WO2018198384A1 - 水系処理液、化成処理方法および化成処理鋼板 - Google Patents
水系処理液、化成処理方法および化成処理鋼板 Download PDFInfo
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- WO2018198384A1 WO2018198384A1 PCT/JP2017/018775 JP2017018775W WO2018198384A1 WO 2018198384 A1 WO2018198384 A1 WO 2018198384A1 JP 2017018775 W JP2017018775 W JP 2017018775W WO 2018198384 A1 WO2018198384 A1 WO 2018198384A1
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- Prior art keywords
- chemical conversion
- steel plate
- aqueous
- treatment liquid
- iso
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- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- PVEOYINWKBTPIZ-UHFFFAOYSA-N but-3-enoic acid Chemical compound OC(=O)CC=C PVEOYINWKBTPIZ-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- KPSZWAJWFMFMFF-UHFFFAOYSA-N delta-Hexylen-alpha-carbonsaeure Natural products CC=CCCCC(O)=O KPSZWAJWFMFMFF-UHFFFAOYSA-N 0.000 description 1
- KPSZWAJWFMFMFF-NSCUHMNNSA-N delta-heptenoic acid Chemical compound C\C=C\CCCC(O)=O KPSZWAJWFMFMFF-NSCUHMNNSA-N 0.000 description 1
- XUDOZULIAWNMIU-UHFFFAOYSA-N delta-hexenoic acid Chemical compound OC(=O)CCCC=C XUDOZULIAWNMIU-UHFFFAOYSA-N 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- LPLMZAJYUPAYQZ-UHFFFAOYSA-N diazanium;difluoride Chemical compound [NH4+].[NH4+].[F-].[F-] LPLMZAJYUPAYQZ-UHFFFAOYSA-N 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- YCUBDDIKWLELPD-UHFFFAOYSA-N ethenyl 2,2-dimethylpropanoate Chemical compound CC(C)(C)C(=O)OC=C YCUBDDIKWLELPD-UHFFFAOYSA-N 0.000 description 1
- WNMORWGTPVWAIB-UHFFFAOYSA-N ethenyl 2-methylpropanoate Chemical compound CC(C)C(=O)OC=C WNMORWGTPVWAIB-UHFFFAOYSA-N 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- JZRGFKQYQJKGAK-UHFFFAOYSA-N ethenyl cyclohexanecarboxylate Chemical compound C=COC(=O)C1CCCCC1 JZRGFKQYQJKGAK-UHFFFAOYSA-N 0.000 description 1
- GLVVKKSPKXTQRB-UHFFFAOYSA-N ethenyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC=C GLVVKKSPKXTQRB-UHFFFAOYSA-N 0.000 description 1
- LZWYWAIOTBEZFN-UHFFFAOYSA-N ethenyl hexanoate Chemical compound CCCCCC(=O)OC=C LZWYWAIOTBEZFN-UHFFFAOYSA-N 0.000 description 1
- AFSIMBWBBOJPJG-UHFFFAOYSA-N ethenyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC=C AFSIMBWBBOJPJG-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000002462 imidazolines Chemical class 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000011835 investigation Methods 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
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- 230000004224 protection Effects 0.000 description 1
- 150000003236 pyrrolines Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 239000001226 triphosphate Substances 0.000 description 1
- 235000011178 triphosphate Nutrition 0.000 description 1
- 125000002264 triphosphate group Chemical class [H]OP(=O)(O[H])OP(=O)(O[H])OP(=O)(O[H])O* 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- 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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
- C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
- C09D5/084—Inorganic compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- 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
- C23C22/60—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 alkaline aqueous solutions with pH greater than 8
-
- 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
- C23C22/60—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 alkaline aqueous solutions with pH greater than 8
- C23C22/62—Treatment of iron or alloys based thereon
-
- 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
- C23C22/68—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 solutions with pH between 6 and 8
-
- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/10—Metal compounds
- C08K3/11—Compounds containing metals of Groups 4 to 10 or of Groups 14 to 16 of the Periodic Table
-
- 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
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/20—Use of solutions containing silanes
Definitions
- the present invention relates to an aqueous treatment liquid, a chemical conversion treatment method, and a chemical conversion treatment steel sheet.
- the steel plate and the plated steel plate are often used as molded products such as round tubes, square tubes, C channels, H-shaped steels, and L-shaped steels.
