKGQ-UHFFFAOYSA-J zirconium(4+) tetranitrite Chemical compound [Zr+4].[O-]N=O.[O-]N=O.[O-]N=O.[O-]N=O LBVWQMVSUSYKGQ-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
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical compound Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
- C23C22/44—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates containing also fluorides or complex fluorides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- 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
-
- 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
- C23C22/82—After-treatment
- C23C22/83—Chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
- C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes
Definitions
- the present invention relates to the treating solution for surface treatment of metal which may deposit a surface treated film having excellent corrosion resistance after being coated on the surface of a metal material of a structural construction such as car body consisting of a single material or two to four materials selected from the group consisting of ferriferous material, zinciferous material, aluminiferous material and magnesiferous material independently or simultaneously.
- a zinc phosphate treatment and a chromate treatment are currently used as ordinary methods.
- the zinc phosphate treatment it is possible to deposit a film having excellent corrosion resistance on the surface of steel such as cold rolled steel plate, zinc plated steel plate and some of aluminum alloys.
- the generation of sludge, which is the byproduct of the reaction can not be avoided, and depending on the kind of aluminum alloy, the sufficient corrosion resistance after coated can not be obtained.
- the chromate treatment which contains harmful hexavalent chrome in the treating solution is more likely to be avoided.
- various methods have been proposed as described below.
- JP 2000-204485 A a compound containing nitrogen atom having a lone electron-pair and a non-chrome coating agent for metal surface treatment containing said compound and zirconium compound are suggested.
- This method may obtain a surface treated film which is excellent in corrosion resistance and adhesiveness after being coated, and yet does not contain harmful hexavalent chrome by coating above mentioned coating agent.
- the metal material which can be treated is limited to aluminum alloys only, and, it is difficult to be applied to a structural construction having complex structure such as car body, because the surface treated film is formed by coating and drying.
- metal materials to be treated may include magnesium, magnesium alloy, zinc and zinc plated alloy other than aluminum alloy.
- a method for metal surface treatment by chrome free coating acid composition by coating aqueous solution containing component which can be a film having excellent corrosion resistance over the surface of metal, then baking and drying without rinsing with water so as the film to be fixed (see JP 5-195244 A).
- This method does not involve any chemical reaction to form a film, so this method may form a film on the surface of metal such as zinc plated steel plate, cold rolled steel plate or aluminum alloy.
- JP 2000-204485 A since the film is formed by coating and drying, it is difficult to form a uniform film on the surface of a structural construction having complex structure such as car body.
- the object of the present invention is to provide a treating solution for surface treatment of metal to form a surface treated film having excellent corrosion resistance after coated on the surface of ferriferous material, zinciferous material, aluminiferous material and magnesiferous material, which does not contain harmful component to the environment and does not generate sludge to be wasted, which was not accomplished by the prior arts.
- the object of the present invention is to provide a treating solution for metal surface treatment to form a surface treated film of a uniform component having excellent corrosion resistance after coated on the surface of a metal material composing a structural construction such as car body consisting of two to four materials selecting from the group consisting of ferriferous material, zinciferous material, aluminiferous material and magnesiferous material by same component simultaneously under a uniform condition.
- a metal material composing a structural construction such as car body consisting of two to four materials selecting from the group consisting of ferriferous material, zinciferous material, aluminiferous material and magnesiferous material by same component simultaneously under a uniform condition.
- another object of the present invention is to provide a method for treatment using the treating solution.
- the inventors of the present invention have conducted intensive study to dissolve the above mentioned problem and have accomplished a treating solution for surface treatment of metal and a method for surface treatment which were not provided by the prior art.
- the present invention is the treating solution for surface treatment of metal, which is aqueous surface treating solution to treat independently each metal material or simultaneously two or more metal materials selected from the group consisting of ferriferous material, zinciferous material, aluminiferous material and magnesiferous material, the treating solution containing 5 to 5000 ppm of at least one compound selected from the group consisting of zirconium compound and titanium compound calculated as metal element, and 0.1 to 100 ppm of free fluorine ion, and having pH 2 to 6.
- the treating solution for surface treatment of metal may further contain at least one compound selected from the group consisting of calcium compound, magnesium compound and strontium compound, wherein concentration of the compound calculated as metal element is 5 to 100 ppm in the case of the calcium compound, 10 to 5000 ppm in the case of the magnesium and 10 to 5000 ppm in the case of the strontium compound. It is desirable that the treating solution for surface treatment of metal further contains 1000 to 50000 ppm of nitrate group.
- the treating solution for surface treatment of metal further contains at least one oxygen acid and/or salt of oxygen acid selected from the group consisting of HClO 3 , HBrO 3 , HNO 2 , HNO 3 , HMnO 4 , HVO 3 , H 2 O 2 , H 2 WO 4 , H 2 MoO 4 and salts thereof.
- the treating solution for surface treatment of metal may further contain at least one polymer compound selected from the group consisting of water soluble polymer compounds and water dispersible polymer compounds, and may further contain at least one surface active agent selected from the group consisting of nonionic surface active agents, anionic surface active agents and cationic surface active agents.
- the present invention is the method for surface treatment of metal comprising, contacting independently each metal material or simultaneously two or more metal materials selected from the group consisting of ferriferous material, zinciferous material, aluminiferous material and magnesiferous material with the treating solution for surface treatment.
- the metal material or the two or more metal materials after contacting with the treating solution for surface treatment, it is possible to further contact the metal material or the two or more metal materials with acidic aqueous solution of compound containing at least one element selected from the group consisting of cobalt, nickel, tin, copper, titanium and zirconium, with or without washing by water, or it is possible to further contact the metal material or the two or more metal materials with treating solution containing at least one polymer compound selected from water soluble polymer compounds and water dispersible polymer compounds.
- the present invention is the method for surface treatment of metal comprising, electrolytic treating in the treating solution for surface treatment, wherein independently each metal material or simultaneously two or more metal materials selected from the group consisting of ferriferous material, zinciferous material, aluminiferous material and magnesiferous material are a cathode.
- the metal material or the two or more metal materials after electrolytic treating in the treating solution for surface treatment, it is possible to further contact the metal material or the two or more metal materials with acidic aqueous solution of compound containing at least one element selected from the group consisting of cobalt, nickel, tin, copper, titanium and zirconium, with or without washing by water, or it is possible to further contact the metal material or the two or more metal materials with treating solution containing at least one polymer compound selected from water soluble polymer compounds and water dispersible polymer compounds, with or without washing by water.
- the present invention is the method for surface treatment of metal comprising, contacting independently each metal material or simultaneously two or more metal materials selected from the group consisting of ferriferous material, zinciferous material, aluminiferous material and magnesiferous material whose surfaces are not degreased and cleaned, with the treating solution for surface treatment containing at least one surface active agent selected from the group consisting of the above described nonionic surface active agents, anionic surface active agents and cationic surface active agents.
- the present invention is the metal material having a surface treated film containing at least one metal element selected from the group consisting of titanium and zirconium formed on a surface of iron metal material by the method for surface treatment, wherein an adhesion amount of the surface treated film calculated as the metal element is 30 mg/m 2 or more; in the case where formed on a surface of zinc metal material, an adhesion amount of the surface treated film calculated as the metal element is 20mg/m 2 or more; in the case where formed on a surface of aluminum metal material, an adhesion amount of the surface treated film calculated as the metal element is 10mg/m 2 or more; and in the case where formed on a surface of magnesium metal material, an adhesion amount of the surface treated film calculated as the metal element is 10mg/m 2 or more.
- the present invention relates to the art characterizing to deposit a surface treated film having excellent corrosion resistance after coated, by surface treatment on independently each metal material or simultaneously two or more metal materials selected from the group consisting of ferriferous material, zinciferous material, aluminiferous material and magnesiferous material.
- ferriferous material is an iron metal such as cold rolled steel plate, hot rolled steel plate, cast iron or sintered steel.
- Zinciferous material is a die casting zinc or a zinc contaiing plating.
- This zinc containing plating means a metal plating with zinc or zinc alloy composed of zinc and other metals (for example, at least one metal selected from the group consisting of nickel, iron, aluminum, manganese, chromium, magnesium, cobalt, lead or antimony) and inevitable impurities, and the methods for such plating includes hot galvanizing, electric plating and vapor deposition plating, and are not limited to these methods.
- the aluminiferous material is an aluminum alloy board such as JIS 5000 series aluminum alloy or JIS 6000 series aluminum alloy, or an aluminum alloy die cast represented by ADC-12. Still more, the magnesiferous material is a metal board or a die cast made of magnesium alloy.
- the present invention can be applied to the structural construction which contains one metal material mentioned above alone in the composing parts or to the structural construction which contains two to four metal materials mentioned above in the composing parts. And, in the case to apply the present invention to the structural construction which contains two to four metal materials mentioned above, it is possible to treat the surfaces of two to four metal materials at the same time. In the case to treat the surfaces of two to four metal materials at the same time, the different metals can be in the condition not contacting each other or in the condition being joined and contacted by means of joining method such as welding, adhesion or riveting.
- the treating solution for surface treatment of metal of the present invention contains 5 to 5000 ppm of at least one compound selected from the group consisting of zirconium compound and titanium compound calculated as the metal element, and 0.1 to 100 ppm of free fluorine ion, further having pH of 2 to 6.
- zirconium compound used in the present invention ZrCl 4 , ZrOCl 2 , Zr(SO 4 ) 2 , ZrOSO 4 , Zr(NO 3 ) 4 , ZrO(NO 3 ) 2 , H 2 ZrF 6 , salt of H 2 ZrF 6 , ZrO 2 , ZrOBr 2 and ZrF 4 can be mentioned.
- titanium compound TiCl 4 , Ti(SO 4 ) 2 , TiOSO 4 , Ti(NO 3 ) 4 , TiO(NO 3 ) 2 , TiO 2 OC 2 O 4 , H 2 TiF 6 , salt of H 2 TiF 6 , TiO 2 and TiF 4 can be mentioned.
- zirconium compound is desirably used.
- the desirable concentration of at least one compound selected from the group consisting of zirconium compound and titanium compound is 5 to 5000 ppm calculated as the metal element (that is, as zirconium and/or titanium), and the more desirable concentration is 10 to 3000 ppm.
- the film obtained by using the treating solution for surface treatment of metal and the method for surface treatment of the present invention is oxide or hydroxide of zirconium or titanium. Therefore, when the concentration of the compound selected from the group consisting of zirconium compound and titanium compound calculated as zirconium and/or titanium is smaller than 5 ppm, it is difficult to obtain sufficient adhesion amount to attain corrosion resistance in a practical period of time for treating, because the concentration of main component of film is too low. On the contrary, when the concentration is larger than 5000 ppm, the sufficient adhesion amount can be obtained, but it is not effective to improve the corrosion resistance and is disadvantageous from the economical view point.
- the zirconium compound and the titanium compound can be easily dissolved in the acidic solution, but are not stable in the alkaline solution, and easily deposit as the oxide or the hydroxide of zirconium or titanium.
- the desirable pH of the treating solution for surface treatment of metal of the present invention is pH 2 to 6, more desirably pH 3 to 6.
- the dissolving reaction of the metal material to be treated occurs.
- the pH becomes higher at the surface of the metal material to be treated, and the oxide or the hydroxide of zirconium or titanium deposits as a film on the surface of the metal material to be treated.
- the treating solution for surface treatment of metal of the present invention has free fluorine ion existing therein.
- the fluorine compound is added into the treating solution for surface treatment of metal.
- hydrofluoric acid, H 2 ZrF 6 and salt of H 2 ZrF 6 , H 2 TiF 6 , salt of H 2 TiF 6 , H 2 SiF 6 , salt of H 2 SiF 6 , HBF 4 and salt of HBF 4 , NaHF 2 , KHF 2 , NH 4 HF 2 , NaF, KF and NH 4 F can be mentioned.
- the free fluorine ion has an effect to improve the stability of the zirconium compound and the titanium compound in the treating solution for surface treatment of metal. Further, the free fluorine ion has the function to promote the dissolving reaction of any of ferriferous material, zinciferous material, aluminiferous material and magnesiferous material which are the metal materials to be surface treated in the present invention. Therefore, by allowing free fluorine ion to exist therein by adding fluorine compound, the stability of the treating solution for surface treatment of metal of the present invention is improved, and further the reactivity to the metal material to be treated can be improved.
- composition for surface treatment and treating solution for surface treatment of metal containing at least one of iron and zinc in WO02/103080 as follows. That is, the composition for surface treatment and treating solution for surface treatment of metal use titanium compound or zirconium compound and fluorine containing compound, wherein the ratio A/B is set within the specific range from 0.06 to 0.18, where A refers to the total mole weight of metal elements in the composition for surface treatment and treating solution for surface treatment of metal and B refers to the mole weight which when total fluorine atom in fluorine containing compound is calculated as HF.