- a chemical conversion treatment film may be formed before forming such as bending, welding, and thermal spraying for the purpose of improving galling resistance (pre-coating method).
- pre-coating method there is a possibility that defects may occur in the chemical conversion treatment film during the forming process, and because the end surface generated by cutting the steel sheet cannot be precoated, a chemical conversion treatment film is formed after the forming process, etc.
- post-coating method There is also (post-coating method).
- a base steel plate may be exposed by a forming process etc. with a plating steel plate, and the chemical conversion treatment film
- Patent Document 1 discloses a co-polymer obtained mainly by reacting an acrylic acid or methacrylic acid ester with a vinyl monomer such as styrene and vinyl acetate. An acrylic lacquer in which a coalesced resin or the like is blended is described.
- Patent Document 2 discloses unsaturated alcohols, saturated linear primary amines, saturated linear secondary amines, saturated linear tertiary amines, thioureas, phosphonic acids, morpholine. And an aqueous solution in which an organic corrosion inhibitor selected from imidazolines is dissolved.
- Patent Document 3 describes a solution containing a titanate coupling agent having 3 or more hydrophobic groups having 5 or more carbon atoms.
- Patent Document 1 Since the acrylic lacquer described in Patent Document 1 contains an organic solvent, a process for recovering the volatilized solvent is required. Moreover, since the process liquid of patent document 2 and patent document 3 has a thin film thickness of the chemical conversion treatment film formed, it has poor rust prevention property, and may not be able to maintain the rust prevention effect particularly for a long period of time.
- a chemical conversion treatment film having a thicker film thickness may be formed using an aqueous treatment liquid containing an aqueous organic resin such as an aqueous fluororesin.
- Patent Documents 4 to 8 describe chemical conversion treatment liquids that can increase the water resistance of an organic resin film containing a fluororesin by crosslinking the fluororesin with a compound containing a Group 4 metal.
- JP-A-7-224391 Japanese Patent Laid-Open No. 2003-3280 JP 2005-254106 A International Publication No. 2011/158513 International Publication No. 2011/158516 JP 2012-21207 A JP 2012-177146 A JP 2012-177147 A
- the present invention provides an aqueous treatment liquid capable of forming a chemical conversion treatment film with improved corrosion resistance, a chemical conversion treatment method using the aqueous treatment liquid, and a chemical conversion treatment film formed by the chemical conversion treatment method. It is an object of the present invention to provide a chemical conversion treated steel sheet.
- one embodiment of the present invention relates to an aqueous treatment liquid for chemical conversion treatment of a steel plate or a plated steel plate.
- the aqueous treatment liquid includes an organic resin containing a fluororesin, a group 4A metal compound, dimethyl adipate, diethyl adipate, di (iso) propyl adipate, di (iso) butyl adipate, dimethyl phthalate, diethyl phthalate, di (iso) One or more bond promoters selected from the group consisting of propyl phthalate and di (iso) butyl phthalate.
- the other aspect of this invention is related with the chemical conversion treatment method of a steel plate or a plated steel plate.
- the said chemical conversion treatment method includes the process of providing the aqueous processing liquid for the chemical conversion treatment of a steel plate or a plated steel plate on the surface of a steel plate or a plated steel plate.
- the aqueous treatment liquid includes an organic resin containing a fluororesin, a group 4A metal compound, dimethyl adipate, diethyl adipate, di (iso) propyl adipate, di (iso) butyl adipate, dimethyl phthalate, diethyl phthalate, di (iso) One or more bond promoters selected from the group consisting of propyl phthalate and di (iso) butyl phthalate.
- Still another embodiment of the present invention relates to a chemical conversion treated steel sheet having a steel sheet or a plated steel sheet and a chemical conversion film formed on the surface of the steel sheet or the plated steel sheet.
- the chemical conversion treatment film includes an organic resin containing a fluororesin, a group 4A metal compound, dimethyl adipate, diethyl adipate, di (iso) propyl adipate, di (iso) butyl adipate, dimethyl phthalate, diethyl phthalate, di (iso) One or more bond promoters selected from the group consisting of propyl phthalate and di (iso) butyl phthalate.
- an aqueous treatment liquid capable of forming a chemical conversion treatment film with further improved corrosion resistance, a chemical conversion treatment method using the aqueous treatment liquid, and a chemical conversion treatment steel sheet having a chemical conversion treatment film formed by the chemical conversion treatment method.