- the present invention it is possible to perform surface treatment on independently one metal material or simultaneously two or more metal materials selected from the group consisting of ferriferous material, zinciferous material, aluminiferous material and magnesiferous material, even if out of above mentioned specific range of the ratio, by regulating the concentration of metal element in the titanium compound and zirconium compound, pH and the concentration of free fluorine ion.
- the concentration of free fluorine ion means the concentration of fluorine ion measured by an ion electrode which is on the market.
- the concentration of free fluorine ion in the treating solution for surface treatment of metal of the present invention is desirably 0.1 to 100 ppm, and more desirably 2 to 70 ppm.
- the concentration of free fluorine ion is higher than 100 ppm, the dissolving reaction of the metal material to be treated is promoted.
- zirconium compound and titanium compound in the treating solution for surface treatment of metal are very stable, even if the pH of the surface of metal material to be treated increases, it becomes difficult to deposit as a film.
- the concentration of free fluorine ion is lower than 0.1 ppm, the effect for the improvement of the stability of the treating solution for surface treatment of metal and the reactivity thereof is small, and thus, it is no longer advantageous for the treating solution to contain free fluorine ion.
- the free fluorine ion of the present invention has a role to keep the eluted component by dissolution of the metal material to be treated stable in the treating solution for surface treatment of metal.
- sludge generates, because, for example, iron ion eluted from iron metal material reacts with phosphoric acid and forms iron phosphate which is an insoluble salt.
- the treating solution for surface treatment of metal of the present invention may also contain phosphoric acid group, but, if the concentration of phosphoric acid group excesses 1.0g/L, sludge can be generated.
- one or more compounds selected from the group, for example, consisting of inorganic acid such as sulfuric acid or hydrochloric; organic acid such as acetic acid, oxalic acid, tartaric acid, citric acid, succinic acid, gluconic acid or phthalic acid; and chelating agent which can chelete eluted component, may be added in the treating solution to thereby solubilize the eluted component.
- the treating solution for surface treatment of metal in the present invention may contain at least one compound selected from the group consisting of calcium compound, magnesium compound and strontium compound.
- the present invention realizes to perform surface treatment on each metal material independently or two to four materials simultaneously selected from the group consisting of ferriferous material, zinciferous material, aluminiferous material and magnesiferous material by regulating the concentration of free fluorine ion in the aqueous solution containing zirconium compound and titanium compound of specific concentration within the specified range.
- the metal elements (calcium, magnesium or strontium) contained in above mentioned calcium compound, magnesium compound or strontium compound have a function to maintain the concentration of free fluorine ion in aqueous solution to a certain value by generating salt of fluorine and fluorinated compound in the aqueous solution. Due to the function, when the surface of various kinds of metal materials are treated at the same time, the optimum deposit amount of film can be obtained on each metal material to be treated, because certain concentration of free fluorine ion can be maintained regardless of the ratio among the materials used.
- calcium compound, magnesium compound or strontium compound which can be used in the present invention for example, oxide, hydroxide, chloride, sulfate, nitrate and carbonate of these metal elements can be mentioned. Further, besides calcium compound, magnesium compound and strontium compound, the compound which has a function to maintain the concentration of free fluorine ion constant can be used regardless of whether an organic compound or an inorganic compound.
- the concentration of the magnesium compound or the strontium compound which can be used in the present invention is desirably 10 to 5000 ppm as the metal element, and more desirably is 100 to 3000 ppm.
- the desirable concentration as calcium is 5 to 100 ppm and more desirable concentration is 5 to 50 ppm, because the solubility of calcium is remarkably small.
- the concentration of these compounds is higher than the upper limit, the stability of the treating solution for surface treatment of metal may decrease, and the continuous treatment is interrupted. And, when the concentration of these compounds is lower than the lower limit, the deposit amount of film particularly on ferriferous material decreases.
- Nitric acid group acts as an oxidizing agent, and has a function to promote film depositing reaction of the present invention and a function to improve the solubility of above mentioned calcium compound, magnesium compound or strontium compound in the treating solution for surface treatment of metal. Therefore, even if the concentration of nitric acid group is lower than 1000 ppm, the film having excellent corrosion resistance can be deposited. However, in the case where the concentration of above mentioned calcium compound, magnesium compound or strontium compound is high, the stability of the treating solution for surface treatment of metal may decrease. The concentration of nitric acid group of 50000 ppm is sufficient, and it is disadvantageous to add more nitric acid group from the economical view point.
- At least one oxygen acid and/or salt of oxygen acid selected from the group consisting of HClO 3 , HBrO 3 , HNO 3 , HNO 2 , HMnO 4 , HVO 3 , H 2 O 2 , H 2 WO 4 , H 2 MoO 4 .
- Oxygen acid or salt thereof acts as oxidizing agent to the materials to be treated, and promotes the film forming reaction in the present invention.
- the concentration of these oxygen acid or salts thereof to be added is not restricted, but adding an amount to 10 to 5000 ppm exhibits sufficient effect as the oxidizing agent.
- At least one polymer compound selected from the group consisting of water soluble polymer compounds and water dispersible polymer compounds may be added.
- the metal element whose surface is treated by using the treating solution for surface treatment of metal of the present invention has an enough corrosion resistance, but, if additional function such as lubricity is required, it is possible to improve the physical property of the film by adding preferably selected polymer according to the desired function.
- polymer compounds which are generally used for the surface treatment of metal such as polyvinyl alcohol, poly(metha)acrylic acid, copolymer of acrylic acid and methacrylic acid, copolymer of ethylene with acrylic monomer such as (metha)acrylic acid or (metha)acrylate, copolymer of ethylene and vinyl acetate, polyurethane, amino-modified phenol resin, polyester resin and epoxy resin can be used.
- metal such as polyvinyl alcohol, poly(metha)acrylic acid, copolymer of acrylic acid and methacrylic acid, copolymer of ethylene with acrylic monomer such as (metha)acrylic acid or (metha)acrylate, copolymer of ethylene and vinyl acetate, polyurethane, amino-modified phenol resin, polyester resin and epoxy resin
- metal such as polyvinyl alcohol, poly(metha)acrylic acid, copolymer of acrylic acid and methacrylic acid, copolymer of ethylene with acrylic monomer such as (metha)acrylic acid
- the method for surface treatment of the present invention can be illustrated as follows. Namely, the surface is merely treated by degreasing treatment according to an ordinary method, and the cleaned metal material to be treated is brought into contact with the treating solution for surface treatment of metal. Accordingly, the film composed of oxide and/or hydroxide of a metal element selected from the group consisting of zirconium and titanium is deposited and the surface treated film layer having good adhesiveness and corrosion resistance is formed.
- any kind of treatment e.g., spraying treatment, immersion treatment or pouring treatment can be used, and the properties of the product will not be influenced by the treating method.
- the structure of the surface treated layer of the present invention is considered to be a state where oxide and hydroxide are mixed when dried at an ordinary temperature or at a low temperature after surface treatment. And, when dried at a high temperature after surface treatment, the structure of the surface treated layer is considered to be a state of oxide alone or oxide rich.
- the condition to use the treating solution for surface treatment of metal is not restricted.
- the reactivity of the treating solution for surface treatment of metal of the present invention can be voluntarily regulated by changing the concentration of zirconium compound or titanium compound and the concentration of free fluorine ion in the treating solution for surface treatment of metal. Therefore, the treating temperature and treating period of time can be changed voluntarily in combination of the reactivity of the treating bath.
- At least one surface active agent selected from the group consisting of nonionic surface active agent, anionic surface active agent and cationic surface active agent can be added to the treating solution for surface treatment of metal.
- this treating solution for surface treatment of a metal can be used also as a surface treating agent and a degreasing agent.
- the method to carry out the electrolysis in the treating solution for surface treatment of metal having a metal material to be treated as a cathode When the electrolysis treatment is carried out using the metal material to be treated as a cathode, the reduction occurs at the surface of the cathode and the pH goes up. Along with the elevation of the pH, the stability of zirconium compound and/or titanium compound at the surface of cathode is deteriorated, and the surface treated film is deposited as an oxide or a hydroxide containing water.
- the effect of the present invention can be improved when, after contacting with treating solution for surface treatment of metal, or after being electrolyzed in the treating solution for surface treatment of metal with or without washed by water, the metal material is brought into contact with the acidic solution of the compound containing at least one element selected from the group consisting of cobalt, nickel, tin, copper, titanium and zirconium, or with the treating solution containing at least one polymer compound selected from the group consisting of water soluble polymer compound and water dispersible polymer.
- the surface treated film layer obtained by the present invention is characterized in a thin film and exhibits excellent coating property, but depending on the surface condition of the metal material to be treated, sometimes tiny defects may be formed on the surface treated film layer.
- the layer in contact with the acidic solution of the compound containing at least one element selected from the group consisting of cobalt, nickel, tin, copper, titanium and zirconium or the treating solution containing at least one polymer compound selected from the group consisting of water soluble polymer compound and water dispersible polymer the tiny defects are covered and the corrosion resistance can be further improved.
- the compound containing at least one element selected from the group consisting of cobalt, nickel, tin, copper, titanium and zirconium is not restricted, and, it is possible to use oxide, hydroxide, fluoride, complex fluoride, chloride, nitrate, oxynitrate, sulfate, oxysulfate, carbonate, oxycarbonate, phosphate, oxyphosphate, oxalate, oxyoxalate, and organic metal compounds and the like.
- the pH of acidic solution containing the metal element is 2 to 6, and can be adjusted with 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, salts of alkali metal, ammonium salt or amines.
- 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, salts of alkali metal, ammonium salt or amines.
- At least one polymer compound selected from above mentioned water soluble polymer compound or water dispersible polymer compound for example, polyvinyl alcohol, poly(metha)acrylic acid, copolymer of acrylic acid and methacrylic acid, copolymer of ethylene with acrylic monomer such as (metha)acrylic acid or (metha)acrylate, copolymer of ethylene and vinyl acetate, polyurethane, amino-modified phenol resin, polyester resin or epoxy resin, tannin and tannic acid and salts thereof, and phytic acid can be used.
- the present invention may remarkably improve the corrosion resistance of metal material by providing a surface treated film layer composed of oxide and/or hydroxide of metal elements selected from zirconium and/or titanium on the surface of metal material to be treated.
- the oxide and hydroxide of above mentioned metal elements have a physical property characterized not to be damaged by acid or alkali, and chemically stabilized.
- the pH becomes lower, while, at the cathode where reduction occurs, the pH becomes higher. Therefore, the surface treated film of less resistant to acid and alkali may be dissolved under the corrosive environment and its effect would be lost. Since the main component of the surface treated film layer of the present invention is resistive to acid or alkali, the excellent effect can be maintained under the corrosive environment.
- the oxide and hydroxide of above mentioned metal elements form a network structure mediated by metal and oxide, it becomes a very good barrier film.
- the corrosion of metal material which can be varied depending on the environment for use, generally, is oxygen demanding type corrosion in the atmosphere in which water and oxygen exist, and the speed of corrosion is promoted by the presence of the components such as chloride. Having a barrier effect against water, an acid and a corrosion promoting component, the surface treated film layer of the present invention may exhibit excellent corrosion resistance.
- the adhesion amount over 30 mg/m 2 calculated as the metal element is necessary, desirably over 40 mg/m 2 and more desirably over 50 mg/m 2 .
- the adhesion amount over 20 mg/m 2 calculated as the metal element is necessary, desirably over 30 mg/m 2 .
- the adhesion amount over than 10 mg/m 2 calculated as the metal element is necessary, desirably over 20 mg/m 2 .
- the adhesion amount over than 10 mg/m 2 calculated as the metal element is necessary, desirably over than 20 mg/m 2 .
- the adhesion amount there is no upper limit.
- the desirable upper limit of adhesion amount is 1 g/m 2 , more desirably 800 mg/m 2 .
- test plates cold rolled steel plates, hot-dip zinc-coated steel plates, aluminum alloy plates and magnesium alloy plates are used in the Examples and Comparative Examples.
- the abbreviations and specifications of these test plates are shown below.
- the test plate prepared by joining three metal materials of SPC, GA and Al by a spot welding was used.
- each test plate of SPC, GA, Al and Mg, and the test plate prepared by joining three metal materials of SPC, GA and Al by a spot welding were used.
- the coating property the test plate prepared by joining three metal materials of SPC, GA and Al by a spot welding was used and the test from surface treatment, coating and evaluation of coating property were carried out in series.
- Fig.1 is the plane view of the test plate prepared by joining three metal materials of SPC, GA and Al by a spot welding
- Fig.2 is an elevation view of it.
- the numeral 1 indicates a spot welded portion.
- alkali degreasing was carried out as follows. That is, Fine Cleaner L4460 (Trade Mark: Product of Nihon Parkerizing) was diluted to 2% concentration by city water, and was sprayed to a plate to be treated at 40 °C for 120 sec. Rinsing by water and rinsing by pure water after film formation treatment were performed by spraying water and pure water on the plate to be treated at a room temperature for 30 sec both in Examples and Comparative Examples.
- Aqueous solution of zirconium with concentration of 200 ppm was prepared using zirconium oxynitrate reagent and nitric acid. After heating the aqueous solution to 45°C, the pH was adjusted to 3.0 using sodium hydroxide reagent and hydrofluoric acid, and the concentration of free fluorine ion measured by a fluorine ion meter (IM-55G; product of Toa Denpa Industries Co., Ltd) was adjusted to 1 ppm, thus obtaining the treating solution for surface treatment of metal. The total fluorine concentration in the treating solution for surface treatment of metal after adjusting free fluorine ion was 50 ppm.
- test plate rinsed by water after degreasing was immersed into the treating solution for surface treatment of metal for 120 seconds so as to carry out the surface treatment.
- Aqueous solution of zirconium with concentration of 100 ppm, magnesium with concentration of 5000 ppm, strontium with concentration of 2000 ppm and nitric acid group with concentration of 28470 ppm was prepared using zirconium oxynitrate reagent, magnesium nitrate reagent and strontium nitrate reagent. After heating the aqueous solution to 50°C, the pH was adjusted to 4.0 using ammonium water reagent and hydrofluoric acid, and the concentration of free fluorine ion measured by a fluorine ion meter (IM-55G; product of Toa Denpa Industries Co., Ltd) was adjusted to 80 ppm, thus obtaining the treating solution for surface treatment of metal. The total fluorine concentration in the treating solution for surface treatment of metal after adjusting free fluorine ion was 2000 ppm.
- IM-55G fluorine ion meter
- test plate rinsed by water after degreasing was immersed into the treating solution for surface treatment of metal for 60 seconds so as to carry out the surface treatment.
- Aqueous solution of zirconium with concentration of 1000 ppm, titanium with concentration of 2000 ppm, calcium with concentration of 5 ppm and nitric acid group with concentration of 1000 ppm was prepared using aqueous solution of hexafluorozirconic acid (IV), aqueous solution of titanium sulfate (IV) and calcium sulfate reagent.
- the pH was adjusted to 5.0 using potassium hydroxide reagent and hydrofluoric acid, and the concentration of free fluorine ion measured by a fluorine ion meter (IM-55G; product of Toa Denpa Industries Co., Ltd) was adjusted to 25 ppm, thus obtaining the treating solution for surface treatment of metal.
- IM-55G fluorine ion meter
- the total fluorine concentration in the treating solution for surface treatment of metal after adjusting free fluorine ion was 2250 ppm.
- test plate rinsed by water after degreasing was immersed into the treating solution for surface treatment of metal for 90 seconds so as to carry out the surface treatment.
- Aqueous solution of titanium with concentration of 5000 ppm, strontium with concentration of 5000 ppm, nitric acid group with concentration of 7080 ppm and nitrous acid group with concentration of 40 ppm was prepared using aqueous solution of hexafluorotitanium acid (IV), strontium nitrate reagent, and sodium nitrite reagent.
- the pH was adjusted to 4.0 using triethanol amine reagent and hydrofluoric acid, and the concentration of free fluorine ion measured by a fluorine ion meter (IM-55G; product of Toa Denpa Industries Co., Ltd) was adjusted to 10 ppm, thus obtaining the treating solution for surface treatment of metal.
- the total fluorine concentration in the treating solution for surface treatment of metal after adjusting free fluorine ion was 11900 ppm.
- test plate was rinsed by water after degreasing, then the obtained treating solution for surface treatment of metal was sprayed to the surface thereof for 120 sec., thus carrying out the surface treatment.
- Aqueous solution of zirconium with concentration of 5 ppm, titanium with concentration of 5 ppm, magnesium with concentration of 100 ppm, nitric acid group with concentration of 30520 ppm and chloric acid group with concentration of 100 ppm was prepared using zirconium oxynitrate reagent, aqueous solution of hexafluorotitanic acid (IV), magnesium nitrate reagent, nitric acid and sodium chloric acid reagent.
- the pH was adjusted to 6.0 using ammonia water reagent and hydrofluoric acid, and the concentration of free fluorine ion measured by a fluorine ion meter (IM-55G; product of Toa Denpa Industries Co., Ltd) was adjusted to 0.5 ppm, thus obtaining the treating solution for surface treatment of metal.
- IM-55G fluorine ion meter
- the total fluorine concentration in the treating solution for surface treatment of metal after adjusting free fluorine ion was 12 ppm.
- test plate was electrolyzed in the treating solution for surface treatment of metal for 5 seconds under the condition of 5A/dm 2 , thus carrying out the surface treatment.
- Aqueous solution of zirconium with concentration of 150 ppm, magnesium with concentration of 10 ppm, nitric acid group with concentration of 5200 ppm and hydrogen peroxide concentration of 10 ppm was prepared using zirconium oxynitrate reagent, magnesium oxide reagent, nitric acid, and hydrogen peroxide reagent.
- the pH was adjusted to 5.0 using ammonia water reagent and hydrofluoric acid, the concentration of free fluorine ion measured by a fluorine ion meter (IM-55G; product of Toa Denpa Industries Co., Ltd) was adjusted to 50 ppm and 2 g/L of polyoxyethylenenonylphenylether (ethylene oxide addition mole number: 12 mol), which is nonionic surface active agent, was added, thus obtaining the treating solution for surface treatment of metal.
- the total fluorine concentration in the treating solution for surface treatment of metal after adjusting free fluorine ion was 170 ppm.
- Aqueous solution of titanium with concentration of 100 ppm, calcium with concentration of 50 ppm, magnesium with concentration of 5000 ppm, nitric acid group with concentration of 25660 ppm and permanganate with concentration of 10 ppm was prepared using aqueous solution of titanium sulfate (IV), calcium nitrate reagent, magnesium nitrate reagent and potassium permanganate reagent.
- Water soluble acrylic polymer compound (Jurymer AC-10L: product of Nihon Junyaku Co., Ltd.) was added in the aqueous solution so as the concentration of solid to be 1%, then the aqueous solution was heated to 50°C.
- the pH was adjusted to 3.0 using sodium hydroxide reagent and hydrofluoric acid, and the total free fluorine ion concentration in the aqueous solution to be measured by a fluorine ion meter (IM-55G; product of Toa Denpa Industries Co., Ltd) was adjusted to 95 ppm, thus obtaining the treating solution for surface treatment of metal.
- IM-55G fluorine ion meter
- the total fluorine concentration in the treating solution for surface treatment of metal was 2000 ppm.
- test plate rinsed by water after degreasing was immersed into the treating solution for surface treatment of metal for 60 seconds so as to carry out the surface treatment.
- the aqueous solution with 1% of water soluble acrylic polymer compound (Jurymer AC-10L: product of Nihon Junyaku Co., Ltd.) in solid concentration and 2g/L of phosphoric acid reagent as phosphoric acid group was prepared.
- This aqueous solution was heated to 40°C, then the pH was adjusted to 4.5 using ammonia water reagent, thus obtaining the after treating solution.
- the test plate on which film formation was carried out by the surface treatment of Example 5 and rinsed by water was dipped into the above mentioned after treating solution for 30 seconds so as to carry out the after treatment.
- the aqueous solution of zirconium with concentration of 50 ppm and cobalt with concentration of 50 ppm was prepared using aqueous solution of hexafluorozirconic acid (IV) and cobalt nitrate reagent. After heating the aqueous solution to 40°C, the pH was adjusted to 5.0 with ammonia water reagent, thus obtaining the after treating solution.
- the test plate on which film formation was carried out by the surface treatment of Example 6 and rinsed by water was immersed into the above mentioned after treating solution for 30 seconds so as to carry out the after treatment.
- the aqueous solution of zirconium with concentration of 500 ppm, magnesium with concentration of 1000 ppm and nitric acid group with concentration of 6780 ppm was prepared using zirconium oxynitrate reagent, magnesium nitrate and nitric acid. After heating the aqueous solution to 45°C, the pH was adjusted to 4.0 with sodium hydroxide solution, thus obtaining the treating solution for surface treatment of metal.
- the free fluorine ion concentration of the treating solution for surface treatment of metal was measured by a fluorine ion meter on the market (IM-55G; product of Toa Denpa Industries Co., Ltd), and the result was 0 ppm.
- test plate which was rinsed by water after degreasing was immersed into the above mentioned treating solution for surface treatment of metal for 120 seconds so as to carry out the surface treatment.
- the aqueous solution of titanium with concentration of 2000 ppm was prepared by using aqueous solution of titanium sulfate (IV). After heating the aqueous solution to 50°C, the pH was adjusted to 3.5 using ammonia water reagent and hydrofluoric acid, and the concentration of free fluorine ion measured by a fluorine ion meter (IM-55G; product of Toa Denpa Industries Co., Ltd) was adjusted to 400 ppm, thus obtaining the treating solution for surface treatment of metal.
- IM-55G fluorine ion meter
- test plate which was rinsed by water after degreasing was immersed into the above mentioned treating solution for surface treatment of metal for 90 seconds so as to carry out the surface treatment.
- Alchrom 713 (Trade Mark, product of Nihon Parkerizing Co., Ltd.), which is the chromic chromate treating agent on the market, was diluted by city water to the concentration of 3.6%, then total acidity and free acid acidity were adjusted to the center value described in the brochure.
- test plate was rinsed by water after degreasing, then immersed into the chromate treating solution heated to the temperature of 35°C and chromate treatment was carried out for 60 sec.
- Palcoat 3756 (Trade Mark, product of Nihon Parkerizing Co., Ltd.), which is the chrome free treating agent on the market, was diluted by city water to the concentration of 2%, then total acidity and free acid acidity were adjusted to the center value described in the brochure. The test plate was rinsed by water after degreasing, then immersed into the chrome free treating solution heated to the temperature of 40°C and chrome free treatment was carried out for 60 sec.
- the test plate was rinsed by water after degreasing, then the solution prepared by diluting Prepalene ZN (Trade Mark, product of Nihon Pakerizing Co., Ltd.), which is a surface conditioning agent, with city water to the concentration of 0.1% was sprayed thereon at the room temperature for 30 sec.
- Palbond L3020 (Trade Mark, product of Nihon Parkerizing Co., Ltd.) was diluted to the concentration of 4.8% with city water.
- sodium hydrogen fluoride reagent as fluorine was added into the solution to 200 ppm, and then, total acidity and free acid acidity thereof were adjusted to the center value described in the brochure.
- the zinc phosphate treating solution was prepared. Above mentioned test plate was immersed into the zinc phosphate chemical treating solution heated to the temperature of 42°C, and zinc phosphate film was deposited.
- Example 1 uniform interference color uniform dark black uniform white
- Example 2 uniform interference color uniform dark black uniform white
- Example 3 uniform interference color uniform dark black uniform white
- Example 4 uniform interference color uniform dark black uniform white
- Example 5 uniform interference color uniform dark black uniform white
- Example 6 uniform interference color uniform dark black uniform white
- Example 7 uniform interference color uniform dark black uniform white Comparative Example 1 film not deposited film not deposited uneven white Comparative Example 2 pale yellow uneven gray uneven white Comparative Example 3 film not deposited slightly turned to yellow gold Comparative Example 4 film not deposited film not deposited uniform white Comparative Example 5 material partially exposed uniform gray uneven white
- coating was carried out by the following process: cationic electrodeposition coating ⁇ rinsing with pure water ⁇ baking ⁇ surfacer ⁇ baking ⁇ top coating ⁇ baking.
- the coating property in the Examples and Comparative Examples was evaluated and the results thereof are shown in Table 4 and Table 5. Items evaluated and the abbreviations are described below.
- the coated film after electrodeposition coating process is called as electrodeposition coated film and the coated film after top coating is called as 3-coats film.
- Example 4 The results for evaluation of coating property of the electrodeposition coated film are summarized in Table 4. Examples showed good corrosive resistance on all test plates. On the contrary, in Comparative Example 1, since free fluorine ions were not contained in the treating solution for surface treatment of metal at all, the deposition of surface treated film was not sufficient and thus the corrosion resistance was not so good. Further, in Comparative Example 2, since the concentration of free fluorine ion in the treating solution for surface treatment of metal was high, especially, the adhesion amount of film on SPC was small and the corrosion resistance was not so good. The coating properties of Examples 5 and 6 were superior to those of Comparative Examples, but when compared with other Examples, corrosive resistances after electrodeposition coating was inferior to those of other Examples. However, as shown in Examples 8 and 9, the corrosive resistance was further improved by carrying out the after treatment.