- the present inventors further include a specific compound (hereinafter also simply referred to as “binding promoter”) in an aqueous treatment liquid containing an organic resin containing a fluororesin and a group 4A metal compound. And it discovered that the weather resistance of the chemical conversion treatment film formed increased more.
- binding promoter a specific compound
- the present inventors have found that the above-mentioned binding promoters are dimethyl adipate, diethyl adipate, di (iso) propyl adipate, di (iso) butyl adipate, dimethyl phthalate, diethyl
- phthalate, di (iso) propyl phthalate and di (iso) butyl phthalate can be used, thus completing the present invention.
- (iso) propyl means propyl and isopropyl
- (iso) butyl means butyl and isobutyl
- the above binding accelerator can soften the fluororesin that is usually present in the aqueous processing liquid as an emulsion.
- the fluororesin softened by the above bond accelerator is likely to be fused more easily and forms a chemical conversion film having higher water resistance, and thus the weather resistance of the chemical conversion film is considered to be further increased.
- the aqueous treatment liquid contains an organic resin containing a fluororesin, a 4A group metal compound, and the above binding accelerator.
- the aqueous treatment liquid may further contain other components such as an etching agent.
- Organic resin is an organic resin containing a fluororesin.
- the fluororesin can enhance the weather resistance (such as ultraviolet resistance and light resistance) and corrosion resistance (such as prevention of red rust) of the chemical conversion coating.
- the organic resin may contain a resin other than the fluororesin as long as the weather resistance and corrosion resistance of the chemical conversion coating are not significantly reduced.
- Fluororesin is roughly classified into solvent-based fluororesin and water-based fluororesin. Among these, it is preferable to use an aqueous fluororesin that can be easily used for an aqueous treatment liquid in which recovery of the volatilized solvent does not cause a problem.
- An aqueous fluororesin means a fluororesin having a hydrophilic functional group.
- the hydrophilic functional group include a carboxyl group and a sulfonic acid group, and salts thereof.
- the salt of the carboxyl group or sulfonic acid group include ammonium salt, amine salt, alkali metal salt and the like.
- the amount of the hydrophilic functional group in the water-based fluororesin is preferably 0.05% by mass or more and 5% by mass or less.
- a fluororesin having an amount of the hydrophilic functional group of 0.05% by mass or more and 5% by mass or less can be made into an aqueous emulsion without using almost any emulsifier.
- the chemical conversion film containing almost no emulsifier can be a chemical conversion film excellent in water resistance.
- the content of the hydrophilic functional group in the aqueous fluororesin may be determined by dividing the total molar mass of the hydrophilic functional group contained in the aqueous fluororesin by the number average molecular weight of the aqueous fluororesin. Since the molar mass of the carboxyl group is 45 and the molar mass of the sulfonic acid group is 81, the number of each of the carboxyl group and the sulfonic acid group contained in the aqueous fluororesin is determined, and each is multiplied by the molar mass to obtain an aqueous system. The total molar mass of the hydrophilic functional group contained in the fluororesin is obtained. The number average molecular weight of the water-based fluororesin can be measured by GPC.
- the carboxyl group in the water-based fluororesin forms a hydrogen bond with the surface of the steel plate or plating layer (or base chemical conversion coating), and the adhesion between the chemical conversion coating and the surface of the steel plate or plating layer (or base chemical conversion coating).
- H + is difficult to dissociate, a crosslinking reaction with the 4A group metal compound hardly occurs.
- the sulfonic acid group in the water-based fluororesin tends to dissociate H +, but if it remains unreacted in the film without cross-linking reaction with the 4A group metal compound, the chemical conversion treatment film has a strong water molecule adsorption action. There is a possibility that the water resistance of the water may be significantly reduced.
- the water-based fluororesin contains both a carboxyl group and a sulfonic acid group in order to make use of each feature.
- the ratio of the carboxyl group to the sulfonic acid group is preferably in the range of 5 to 60 in terms of the molar ratio of carboxyl group / sulfonic acid group.
- the number average molecular weight of the water-based fluororesin is preferably 1000 or more, more preferably 10,000 or more, and particularly preferably 200,000 or more.
- the lower limit of the number average molecular weight of the water-based fluororesin is the above value, the water permeability and water resistance of the chemical conversion coating can be sufficiently increased, and a steel plate or a steel plate by moisture or corrosive gas penetrating the chemical conversion coating Corrosion of the plated steel sheet can be suppressed.