- Comparative Example 3 Because in Comparative Example 3, a chromate treating agent for aluminum alloy was used and in Comparative Example 4, a chrome free treating agent for aluminum alloy was used, the corrosion resistance of Al was good, but the corrosion resistance of other test plates were obviously inferior to those of Examples.
- Comparative Example 5 a zinc phosphate treating agent, which is now usually used as the base for coating was used. However, Comparative Example 5, in the condition where each of the test plates was joined by welding, showed the test results inferior to those of Examples.
- Table 5 shows the evaluation results of adhesion of a 3-coats plate. Examples showed good adhesion to all test plates. Regarding to 1st ADH, good results were obtained in all Comparative Examples. However, regarding to 2nd ADH, Comparative Examples did not show the good level of adhesion to all test plates same as the corrosive resistance of the electrodeposition coating. Further, in Comparative Example 5, the generation of sludge, which is the by-product of zinc phosphate treatment, was observed in the treating bath after surface treatment. However, in Examples of the present invention, the generation of sludge was not observed.
- the treating solution for metal surface treatment and the method for surface treatment of the present invention it is possible to deposit a surface treated film having excellent corrosion resistance after coating on the surface of a metal made of two or more, or each of ferriferous material, zinciferous material, aluminiferous material and magnesiferous material in the treating bath containing no harmful component to the environment and without generating sludge, which have never been achieved in the prior art. Further, since the present invention does not need a process for surface conditioning on the metal material to be treated, it is possible to shorten the treatment time and to reduce space for the treatment.
Abstract
Treating solution for surface treatment of metal to
treat one metal material selected from the group consisting
of ferriferous material, zinciferous material,
aluminiferous material and magnesiferous material or to
treat two or more metal materials selected from the group
consisting of ferriferous material, zinciferous material,
aluminiferous material and magnesiferous material at the
same time, wherein the aqueous surface treating solution
contains from 5 to 5000 ppm of at least one compound
selected from the group consisting of zirconium compound
and titanium compound by the metal element, and from 0.1 to
100 ppm of free fluorine ion, further the pH of the
treating solution is from 2 to 6. To the treating solution,
calcium compound, magnesium compound, strontium compound,
nitric acid group, oxygen acid and/or salt of oxygen acid,
polymer compound and surface active agent can be added.
Description
The present invention relates to the treating
solution for surface treatment of metal which may deposit a
surface treated film having excellent corrosion resistance
after being coated on the surface of a metal material of a
structural construction such as car body consisting of a
single material or two to four materials selected from the
group consisting of ferriferous material, zinciferous
material, aluminiferous material and magnesiferous material
independently or simultaneously.
As the method to form on metal surface a surface
treated film having excellent corrosion resistance after
coated, a zinc phosphate treatment and a chromate treatment
are currently used as ordinary methods. According to the
zinc phosphate treatment, it is possible to deposit a film
having excellent corrosion resistance on the surface of
steel such as cold rolled steel plate, zinc plated steel
plate and some of aluminum alloys. However, in the zinc
phosphate treatment, the generation of sludge, which is the
byproduct of the reaction can not be avoided, and depending
on the kind of aluminum alloy, the sufficient corrosion
resistance after coated can not be obtained. While, in the
case of aluminum alloy, it is possible to obtain sufficient
properties after coated by applying the chromate treatment.
Concerning the recent environmental regulations, the
chromate treatment which contains harmful hexavalent chrome
in the treating solution is more likely to be avoided. As
the method for metal surface treatment, which does not
contain harmful component in the treating solution, various
methods have been proposed as described below.
For example, in JP 2000-204485 A, a compound
containing nitrogen atom having a lone electron-pair and a
non-chrome coating agent for metal surface treatment
containing said compound and zirconium compound are
suggested. This method may obtain a surface treated film
which is excellent in corrosion resistance and adhesiveness
after being coated, and yet does not contain harmful
hexavalent chrome by coating above mentioned coating agent.
However, in the case of the method, the metal material
which can be treated is limited to aluminum alloys only,
and, it is difficult to be applied to a structural
construction having complex structure such as car body,
because the surface treated film is formed by coating and
drying.
Further, as the method to deposit a metal surface
treated film having excellent adhesiveness and corrosion
resistance after coated due to the chemical reaction,
various methods such as those disclosed in JP 56-136978 A,
JP 8-176841 A, JP 9-25436 A and JP 9-31404 A have been
suggested. However, in any of these methods, the metal
material which can be treated is limited to the aluminum
alloy only, originally having excellent corrosion
resistance; these methods may not deposit a surface treated
film on the surface of ferriferous material or zinciferous
material.
Furthermore, proposed is a method to form a metal
surface treated film having excellent corrosion resistance
and adhesion after coated, by using a surface treating
agent composed of metal acetylacetonate and water soluble
inorganic titanium compound or water soluble inorganic
zirconium compound (see JP 2000-199077). By this method,
metal materials to be treated may include magnesium,
magnesium alloy, zinc and zinc plated alloy other than
aluminum alloy. However, by this method, it is difficult to
form a surface treated film on a surface of ferriferous
material such as cold rolled steel, and is not possible to
treat ferriferous material at the same time.
Still further, a method for metal surface treatment by
chrome free coating acid composition by coating aqueous
solution containing component which can be a film having
excellent corrosion resistance over the surface of metal,
then baking and drying without rinsing with water so as the
film to be fixed (see JP 5-195244 A). This method does not
involve any chemical reaction to form a film, so this
method may form a film on the surface of metal such as zinc
plated steel plate, cold rolled steel plate or aluminum
alloy. However, similarly to the invention disclosed in
above mentioned JP 2000-204485 A, since the film is formed
by coating and drying, it is difficult to form a uniform
film on the surface of a structural construction having
complex structure such as car body.
As mentioned above, according to the prior arts, it
was impossible to perform surface treatment excellent in
corrosion resistance and adhesion on car body and the like
composed of two to four metal materials of ferriferous
material such as cold rolled steel plate, zinciferous
material such as zinc plated steel plate, aluminiferous
material and magnesiferous material simultaneously with a
treating solution containing no harmful component to the
environment and not generating waste sludge.
The object of the present invention is to provide a
treating solution for surface treatment of metal to form a
surface treated film having excellent corrosion resistance
after coated on the surface of ferriferous material,
zinciferous material, aluminiferous material and
magnesiferous material, which does not contain harmful
component to the environment and does not generate sludge
to be wasted, which was not accomplished by the prior arts.
Further, the object of the present invention is to provide
a treating solution for metal surface treatment to form a
surface treated film of a uniform component having
excellent corrosion resistance after coated on the surface
of a metal material composing a structural construction
such as car body consisting of two to four materials
selecting from the group consisting of ferriferous material,
zinciferous material, aluminiferous material and
magnesiferous material by same component simultaneously
under a uniform condition. And another object of the
present invention is to provide a method for treatment
using the treating solution.
The inventors of the present invention have conduced
intensive study to dissolve the above mentioned problem and
have accomplished a treating solution for surface treatment
of metal and a method for surface treatment which were not
provided by the prior art.
That is, the present invention is the treating
solution for surface treatment of metal, which is aqueous
surface treating solution to treat independently each metal
material or simultaneously two or more metal materials
selected from the group consisting of ferriferous material,
zinciferous material, aluminiferous material and
magnesiferous material, the treating solution containing 5
to 5000 ppm of at least one compound selected from the
group consisting of zirconium compound and titanium
compound calculated as metal element, and 0.1 to 100 ppm of
free fluorine ion, and having pH 2 to 6.
The treating solution for surface treatment of metal
may further contain at least one compound selected from the
group consisting of calcium compound, magnesium compound
and strontium compound, wherein concentration of the
compound calculated as metal element is 5 to 100 ppm in the
case of the calcium compound, 10 to 5000 ppm in the case of
the magnesium and 10 to 5000 ppm in the case of the
strontium compound. It is desirable that the treating
solution for surface treatment of metal further contains
1000 to 50000 ppm of nitrate group. And, it is desirable
that the treating solution for surface treatment of metal
further contains at least one oxygen acid and/or salt of
oxygen acid selected from the group consisting of HClO3,
HBrO3, HNO2, HNO3, HMnO4, HVO3, H2O2, H2WO4, H2MoO4 and salts
thereof. The treating solution for surface treatment of
metal may further contain at least one polymer compound
selected from the group consisting of water soluble polymer
compounds and water dispersible polymer compounds, and may
further contain at least one surface active agent selected
from the group consisting of nonionic surface active agents,
anionic surface active agents and cationic surface active
agents.
And, the present invention is the method for surface
treatment of metal comprising, contacting independently
each metal material or simultaneously two or more metal
materials selected from the group consisting of ferriferous
material, zinciferous material, aluminiferous material and
magnesiferous material with the treating solution for
surface treatment. In the method for surface treatment,
after contacting with the treating solution for surface
treatment, it is possible to further contact the metal
material or the two or more metal materials with acidic
aqueous solution of compound containing at least one
element selected from the group consisting of cobalt,
nickel, tin, copper, titanium and zirconium, with or
without washing by water, or it is possible to further
contact the metal material or the two or more metal
materials with treating solution containing at least one
polymer compound selected from water soluble polymer
compounds and water dispersible polymer compounds.
Moreover, the present invention is the method for
surface treatment of metal comprising, electrolytic
treating in the treating solution for surface treatment,
wherein independently each metal material or simultaneously
two or more metal materials selected from the group
consisting of ferriferous material, zinciferous material,
aluminiferous material and magnesiferous material are a
cathode. In the method for surface treatment, after
electrolytic treating in the treating solution for surface
treatment, it is possible to further contact the metal
material or the two or more metal materials with acidic
aqueous solution of compound containing at least one
element selected from the group consisting of cobalt,
nickel, tin, copper, titanium and zirconium, with or
without washing by water, or it is possible to further
contact the metal material or the two or more metal
materials with treating solution containing at least one
polymer compound selected from water soluble polymer
compounds and water dispersible polymer compounds, with or
without washing by water.
And, the present invention is the method for surface
treatment of metal comprising, contacting independently
each metal material or simultaneously two or more metal
materials selected from the group consisting of ferriferous
material, zinciferous material, aluminiferous material and
magnesiferous material whose surfaces are not degreased and
cleaned, with the treating solution for surface treatment
containing at least one surface active agent selected from
the group consisting of the above described nonionic
surface active agents, anionic surface active agents and
cationic surface active agents.
Furthermore, the present invention is the metal
material having a surface treated film containing at least
one metal element selected from the group consisting of
titanium and zirconium formed on a surface of iron metal
material by the method for surface treatment, wherein an
adhesion amount of the surface treated film calculated as
the metal element is 30 mg/m2 or more; in the case where
formed on a surface of zinc metal material, an adhesion
amount of the surface treated film calculated as the metal
element is 20mg/m2 or more; in the case where formed on a
surface of aluminum metal material, an adhesion amount of
the surface treated film calculated as the metal element is
10mg/m2 or more; and in the case where formed on a surface
of magnesium metal material, an adhesion amount of the
surface treated film calculated as the metal element is
10mg/m2 or more.
The present invention relates to the art
characterizing to deposit a surface treated film having
excellent corrosion resistance after coated, by surface
treatment on independently each metal material or
simultaneously two or more metal materials selected from
the group consisting of ferriferous material, zinciferous
material, aluminiferous material and magnesiferous material.
In the present invention, ferriferous material is an iron
metal such as cold rolled steel plate, hot rolled steel
plate, cast iron or sintered steel. Zinciferous material is
a die casting zinc or a zinc contaiing plating. This zinc
containing plating means a metal plating with zinc or zinc
alloy composed of zinc and other metals (for example, at
least one metal selected from the group consisting of
nickel, iron, aluminum, manganese, chromium, magnesium,
cobalt, lead or antimony) and inevitable impurities, and
the methods for such plating includes hot galvanizing,
electric plating and vapor deposition plating, and are not
limited to these methods. Further, the aluminiferous
material is an aluminum alloy board such as JIS 5000 series
aluminum alloy or JIS 6000 series aluminum alloy, or an
aluminum alloy die cast represented by ADC-12. Still more,
the magnesiferous material is a metal board or a die cast
made of magnesium alloy.