- the lower limit of the number average molecular weight of the water-based fluororesin is the above value, radicals generated by the action of light energy and the like are unlikely to act on the end of the polymer chain, so the water-based fluororesin is hydrolyzed by a synergistic action such as water.
- the number average molecular weight of the water-based fluororesin is preferably 2 million or less. If the upper limit of the number average molecular weight of the water-based fluororesin is 2 million or less, gelation of the water-based processing solution is difficult to occur, and the storage stability of the water-based processing solution is further increased.
- the water-based fluororesin preferably contains 8% by mass or more of fluorine (F) atoms with respect to the total mass of the fluororesin from the viewpoint of further improving the weather resistance and corrosion resistance of the chemical conversion coating.
- the water-based fluororesin makes it easy to paint, and further improves the adhesion and drying properties of the chemical conversion coating film, so that the fluorine (F) atom is 20% by mass or less based on the total mass of the fluororesin. It is preferable to include.
- the content of fluorine (F) atoms in the aqueous fluororesin can be measured by using a fluorescent X-ray analyzer.
- the water-based fluororesin is preferably a fluorine-containing olefin resin.
- the fluorine-containing olefin resin include a copolymer of a fluoroolefin and a hydrophilic functional group-containing monomer.
- fluoroolefin examples include tetrafluoroethylene, trifluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, vinyl fluoride, vinylidene fluoride, pentafluoropropylene, 2,2,3,3-tetrafluoropropylene, 3 , 3,3-trifluoropropylene, bromotrifluoroethylene, 1-chloro-1,2-difluoroethylene, 1,1-dichloro-2,2-difluoroethylene, and the like. These fluoroolefins may be used alone or in combination of two or more.
- fluoroolefins including tetrafluoroethylene and hexafluoropropylene, vinylidene fluoride, and the like are preferable from the viewpoint of further improving ultraviolet resistance.
- the content of fluoroolefins containing chlorine such as chlorotrifluoroethylene is preferably small (for example, 0.1 mol% or less).
- hydrophilic functional group-containing monomer examples include known carboxyl group-containing monomers and sulfonic acid group-containing monomers. These hydrophilic functional group-containing monomers may be used alone or in combination of two or more.
- carboxyl group-containing monomer examples include unsaturated carboxylic acids represented by the following formula (1), and unsaturated carboxylic acids containing esters or acid anhydrides thereof.
- R 1 , R 2 and R 3 independently represent a hydrogen atom, an alkyl group, a carboxyl group or an ester group.
- N is an integer of 0 to 20
- unsaturated carboxylic acid represented by the above formula (1) include acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, cinnamic acid, itaconic acid, itaconic acid monoester, maleic acid, maleic acid monoester, fumaric acid. Acid, fumaric acid monoester, 5-hexenoic acid, 5-heptenoic acid, 6-heptenoic acid, 7-octenoic acid, 8-nonenoic acid, 9-decenoic acid, 10-undecylene acid, 11-dodecylene acid, 17-octadecylene Acid, oleic acid and the like are included.
- carboxyl group-containing monomer is a carboxyl group-containing vinyl ether monomer represented by the following formula (2).
- R 4 and R 5 independently represent a saturated or unsaturated linear or cyclic alkyl group.
- N is 0 or 1.
- m is 0 or 1.
- carboxyl group-containing vinyl ether monomer represented by the above formula (2) examples include 3- (2-allyloxyethoxycarbonyl) propionic acid, 3- (2-allyloxybutoxycarbonyl) propionic acid, 3- (2- Vinyloxyethoxycarbonyl) propionic acid, 3- (2-vinyloxybutoxycarbonyl) propionic acid, and the like.
- sulfonic acid group-containing monomer examples include vinyl sulfonic acid, allyl sulfonic acid, methallyl sulfonic acid, styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, 2-methacryloyloxyethane sulfonic acid, 3- Methacryloyloxypropanesulfonic acid, 4-methacryloyloxybutanesulfonic acid, 3-methacryloyloxy-2-hydroxypropanesulfonic acid, 3-acryloyloxypropanesulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, isoprenesulfone Acid, and 3-allyloxy-2-hydroxypropanesulfonic acid.
- the copolymer of the fluoroolefin and the hydrophilic functional group-containing monomer may be further copolymerized with another copolymerizable monomer, if necessary.