The present invention can be applied to the structural
construction which contains one metal material mentioned
above alone in the composing parts or to the structural
construction which contains two to four metal materials
mentioned above in the composing parts. And, in the case to
apply the present invention to the structural construction
which contains two to four metal materials mentioned above,
it is possible to treat the surfaces of two to four metal
materials at the same time. In the case to treat the
surfaces of two to four metal materials at the same time,
the different metals can be in the condition not contacting
each other or in the condition being joined and contacted
by means of joining method such as welding, adhesion or
riveting.
The treating solution for surface treatment of metal
of the present invention contains 5 to 5000 ppm of at least
one compound selected from the group consisting of
zirconium compound and titanium compound calculated as the
metal element, and 0.1 to 100 ppm of free fluorine ion,
further having pH of 2 to 6. Here, as the zirconium
compound used in the present invention, ZrCl4, ZrOCl2,
Zr(SO4)2, ZrOSO4, Zr(NO3)4, ZrO(NO3)2, H2ZrF6, salt of H2ZrF6,
ZrO2, ZrOBr2 and ZrF4 can be mentioned. And as the titanium
compound, TiCl4, Ti(SO4)2, TiOSO4, Ti(NO3)4, TiO(NO3)2,
TiO2OC2O4, H2TiF6, salt of H2TiF6, TiO2 and TiF4 can be
mentioned. In the present invention, zirconium compound is
desirably used.
The desirable concentration of at least one compound
selected from the group consisting of zirconium compound
and titanium compound is 5 to 5000 ppm calculated as the
metal element (that is, as zirconium and/or titanium), and
the more desirable concentration is 10 to 3000 ppm. The
film obtained by using the treating solution for surface
treatment of metal and the method for surface treatment of
the present invention is oxide or hydroxide of zirconium or
titanium. Therefore, when the concentration of the compound
selected from the group consisting of zirconium compound
and titanium compound calculated as zirconium and/or
titanium is smaller than 5 ppm, it is difficult to obtain
sufficient adhesion amount to attain corrosion resistance
in a practical period of time for treating, because the
concentration of main component of film is too low. On the
contrary, when the concentration is larger than 5000 ppm,
the sufficient adhesion amount can be obtained, but it is
not effective to improve the corrosion resistance and is
disadvantageous from the economical view point.
The zirconium compound and the titanium compound can
be easily dissolved in the acidic solution, but are not
stable in the alkaline solution, and easily deposit as the
oxide or the hydroxide of zirconium or titanium. The
desirable pH of the treating solution for surface treatment
of metal of the present invention is pH 2 to 6, more
desirably pH 3 to 6. When the metal material to be treated
is in contact with the treating solution for surface
treatment of metal of the present invention in the pH range,
the dissolving reaction of the metal material to be treated
occurs. And by the dissolving of the metal material to be
treated, the pH becomes higher at the surface of the metal
material to be treated, and the oxide or the hydroxide of
zirconium or titanium deposits as a film on the surface of
the metal material to be treated.
The treating solution for surface treatment of metal
of the present invention has free fluorine ion existing
therein. To allow free fluorine ion to exist, the fluorine
compound is added into the treating solution for surface
treatment of metal. As the supplying source of the free
fluorine ion, hydrofluoric acid, H2ZrF6 and salt of H2ZrF6,
H2TiF6, salt of H2TiF6, H2SiF6, salt of H2SiF6, HBF4 and salt
of HBF4, NaHF2, KHF2, NH4HF2, NaF, KF and NH4F can be
mentioned. The free fluorine ion has an effect to improve
the stability of the zirconium compound and the titanium
compound in the treating solution for surface treatment of
metal. Further, the free fluorine ion has the function to
promote the dissolving reaction of any of ferriferous
material, zinciferous material, aluminiferous material and
magnesiferous material which are the metal materials to be
surface treated in the present invention. Therefore, by
allowing free fluorine ion to exist therein by adding
fluorine compound, the stability of the treating solution
for surface treatment of metal of the present invention is
improved, and further the reactivity to the metal material
to be treated can be improved.
The inventors of the present invention have previously
suggested a composition for surface treatment and treating
solution for surface treatment of metal containing at least
one of iron and zinc in WO02/103080 as follows. That is,
the composition for surface treatment and treating solution
for surface treatment of metal use titanium compound or
zirconium compound and fluorine containing compound,
wherein the ratio A/B is set within the specific range from
0.06 to 0.18, where A refers to the total mole weight of
metal elements in the composition for surface treatment and
treating solution for surface treatment of metal and B
refers to the mole weight which when total fluorine atom in
fluorine containing compound is calculated as HF. According
to the present invention, it is possible to perform surface
treatment on independently one metal material or
simultaneously two or more metal materials selected from
the group consisting of ferriferous material, zinciferous
material, aluminiferous material and magnesiferous material,
even if out of above mentioned specific range of the ratio,
by regulating the concentration of metal element in the
titanium compound and zirconium compound, pH and the
concentration of free fluorine ion.
It was impossible in the prior arts to perform the
surface treatment on two or more metal materials mentioned
above at the same time, because the respective reactivity
of ferriferous material, zinciferous material,
aluminiferous material and magnesiferous material are
different. In the present invention, it is possible to
perform the surface treatment independently on each metal
material or simultaneously on each metal material or two or
more metal materials selected from the group consisting of
ferriferous material, zinciferous material, aluminiferous
material and magnesiferous material, because the stability
of the treating solution for surface treatment of metal and
the reactivity can be balanced arbitrarily by regulating
the concentration of free fluorine ion.
In the present invention, the concentration of free
fluorine ion means the concentration of fluorine ion
measured by an ion electrode which is on the market. The
concentration of free fluorine ion in the treating solution
for surface treatment of metal of the present invention is
desirably 0.1 to 100 ppm, and more desirably 2 to 70 ppm.
In the case where the concentration of free fluorine ion is
higher than 100 ppm, the dissolving reaction of the metal
material to be treated is promoted. However, since
zirconium compound and titanium compound in the treating
solution for surface treatment of metal are very stable,
even if the pH of the surface of metal material to be
treated increases, it becomes difficult to deposit as a
film. And, in the case where the concentration of free
fluorine ion is lower than 0.1 ppm, the effect for the
improvement of the stability of the treating solution for
surface treatment of metal and the reactivity thereof is
small, and thus, it is no longer advantageous for the
treating solution to contain free fluorine ion.
Other than the effect for improvement of the stability
and reactivation of the treating solution for surface
treatment of metal, the free fluorine ion of the present
invention has a role to keep the eluted component by
dissolution of the metal material to be treated stable in
the treating solution for surface treatment of metal. In
the case of a zinc phosphate treatment of the prior arts,
sludge generates, because, for example, iron ion eluted
from iron metal material reacts with phosphoric acid and
forms iron phosphate which is an insoluble salt. The
treating solution for surface treatment of metal of the
present invention may also contain phosphoric acid group,
but, if the concentration of phosphoric acid group excesses
1.0g/L, sludge can be generated. And, in the case where the
treating amount of the metal material to be treated is
remarkably large with respect to the volume of the bath for
treatment, one or more compounds selected from the group,
for example, consisting of inorganic acid such as sulfuric
acid or hydrochloric; organic acid such as acetic acid,
oxalic acid, tartaric acid, citric acid, succinic acid,
gluconic acid or phthalic acid; and chelating agent which
can chelete eluted component, may be added in the treating
solution to thereby solubilize the eluted component.
The treating solution for surface treatment of metal
in the present invention may contain at least one compound
selected from the group consisting of calcium compound,
magnesium compound and strontium compound. The present
invention realizes to perform surface treatment on each
metal material independently or two to four materials
simultaneously selected from the group consisting of
ferriferous material, zinciferous material, aluminiferous
material and magnesiferous material by regulating the
concentration of free fluorine ion in the aqueous solution
containing zirconium compound and titanium compound of
specific concentration within the specified range. Here,
the metal elements (calcium, magnesium or strontium)
contained in above mentioned calcium compound, magnesium
compound or strontium compound have a function to maintain
the concentration of free fluorine ion in aqueous solution
to a certain value by generating salt of fluorine and
fluorinated compound in the aqueous solution. Due to the
function, when the surface of various kinds of metal
materials are treated at the same time, the optimum deposit
amount of film can be obtained on each metal material to be
treated, because certain concentration of free fluorine ion
can be maintained regardless of the ratio among the
materials used.
As the example of calcium compound, magnesium compound
or strontium compound which can be used in the present
invention, for example, oxide, hydroxide, chloride, sulfate,
nitrate and carbonate of these metal elements can be
mentioned. Further, besides calcium compound, magnesium
compound and strontium compound, the compound which has a
function to maintain the concentration of free fluorine ion
constant can be used regardless of whether an organic
compound or an inorganic compound.
The concentration of the magnesium compound or the
strontium compound which can be used in the present
invention is desirably 10 to 5000 ppm as the metal element,
and more desirably is 100 to 3000 ppm. In the case of
calcium compound, the desirable concentration as calcium is
5 to 100 ppm and more desirable concentration is 5 to 50
ppm, because the solubility of calcium is remarkably small.
When the concentration of these compounds is higher than
the upper limit, the stability of the treating solution for
surface treatment of metal may decrease, and the continuous
treatment is interrupted. And, when the concentration of
these compounds is lower than the lower limit, the deposit
amount of film particularly on ferriferous material
decreases.
In the treating solution for surface treatment of
metal of the present invention, desirably 1000 to 50000 ppm,
more desirably 1000 to 30000 ppm of nitric acid group may
be added. Nitric acid group acts as an oxidizing agent, and
has a function to promote film depositing reaction of the
present invention and a function to improve the solubility
of above mentioned calcium compound, magnesium compound or
strontium compound in the treating solution for surface
treatment of metal. Therefore, even if the concentration of
nitric acid group is lower than 1000 ppm, the film having
excellent corrosion resistance can be deposited. However,
in the case where the concentration of above mentioned
calcium compound, magnesium compound or strontium compound
is high, the stability of the treating solution for surface
treatment of metal may decrease. The concentration of
nitric acid group of 50000 ppm is sufficient, and it is
disadvantageous to add more nitric acid group from the
economical view point.
Further, in the treating solution for surface
treatment of metal of the present invention, at least one
oxygen acid and/or salt of oxygen acid selected from the
group consisting of HClO3, HBrO3, HNO3, HNO2, HMnO4, HVO3,
H2O2, H2WO4, H2MoO4. Oxygen acid or salt thereof acts as
oxidizing agent to the materials to be treated, and
promotes the film forming reaction in the present invention.
The concentration of these oxygen acid or salts thereof to
be added is not restricted, but adding an amount to 10 to
5000 ppm exhibits sufficient effect as the oxidizing agent.
Still further, in the treating solution for surface
treatment of metal of the present invention, at least one
polymer compound selected from the group consisting of
water soluble polymer compounds and water dispersible
polymer compounds may be added. The metal element whose
surface is treated by using the treating solution for
surface treatment of metal of the present invention has an
enough corrosion resistance, but, if additional function
such as lubricity is required, it is possible to improve
the physical property of the film by adding preferably
selected polymer according to the desired function. As the
examples of above mentioned water soluble polymer compounds
and water dispersible polymer compounds, polymer compounds
which are generally used for the surface treatment of metal
such as polyvinyl alcohol, poly(metha)acrylic acid,
copolymer of acrylic acid and methacrylic acid, copolymer
of ethylene with acrylic monomer such as (metha)acrylic
acid or (metha)acrylate, copolymer of ethylene and vinyl
acetate, polyurethane, amino-modified phenol resin,
polyester resin and epoxy resin can be used.
The method for surface treatment of the present
invention can be illustrated as follows. Namely, the
surface is merely treated by degreasing treatment according
to an ordinary method, and the cleaned metal material to be
treated is brought into contact with the treating solution
for surface treatment of metal. Accordingly, the film
composed of oxide and/or hydroxide of a metal element
selected from the group consisting of zirconium and
titanium is deposited and the surface treated film layer
having good adhesiveness and corrosion resistance is formed.
As the substantial method for this contacting process, any
kind of treatment, e.g., spraying treatment, immersion
treatment or pouring treatment can be used, and the
properties of the product will not be influenced by the
treating method. From the chemical view point, it is
difficult to obtain the hydroxide of above mentioned metal
as a pure hydroxide, and in general, the oxide of above
mentioned metal to which hydrated water is attached is
considered as hydroxide. Therefore, the hydroxide of the
metal finally becomes the oxide by heating. The structure
of the surface treated layer of the present invention is
considered to be a state where oxide and hydroxide are
mixed when dried at an ordinary temperature or at a low
temperature after surface treatment. And, when dried at a
high temperature after surface treatment, the structure of
the surface treated layer is considered to be a state of
oxide alone or oxide rich.
In the present invention, the condition to use the
treating solution for surface treatment of metal is not
restricted. The reactivity of the treating solution for
surface treatment of metal of the present invention can be
voluntarily regulated by changing the concentration of
zirconium compound or titanium compound and the
concentration of free fluorine ion in the treating solution
for surface treatment of metal. Therefore, the treating
temperature and treating period of time can be changed
voluntarily in combination of the reactivity of the
treating bath.
Further, to the treating solution for surface
treatment of metal, at least one surface active agent
selected from the group consisting of nonionic surface
active agent, anionic surface active agent and cationic
surface active agent can be added. In the case where the
surface of a metal material is treated with this treating
solution for surface treatment of metal, a good film can be
formed without previous degreasing and cleaning treatment
on the metal material to be treated. That is, this treating
solution for surface treatment of a metal can be used also
as a surface treating agent and a degreasing agent.
Furthermore, for the treatment of the surface of metal
using the treating solution for surface treatment of metal
of the present invention, the method to carry out the
electrolysis in the treating solution for surface treatment
of metal having a metal material to be treated as a cathode.
When the electrolysis treatment is carried out using the
metal material to be treated as a cathode, the reduction
occurs at the surface of the cathode and the pH goes up.
Along with the elevation of the pH, the stability of
zirconium compound and/or titanium compound at the surface
of cathode is deteriorated, and the surface treated film is
deposited as an oxide or a hydroxide containing water.
Still further, the effect of the present invention can
be improved when, after contacting with treating solution
for surface treatment of metal, or after being electrolyzed
in the treating solution for surface treatment of metal
with or without washed by water, the metal material is
brought into contact with the acidic solution of the
compound containing at least one element selected from the
group consisting of cobalt, nickel, tin, copper, titanium
and zirconium, or with the treating solution containing at
least one polymer compound selected from the group
consisting of water soluble polymer compound and water
dispersible polymer.
The surface treated film layer obtained by the present
invention is characterized in a thin film and exhibits
excellent coating property, but depending on the surface
condition of the metal material to be treated, sometimes
tiny defects may be formed on the surface treated film
layer. By bringing the layer in contact with the acidic
solution of the compound containing at least one element
selected from the group consisting of cobalt, nickel, tin,
copper, titanium and zirconium or the treating solution
containing at least one polymer compound selected from the
group consisting of water soluble polymer compound and
water dispersible polymer, the tiny defects are covered and
the corrosion resistance can be further improved.
The compound containing at least one element selected
from the group consisting of cobalt, nickel, tin, copper,
titanium and zirconium is not restricted, and, it is
possible to use oxide, hydroxide, fluoride, complex
fluoride, chloride, nitrate, oxynitrate, sulfate,
oxysulfate, carbonate, oxycarbonate, phosphate,
oxyphosphate, oxalate, oxyoxalate, and organic metal
compounds and the like. Further, desirably the pH of acidic
solution containing the metal element is 2 to 6, and can be
adjusted with 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, salts of alkali metal,
ammonium salt or amines.
Further, as at least one polymer compound selected
from above mentioned water soluble polymer compound or
water dispersible polymer compound, for example, polyvinyl
alcohol, poly(metha)acrylic acid, copolymer of acrylic acid
and methacrylic acid, copolymer of ethylene with acrylic
monomer such as (metha)acrylic acid or (metha)acrylate,
copolymer of ethylene and vinyl acetate, polyurethane,
amino-modified phenol resin, polyester resin or epoxy resin,
tannin and tannic acid and salts thereof, and phytic acid
can be used.
The present invention may remarkably improve the
corrosion resistance of metal material by providing a
surface treated film layer composed of oxide and/or
hydroxide of metal elements selected from zirconium and/or
titanium on the surface of metal material to be treated.
The oxide and hydroxide of above mentioned metal elements
have a physical property characterized not to be damaged by
acid or alkali, and chemically stabilized. In the actual
corrosive environment for metal, at the anode where the
metal elution phenomenon occurs, the pH becomes lower,
while, at the cathode where reduction occurs, the pH
becomes higher. Therefore, the surface treated film of less
resistant to acid and alkali may be dissolved under the
corrosive environment and its effect would be lost. Since
the main component of the surface treated film layer of the
present invention is resistive to acid or alkali, the
excellent effect can be maintained under the corrosive
environment.
And since the oxide and hydroxide of above mentioned
metal elements form a network structure mediated by metal
and oxide, it becomes a very good barrier film. The
corrosion of metal material, which can be varied depending
on the environment for use, generally, is oxygen demanding
type corrosion in the atmosphere in which water and oxygen
exist, and the speed of corrosion is promoted by the
presence of the components such as chloride. Having a
barrier effect against water, an acid and a corrosion
promoting component, the surface treated film layer of the
present invention may exhibit excellent corrosion
resistance.
For the purpose to enhance the corrosion resistance of
iron metal material such as cold rolled steel plate, hot
rolled steel plate, cast iron and sintered steel using
above mentioned barrier effect, the adhesion amount over 30
mg/m2 calculated as the metal element is necessary,
desirably over 40 mg/m2 and more desirably over 50 mg/m2.
And for the purpose to enhance the corrosion resistance of
zinc metal material such as zinc, zinc plated steel plate
and alloyed hot-dip zinc-coated steel plate, the adhesion
amount over 20 mg/m2 calculated as the metal element is
necessary, desirably over 30 mg/m2. Further, for the
purpose to enhance the corrosion resistance of
aluminiferous materials such as cast aluminum and aluminum
alloy plate, the adhesion amount over than 10 mg/m2
calculated as the metal element is necessary, desirably
over 20 mg/m2. For the purpose to enhance the corrosion
resistance of magnesiferous materials such as magnesium
alloy plate and cast magnesium, the adhesion amount over
than 10 mg/m2 calculated as the metal element is necessary,
desirably over than 20 mg/m2. Referring to the adhesion
amount, there is no upper limit. However, when the amount
exceeds 1g/m2, cracks easily generate on the surface
treated film layer and it becomes difficult to form a
uniform film. Therefore, in any case of iron metal material
and zinc metal material and aluminiferous material, the
desirable upper limit of adhesion amount is 1 g/m2, more
desirably 800 mg/m2.
The effects of the treating solution for surface
treatment of metal and the method for surface treatment of
the present invention will be illustrated specifically in
accordance with the Examples and Comparative Examples below.
And a material to be treated, a degreasing agent and a
coating used therein are arbitrarily selected from the
materials which are on the market, and not intending to
restrict the actual uses of the treating solution for
surface treatment of metal and the method for surface
treatment of the present invention.
As the test plates, cold rolled steel plates, hot-dip
zinc-coated steel plates, aluminum alloy plates and
magnesium alloy plates are used in the Examples and
Comparative Examples. The abbreviations and specifications
of these test plates are shown below. For the evaluation of
the appearance after surface treatment, the test plate
prepared by joining three metal materials of SPC, GA and Al
by a spot welding was used. For the evaluation of adhesion
amount of surface treated film layer, each test plate of
SPC, GA, Al and Mg, and the test plate prepared by joining
three metal materials of SPC, GA and Al by a spot welding
were used. For the evaluation of the coating property, the
test plate prepared by joining three metal materials of SPC,
GA and Al by a spot welding was used and the test from
surface treatment, coating and evaluation of coating
property were carried out in series. Fig.1 is the plane
view of the test plate prepared by joining three metal
materials of SPC, GA and Al by a spot welding, and Fig.2 is
an elevation view of it. The numeral 1 indicates a spot
welded portion.
- SPC: cold rolled steel plate (JIS-G-3141)
- GA: both-side alloyed hot-dip zinc-coated steel plate (45 g/m2)
- Al: aluminum alloy plate (6000 series aluminum alloy)
- Mg: magnesium alloy plate (JIS-H-4201)
Treating process of Examples and Comparative Examples
are shown as follows.
In above mentioned processes for Examples and
Comparative Examples, alkali degreasing was carried out as
follows. That is, Fine Cleaner L4460 (Trade Mark: Product
of Nihon Parkerizing) was diluted to 2% concentration by
city water, and was sprayed to a plate to be treated at 40
°C for 120 sec. Rinsing by water and rinsing by pure water
after film formation treatment were performed by spraying
water and pure water on the plate to be treated at a room
temperature for 30 sec both in Examples and Comparative
Examples.
Aqueous solution of zirconium with concentration of
200 ppm was prepared using zirconium oxynitrate reagent and
nitric acid. After heating the aqueous solution to 45°C,
the pH was adjusted to 3.0 using sodium hydroxide reagent
and hydrofluoric acid, and the concentration of free
fluorine ion measured by a fluorine ion meter (IM-55G;
product of Toa Denpa Industries Co., Ltd) was adjusted to 1
ppm, thus obtaining the treating solution for surface
treatment of metal. The total fluorine concentration in the
treating solution for surface treatment of metal after
adjusting free fluorine ion was 50 ppm.
The test plate rinsed by water after degreasing was
immersed into the treating solution for surface treatment
of metal for 120 seconds so as to carry out the surface
treatment.
Aqueous solution of zirconium with concentration of
100 ppm, magnesium with concentration of 5000 ppm,
strontium with concentration of 2000 ppm and nitric acid
group with concentration of 28470 ppm was prepared using
zirconium oxynitrate reagent, magnesium nitrate reagent and
strontium nitrate reagent. After heating the aqueous
solution to 50°C, the pH was adjusted to 4.0 using ammonium
water reagent and hydrofluoric acid, and the concentration
of free fluorine ion measured by a fluorine ion meter (IM-55G;
product of Toa Denpa Industries Co., Ltd) was adjusted
to 80 ppm, thus obtaining the treating solution for surface
treatment of metal. The total fluorine concentration in the
treating solution for surface treatment of metal after
adjusting free fluorine ion was 2000 ppm.
The test plate rinsed by water after degreasing was
immersed into the treating solution for surface treatment
of metal for 60 seconds so as to carry out the surface
treatment.
Aqueous solution of zirconium with concentration of
1000 ppm, titanium with concentration of 2000 ppm, calcium
with concentration of 5 ppm and nitric acid group with
concentration of 1000 ppm was prepared using aqueous
solution of hexafluorozirconic acid (IV), aqueous solution
of titanium sulfate (IV) and calcium sulfate reagent. After
heating the aqueous solution to 40°C, the pH was adjusted
to 5.0 using potassium hydroxide reagent and hydrofluoric
acid, and the concentration of free fluorine ion measured
by a fluorine ion meter (IM-55G; product of Toa Denpa
Industries Co., Ltd) was adjusted to 25 ppm, thus obtaining
the treating solution for surface treatment of metal. The
total fluorine concentration in the treating solution for
surface treatment of metal after adjusting free fluorine
ion was 2250 ppm.
The test plate rinsed by water after degreasing was
immersed into the treating solution for surface treatment
of metal for 90 seconds so as to carry out the surface
treatment.
Aqueous solution of titanium with concentration of
5000 ppm, strontium with concentration of 5000 ppm, nitric
acid group with concentration of 7080 ppm and nitrous acid
group with concentration of 40 ppm was prepared using
aqueous solution of hexafluorotitanium acid (IV), strontium
nitrate reagent, and sodium nitrite reagent. After heating
the aqueous solution to 35°C, the pH was adjusted to 4.0
using triethanol amine reagent and hydrofluoric acid, and
the concentration of free fluorine ion measured by a
fluorine ion meter (IM-55G; product of Toa Denpa Industries
Co., Ltd) was adjusted to 10 ppm, thus obtaining the
treating solution for surface treatment of metal. The total
fluorine concentration in the treating solution for surface
treatment of metal after adjusting free fluorine ion was
11900 ppm.
The test plate was rinsed by water after degreasing,
then the obtained treating solution for surface treatment
of metal was sprayed to the surface thereof for 120 sec.,
thus carrying out the surface treatment.
Aqueous solution of zirconium with concentration of 5
ppm, titanium with concentration of 5 ppm, magnesium with
concentration of 100 ppm, nitric acid group with
concentration of 30520 ppm and chloric acid group with
concentration of 100 ppm was prepared using zirconium
oxynitrate reagent, aqueous solution of hexafluorotitanic
acid (IV), magnesium nitrate reagent, nitric acid and
sodium chloric acid reagent. After heating the aqueous
solution to 30°C, the pH was adjusted to 6.0 using ammonia
water reagent and hydrofluoric acid, and the concentration
of free fluorine ion measured by a fluorine ion meter (IM-55G;
product of Toa Denpa Industries Co., Ltd) was adjusted
to 0.5 ppm, thus obtaining the treating solution for
surface treatment of metal. The total fluorine
concentration in the treating solution for surface
treatment of metal after adjusting free fluorine ion was 12
ppm.
Using the test plate rinsed by water after degreasing
as a cathode and a carbon electrode as an anode, the test
plate was electrolyzed in the treating solution for surface
treatment of metal for 5 seconds under the condition of
5A/dm2, thus carrying out the surface treatment.
Aqueous solution of zirconium with concentration of
150 ppm, magnesium with concentration of 10 ppm, nitric
acid group with concentration of 5200 ppm and hydrogen
peroxide concentration of 10 ppm was prepared using
zirconium oxynitrate reagent, magnesium oxide reagent,
nitric acid, and hydrogen peroxide reagent. After heating
the aqueous solution to 50°C, the pH was adjusted to 5.0
using ammonia water reagent and hydrofluoric acid, the
concentration of free fluorine ion measured by a fluorine
ion meter (IM-55G; product of Toa Denpa Industries Co.,
Ltd) was adjusted to 50 ppm and 2 g/L of
polyoxyethylenenonylphenylether (ethylene oxide addition
mole number: 12 mol), which is nonionic surface active
agent, was added, thus obtaining the treating solution for
surface treatment of metal. The total fluorine
concentration in the treating solution for surface
treatment of metal after adjusting free fluorine ion was
170 ppm.
Undegreased test plate on which oil is coated, above
mentioned treating solution for surface treatment of metal
was applied to the surface by spray for 90 sec., thus the
degreasing and surface treatment were carried out at the
same time.
Aqueous solution of titanium with concentration of 100
ppm, calcium with concentration of 50 ppm, magnesium with
concentration of 5000 ppm, nitric acid group with
concentration of 25660 ppm and permanganate with
concentration of 10 ppm was prepared using aqueous solution
of titanium sulfate (IV), calcium nitrate reagent,
magnesium nitrate reagent and potassium permanganate
reagent. Water soluble acrylic polymer compound (Jurymer
AC-10L: product of Nihon Junyaku Co., Ltd.) was added in
the aqueous solution so as the concentration of solid to be
1%, then the aqueous solution was heated to 50°C.
Thereafter, the pH was adjusted to 3.0 using sodium hydroxide reagent and hydrofluoric acid, and the total free fluorine ion concentration in the aqueous solution to be measured by a fluorine ion meter (IM-55G; product of Toa Denpa Industries Co., Ltd) was adjusted to 95 ppm, thus obtaining the treating solution for surface treatment of metal. After adjusting the free fluorine ion concentration, the total fluorine concentration in the treating solution for surface treatment of metal was 2000 ppm.
Thereafter, the pH was adjusted to 3.0 using sodium hydroxide reagent and hydrofluoric acid, and the total free fluorine ion concentration in the aqueous solution to be measured by a fluorine ion meter (IM-55G; product of Toa Denpa Industries Co., Ltd) was adjusted to 95 ppm, thus obtaining the treating solution for surface treatment of metal. After adjusting the free fluorine ion concentration, the total fluorine concentration in the treating solution for surface treatment of metal was 2000 ppm.
The test plate rinsed by water after degreasing was
immersed into the treating solution for surface treatment
of metal for 60 seconds so as to carry out the surface
treatment.
The aqueous solution with 1% of water soluble acrylic
polymer compound (Jurymer AC-10L: product of Nihon Junyaku
Co., Ltd.) in solid concentration and 2g/L of phosphoric
acid reagent as phosphoric acid group was prepared. This
aqueous solution was heated to 40°C, then the pH was
adjusted to 4.5 using ammonia water reagent, thus obtaining
the after treating solution. The test plate on which film
formation was carried out by the surface treatment of
Example 5 and rinsed by water was dipped into the above
mentioned after treating solution for 30 seconds so as to
carry out the after treatment.
The aqueous solution of zirconium with concentration
of 50 ppm and cobalt with concentration of 50 ppm was
prepared using aqueous solution of hexafluorozirconic acid
(IV) and cobalt nitrate reagent. After heating the aqueous
solution to 40°C, the pH was adjusted to 5.0 with ammonia
water reagent, thus obtaining the after treating solution.
The test plate on which film formation was carried out by
the surface treatment of Example 6 and rinsed by water was
immersed into the above mentioned after treating solution
for 30 seconds so as to carry out the after treatment.
The aqueous solution of zirconium with concentration
of 500 ppm, magnesium with concentration of 1000 ppm and
nitric acid group with concentration of 6780 ppm was
prepared using zirconium oxynitrate reagent, magnesium
nitrate and nitric acid. After heating the aqueous solution
to 45°C, the pH was adjusted to 4.0 with sodium hydroxide
solution, thus obtaining the treating solution for surface
treatment of metal. The free fluorine ion concentration of
the treating solution for surface treatment of metal was
measured by a fluorine ion meter on the market (IM-55G;
product of Toa Denpa Industries Co., Ltd), and the result
was 0 ppm.
The test plate which was rinsed by water after
degreasing was immersed into the above mentioned treating
solution for surface treatment of metal for 120 seconds so
as to carry out the surface treatment.
The aqueous solution of titanium with concentration of
2000 ppm was prepared by using aqueous solution of titanium
sulfate (IV). After heating the aqueous solution to 50°C,
the pH was adjusted to 3.5 using ammonia water reagent and
hydrofluoric acid, and the concentration of free fluorine
ion measured by a fluorine ion meter (IM-55G; product of
Toa Denpa Industries Co., Ltd) was adjusted to 400 ppm,
thus obtaining the treating solution for surface treatment
of metal.
The test plate which was rinsed by water after
degreasing was immersed into the above mentioned treating
solution for surface treatment of metal for 90 seconds so
as to carry out the surface treatment.
Alchrom 713 (Trade Mark, product of Nihon Parkerizing
Co., Ltd.), which is the chromic chromate treating agent on
the market, was diluted by city water to the concentration
of 3.6%, then total acidity and free acid acidity were
adjusted to the center value described in the brochure.
The test plate was rinsed by water after degreasing,
then immersed into the chromate treating solution heated to
the temperature of 35°C and chromate treatment was carried
out for 60 sec.
Palcoat 3756 (Trade Mark, product of Nihon Parkerizing
Co., Ltd.), which is the chrome free treating agent on the
market, was diluted by city water to the concentration of
2%, then total acidity and free acid acidity were adjusted
to the center value described in the brochure. The test
plate was rinsed by water after degreasing, then immersed
into the chrome free treating solution heated to the
temperature of 40°C and chrome free treatment was carried
out for 60 sec.
The test plate was rinsed by water after degreasing,
then the solution prepared by diluting Prepalene ZN (Trade
Mark, product of Nihon Pakerizing Co., Ltd.), which is a
surface conditioning agent, with city water to the
concentration of 0.1% was sprayed thereon at the room
temperature for 30 sec. Palbond L3020 (Trade Mark, product
of Nihon Parkerizing Co., Ltd.) was diluted to the
concentration of 4.8% with city water. Further, sodium
hydrogen fluoride reagent as fluorine was added into the
solution to 200 ppm, and then, total acidity and free acid
acidity thereof were adjusted to the center value described
in the brochure. Thus the zinc phosphate treating solution
was prepared. Above mentioned test plate was immersed into
the zinc phosphate chemical treating solution heated to the
temperature of 42°C, and zinc phosphate film was deposited.
The appearance of surface treated plates of the
Examples and Comparative Examples were evaluated by visual
inspection. Results are summarized in Table 1. Further,
adhesion amounts of surface treated film layers were
measured by a fluorescent X-ray analyzer (System 3270,
product of Rigaku Denki Kogyo Co., Ltd.). Results are
summarized in Table 2 and Table 3. The adhesion amount of
surface treated film layer was measured in the case where
metal materials were not joined together and treated
respectively (in the case without joining) and in the case
where materials were subjected to joining treatment by
means of spot welding (in the case with joining).
| appearance after surface treatment | |||
| on SPC | on GA | on Al | |
| Example 1 | uniform interference color | uniform dark black | uniform white |
| Example 2 | uniform interference color | uniform dark black | uniform white |
| Example 3 | uniform interference color | uniform dark black | uniform white |
| Example 4 | uniform interference color | uniform dark black | uniform white |
| Example 5 | uniform interference color | uniform dark black | uniform white |
| Example 6 | uniform interference color | uniform dark black | uniform white |
| Example 7 | uniform interference color | uniform dark black | uniform white |
| Comparative Example 1 | film not deposited | film not deposited | uneven white |
| Comparative Example 2 | pale yellow | uneven gray | uneven white |
| Comparative Example 3 | film not deposited | slightly turned to yellow | gold |
| Comparative Example 4 | film not deposited | film not deposited | uniform white |
| Comparative Example 5 | material partially exposed | uniform gray | uneven white |
In Table 1, the appearance evaluation results of
surface treated films obtained by Examples and Comparative
Examples are shown. In the Examples, it is clear that the
uniform films, were obtained on all metal materials in all
test plates. Further, on the spot welded portions of test
plates used in Examples, the deposition of surface treated
film was observed too. On the contrary, in Comparative
Examples, a uniform film was not formed on all test plates.
Especially, in Comparative Examples 3, 4 and 5, the
deposition of film on spot welded portions was not at all
observed. Further, the Comparative Example 5 used the zinc
phosphate chemical treating solution to be used in the case
where cold rolled steel plate, zinc plated steel plate and
aluminum alloy are treated at the same time. When the test
plates were joined by spot welding as illustrated in the
present test, the portion where the metal material was
exposed, which is called as "Lack of Hiding", was observed
on the cold rolled steel plate.
| adhesion amount of surface treated film layer (without joining) (total adhesion amount of Zr and Ti: mg/m2) | ||||
| on SPC | on GA | on Al | on Mg | |
| Example 1 | 122 | 67 | 48 | 45 |
| Example 2 | 108 | 66 | 49 | 41 |
| Example 3 | 61 | 58 | 42 | 38 |
| Example 4 | 73 | 59 | 14 | 12 |
| Example 5 | 41 | 52 | 38 | 26 |
| Example 6 | 35 | 38 | 25 | 19 |
| Example 7 | 31 | 29 | 24 | 18 |
| Comparative Example 1 | trace | trace | trace | trace |
| Comparative Example 2 | 25 | 15 | 15 | 10 |
| Comparative Example 3 | trace | Cr 33 | Cr 95 | Cr 75 |
| Comparative Example 4 | trace | trace | 25 | 15 |
| Comparative Example 5 | weight of film 2.5g/m2 | weight of film 4.5g/m2 | weight of film 1.2g/m2 | weight of film 0.5g/m2 |
| Adhesion amount of surface treated film layer (with joining) (total adhesion amount of Zr and Ti: mg/m2) | |||
| on SPC | on GA | on Al | |
| Example 1 | 125 | 67 | 48 |
| Example 2 | 118 | 66 | 49 |
| Example 3 | 65 | 58 | 42 |
| Example 4 | 72 | 59 | 14 |
| Example 5 | 45 | 52 | 38 |
| Example 6 | 38 | 38 | 25 |
| Example 7 | 32 | 29 | 24 |
| Comparative Example 1 | trace | trace | trace |
| Comparative Example 2 | 28 | 17 | 12 |
| Comparative Example 3 | trace | Cr 35 | Cr 85 |
| Comparative Example 4 | trace | trace | 21 |
| Comparative Example 5 | weight of film 2.8 g/m2 | weight of film 4.7 g/m2 | Weight of film 0.7 g/m2 |
In Table 2 and Table 3, the results by the measurement
of adhesion amount of surface treated film obtained in
Examples and Comparative Examples. In the Examples, the
aimed adhesion amounts were be obtained on all metal
materials in all test plates. Further, the adhesion amount
of surface treated film layer in Examples was constant
regardless of whether the test plates were joined or not.
On the contrary, as clearly understood from the evaluation
results for appearance of film in Comparative Example, the
uniform film was not deposited on all test plates.
For the purpose to evaluate the coating property of
surface treated plates obtained in Examples and Comparative
Examples, coating was carried out by the following process:
cationic electrodeposition coating → rinsing with pure
water → baking → surfacer → baking → top coating → baking.
Details of the cationic electrodeposition coating,
surfacer, and top coating are as follows:
The coating property in the Examples and Comparative
Examples was evaluated and the results thereof are shown in
Table 4 and Table 5. Items evaluated and the abbreviations
are described below. Hereinafter, the coated film after
electrodeposition coating process is called as
electrodeposition coated film and the coated film after top
coating is called as 3-coats film.
- SST: Cross cut line is notched using a sharp knife on the electrodeposition coated plate, and 5% brine is sprayed to the plate for 840 hours (according to JIS-Z-2371). After spraying, maximum blister widths at both sides from the cross cut line were measured.
- SDT: The electrodeposition coated plate was soaked into aqueous solution of 5 wt% of NaCl at 50°C for 840 hours. After soaking, the test plate washed with city water and dried at the room temperature. The whole surface of the test plate was peeled off using an adhesive tape, and the removed area of coated film on each metal material was evaluated by inspector's eye.
- 1st ADH: Checker lines of 100 squares with 2 mm intervals were marked using a sharpened knife on a 3-coats film. The squares in the checker were peeled using a cellophane tape, and numbers of peeled squares were counted.
- 2nd ADH: A 3-coats film was soaked in pure water of 40
°C for 240 hours. Then, 100 checker squares with 2mm
interval were marked using a sharpened knife on it. The
checker squares were peeled using a cellophane tape, and
numbers of peeled squares were counted.
coating property of electro deposition film SST max blister widths at both sides (mm) SDT removed area (%) on SPC on GA on Al on SPC on GA on Al Example 1 2.0 0.5 0.5 5> 5> 5> Example 2 2.0 0.5 0.5 5> 5> 5> Example 3 3.0 0.5 0.5 5> 5> 5> Example 4 3.0 0.5 0.5 5> 5> 5> Example 5 3.0 0.5 0.5 5 5> 5> Example 6 3.5 1.0 0.5 10 5> 5> Example 7 3.5 1.0 0.5 10 5> 5> Example 8 2.5 0.5 0.5 5> 5> 5> Example 9 2.5 0.5 0.5 5> 5> 5> Comparative Example 1 6.5 3.5 3.0 70 40 15 Comparative Example 2 4.5 2.0 0.5 30 10 5 Comparative Example 3 10.0 5.0 0.5 80 40 5> Comparative Example. 4 10.0 5.0 1.0 90 50 10 Comparative Example 5 5.0 2.0 2.0 40 10 20
The results for evaluation of coating property of the
electrodeposition coated film are summarized in Table 4.
Examples showed good corrosive resistance on all test
plates. On the contrary, in Comparative Example 1, since
free fluorine ions were not contained in the treating
solution for surface treatment of metal at all, the
deposition of surface treated film was not sufficient and
thus the corrosion resistance was not so good. Further, in
Comparative Example 2, since the concentration of free
fluorine ion in the treating solution for surface treatment
of metal was high, especially, the adhesion amount of film
on SPC was small and the corrosion resistance was not so
good. The coating properties of Examples 5 and 6 were
superior to those of Comparative Examples, but when
compared with other Examples, corrosive resistances after
electrodeposition coating was inferior to those of other
Examples. However, as shown in Examples 8 and 9, the
corrosive resistance was further improved by carrying out
the after treatment.
Because in Comparative Example 3, a chromate treating
agent for aluminum alloy was used and in Comparative
Example 4, a chrome free treating agent for aluminum alloy
was used, the corrosion resistance of Al was good, but the
corrosion resistance of other test plates were obviously
inferior to those of Examples. In Comparative Example 5, a
zinc phosphate treating agent, which is now usually used as
the base for coating was used. However, Comparative Example
5, in the condition where each of the test plates was
joined by welding, showed the test results inferior to
those of Examples.
| coating properties of 3-coats film | ||||||
| 1st ADH | 2nd ADH | |||||
| on SPC | on GA | on Al | on SPC | on GA | on Al | |
| Example 1 | 0 | 0 | 0 | 0 | 0 | 0 |
| Example 2 | 0 | 0 | 0 | 0 | 0 | 0 |
| Example 3 | 0 | 0 | 0 | 0 | 0 | 0 |
| Example 4 | 0 | 0 | 0 | 0 | 0 | 0 |
| Example 5 | 0 | 0 | 0 | 0 | 0 | 0 |
| Example 6 | 0 | 0 | 0 | 0 | 0 | 0 |
| Example 7 | 0 | 0 | 0 | 0 | 0 | 0 |
| Example 8 | 0 | 0 | 0 | 0 | 0 | 0 |
| Example 9 | 0 | 0 | 0 | 0 | 0 | 0 |
| Comparative Example 1 | 0 | 0 | 0 | 5 | 8 | 0 |
| Comparative Example 2 | 0 | 0 | 0 | 0 | 0 | 0 |
| Comparative Example 3 | 6 | 0 | 0 | 17 | 3 | 0 |
| Comparative Example 4 | 0 | 0 | 0 | 5 | 0 | 0 |
| Comparative Example 5 | 5 | 0 | 0 | 8 | 0 | 6 |
Table 5 shows the evaluation results of adhesion of a
3-coats plate. Examples showed good adhesion to all test
plates. Regarding to 1st ADH, good results were obtained in
all Comparative Examples. However, regarding to 2nd ADH,
Comparative Examples did not show the good level of
adhesion to all test plates same as the corrosive
resistance of the electrodeposition coating. Further, in
Comparative Example 5, the generation of sludge, which is
the by-product of zinc phosphate treatment, was observed in
the treating bath after surface treatment. However, in
Examples of the present invention, the generation of sludge
was not observed.
From above mentioned results, it is obviously
understood following facts. That is, simultaneous
treatments of SPC, GA, and Al and the deposition of surface
treated film having good adhesion and corrosion resistance
on the surface thereof without changing treating bath and
treating condition are possible only by using the treating
solution for surface treatment of metal and the surface
treating method of the present invention. According to the
present invention, it is possible to deposit the surface
treated film having good corrosion resistance even on a
welded portion. Further, since the method for surface
treatment of the present invention requires only to bring
the metal material to be treated in contact with the
treating solution for surface treatment of metal, it is
possible to deposit surface treated film and to improve the
corrosive resistance in the portion where the solution may
not be stirred such as inside of bag shape structure.
Industrial Applicability
According to the treating solution for metal surface
treatment and the method for surface treatment of the
present invention, it is possible to deposit a surface
treated film having excellent corrosion resistance after
coating on the surface of a metal made of two or more, or
each of ferriferous material, zinciferous material,
aluminiferous material and magnesiferous material in the
treating bath containing no harmful component to the
environment and without generating sludge, which have never
been achieved in the prior art. Further, since the present
invention does not need a process for surface conditioning
on the metal material to be treated, it is possible to
shorten the treatment time and to reduce space for the
treatment.
Claims (17)
- Treating solution for surface treatment of metal, which is aqueous surface treating solution to treat independently each metal material or simultaneously two or more metal materials selected from the group consisting of ferriferous material, zinciferous material, aluminiferous material and magnesiferous material, the treating solution containing 5 to 5000 ppm of at least one compound selected from the group consisting of zirconium compound and titanium compound calculated as metal element, and 0.1 to 100 ppm of free fluorine ion, and having pH 2 to 6.
- The treating solution for surface treatment of metal according to claim 1, further containing at least one compound selected from the group consisting of calcium compound, magnesium compound and strontium compound, wherein concentration of the compound calculated as metal element is 5 to 100 ppm in the case of the calcium compound, 10 to 5000 ppm in the case of the magnesium and 10 to 5000 ppm in the case of the strontium compound.
- The treating solution for surface treatment of metal according to claim 1 or 2, further containing 1000 to 50000 ppm of nitrate group.
- The treating solution for surface treatment of metal according to any one of claims 1 to 3, further containing at least one oxygen acid and/or salt of oxygen acid selected from the group consisting of HClO3, HBrO3, HNO2, HNO3, HMnO4, HVO3, H2O2, H2WO4, H2MoO4 and salts thereof.
- The treating solution for surface treatment of metal according to any one of claims 1 to 4, further containing at least one polymer compound selected from the group consisting of water soluble polymer compounds and water dispersible polymer compounds.
- The treating solution for surface treatment of metal according to any one of claims 1 to 5, further containing at least one surface active agent selected from the group consisting of nonionic surface active agents, anionic surface active agents and cationic surface active agents.
- A method for surface treatment of metal comprising, contacting independently each metal material or simultaneously two or more metal materials selected from the group consisting of ferriferous material, zinciferous material, aluminiferous material and magnesiferous material with the treating solution for surface treatment according to any one of claims 1 to 6.
- The method for surface treatment of metal according to claim 7, comprising, further contacting the metal material or the two or more metal materials with acidic aqueous solution of compound containing at least one element selected from the group consisting of cobalt, nickel, tin, copper, titanium and zirconium, after contacting with the treating solution for surface treatment, with or without washing by water.
- The method for surface treatment of metal according to claim 7, comprising, further contacting the metal material or the two or more metal materials with treating solution containing at least one polymer compound selected from water soluble polymer compounds and water dispersible polymer compounds, after contacting with the treating solution for surface treatment, with or without washing by water.
- A method for surface treatment of metal comprising, electrolytic treating in the treating solution for surface treatment according to any one of claims 1 to 6, wherein independently each metal material or simultaneously two or more metal materials selected from the group consisting of ferriferous material, zinciferous material, aluminiferous material and magnesiferous material are a cathode.
- The method for surface treatment of metal according to claim 10, comprising, further contacting the metal material or the two or more metal materials with acidic aqueous solution of compound containing at least one element selected from the group consisting of cobalt, nickel, tin, copper, titanium and zirconium, after electrolytic treating in the treating solution for surface treatment, with or without washing by water.
- The method for surface treatment of metal according to claim 10, comprising, further contacting the metal material or the two or more metal materials with treating solution containing at least one polymer compound selected from water soluble polymer compounds and water dispersible polymer compounds, after electrolytic treating in the treating solution for surface treatment, with or without washing by water.
- A method for surface treatment of metal comprising, contacting independently each metal material or simultaneously two or more metal materials selected from the group consisting of ferriferous material, zinciferous material, aluminiferous material and magnesiferous material, whose surface is not degreased and cleaned with the treating solution for surface treatment according to claim 6.
- A metal material having a surface treated film containing at least one metal element selected from the group consisting of titanium and zirconium formed on a surface of iron metal material by the method for surface treatment according to any one of claims 7 to 13, wherein an adhesion amount of the surface treated film calculated as the metal element is 30mg/m2 or more.
- A metal material having a surface treated film containing at least one metal element selected from the group consisting of titanium and zirconium formed on a surface of zinc metal material by the method for surface treatment according to any one of claims 7 to 13, wherein an adhesion amount of the surface treated film calculated as the metal element is 20mg/m2 or more.
- A metal material having a surface treated film containing at least one metal element selected from the group consisting of titanium and zirconium formed on a surface of aluminum metal material by the method for surface treatment according to any one of claims 7 to 13, wherein an adhesion amount of the surface treated film calculated as the metal element is 10mg/m2 or more.
- A metal material having a surface treated film containing at least one metal element selected from the group consisting of titanium and zirconium formed on a surface of magnesium metal material by the method for surface treatment according to any one of claims 7 to 13, wherein an adhesion amount of the surface treated film calculated as the metal element is 10mg/m2 or more.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002362640 | 2002-12-13 | ||
| JP2002362640A JP4205939B2 (en) | 2002-12-13 | 2002-12-13 | Metal surface treatment method |
| PCT/JP2003/015868 WO2004055237A1 (en) | 2002-12-13 | 2003-12-11 | Treating fluid for surface treatment of metal and method for surface treatment |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP1571237A1 true EP1571237A1 (en) | 2005-09-07 |
| EP1571237A4 EP1571237A4 (en) | 2007-11-21 |
| EP1571237B1 EP1571237B1 (en) | 2019-03-20 |
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ID=32588165
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|---|---|---|---|
| EP03780727.8A Expired - Lifetime EP1571237B1 (en) | 2002-12-13 | 2003-12-11 | Treating fluid for surface treatment of metal and method for surface treatment |
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| Country | Link |
|---|---|
| US (1) | US20060185769A1 (en) |
| EP (1) | EP1571237B1 (en) |
| JP (1) | JP4205939B2 (en) |
| KR (1) | KR100674778B1 (en) |
| CN (2) | CN101487115B (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) |
Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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Also Published As
| Publication number | Publication date |
|---|---|
| CA2509772A1 (en) | 2004-07-01 |
| CN100537845C (en) | 2009-09-09 |
| US20060185769A1 (en) | 2006-08-24 |
| CN1726304A (en) | 2006-01-25 |
| KR100674778B1 (en) | 2007-01-25 |
| EP1571237A4 (en) | 2007-11-21 |
| TW200416300A (en) | 2004-09-01 |
| JP4205939B2 (en) | 2009-01-07 |
| WO2004055237A1 (en) | 2004-07-01 |
| MXPA05006156A (en) | 2005-12-05 |
| EP1571237B1 (en) | 2019-03-20 |
| ES2730576T3 (en) | 2019-11-12 |
| AU2003289323A8 (en) | 2004-07-09 |
| CN101487115B (en) | 2013-05-22 |
| JP2004190121A (en) | 2004-07-08 |
| CN101487115A (en) | 2009-07-22 |
| KR20050097916A (en) | 2005-10-10 |
| AU2003289323A1 (en) | 2004-07-09 |
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