- the other copolymerizable monomer include carboxylic acid vinyl esters, alkyl vinyl ethers, and non-fluorinated olefins.
- the carboxylic acid vinyl esters can improve the compatibility of the water-based fluororesin and the gloss of the chemical conversion film, and can increase the glass transition temperature.
- the vinyl carboxylates include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate, vinyl versatate, vinyl laurate, vinyl stearate, vinyl cyclohexyl carboxylate, And vinyl benzoate and vinyl para-t-butylbenzoate.
- alkyl vinyl ethers can improve the gloss and flexibility of the chemical conversion coating.
- alkyl vinyl ethers include methyl vinyl ether, ethyl vinyl ether, and butyl vinyl ether.
- the non-fluorinated olefins can improve the flexibility of the chemical conversion coating.
- Examples of the non-fluorinated olefins include ethylene, propylene, n-butene, and isobutene.
- an emulsion of a fluoroolefin copolymer having a hydrophilic functional group can be obtained by copolymerizing the above monomers by an emulsion polymerization method.
- the emulsifier is almost used by adjusting the amount of fluoroolefin in the raw material monomer composition so that the fluoroolefin copolymer has a hydrophilic functional group in an amount of 0.05% by mass or more and 5% by mass or less.
- an aqueous emulsion of a fluoroolefin copolymer can be produced.
- the chemical conversion film formed by using an emulsion of a fluoroolefin copolymer containing almost no emulsifier (1% by mass or less) contains almost no emulsifier and therefore hardly shows deterioration of water resistance due to residual emulsifier. Demonstrates excellent water resistance.
- the average particle size of the fluororesin emulsion is preferably 50 nm or more and 300 nm or less.
- the average particle size of the emulsion is preferably 50 nm or more and 300 nm or less.
- the storage stability of the aqueous treatment liquid can be enhanced.
- the average particle size of the emulsion is set to 300 nm or less, it is possible to increase the surface area of the emulsion to facilitate fusion with each other, and to form a film more easily when baked at a low temperature (for example, 55 ° C.).
- the average particle diameter of the emulsion can be set within the above range by optimizing the shear rate and the stirring time.
- the content of the fluororesin in the aqueous treatment liquid is preferably 10 parts by mass or more and 70 parts by mass or less with respect to 100 parts by mass of water.
- the content of the fluororesin is 10 parts by mass or more, the film formability and denseness of the chemical conversion film are less likely to be deteriorated due to evaporation of a large amount of water during the drying process.
- the content of the fluororesin is 70 parts by mass or less, the storage stability of the aqueous treatment liquid is further increased.
- the content of the fluororesin in the aqueous treatment liquid is preferably 70% by mass or more and 99% by mass or less with respect to the total amount of the solid content (component excluding water and other solvents).
- the Group 4A metal compound easily reacts with a functional group such as a carboxyl group or a sulfonic acid group in a fluororesin, particularly an aqueous fluororesin, and accelerates the curing or crosslinking reaction of the aqueous fluororesin. . Therefore, the group 4A metal compound can improve the water resistance of the chemical conversion coating even at low temperature drying.
- the group 4A metal compound may be a group 4A metal oxyacid salt, fluoride, hydroxide, organic acid salt, carbonate, peroxide salt, ammonium salt, alkali metal salt, alkaline earth metal salt, or the like. it can.
- the oxyacid salt means a salt with an acid (carbonic acid, sulfuric acid, etc.) having oxygen and another element. Examples of oxyacid salts include hydrogenates, carbonates, sulfates, and the like.
- Examples of the group 4A metal compound include a titanium (Ti) compound, a zirconium (Zr) compound, and a hafnium (Hf) compound.
- a zirconium compound is preferable from the viewpoint of suppressing a decrease in weather resistance due to a photocatalyst described later.
- the group 4A metal compound is less likely to cause weathering deterioration of the chemical conversion film due to oxidation and hydrolysis of ester bonds and form ether bonds.
- the 4A group metal compound is less likely to cause weathering deterioration of the chemical conversion film due to the cross-linked structure being cut by an acidic substance such as sulfate ion or nitrate ion contained in acid rain.
- the group 4A metal compound crosslinks the fluororesin with a stronger bonding force than the urethane bond formed at the cross-linked portion using the isocyanate resin, the weather resistance deterioration due to the cutting of the cross-linked structure is less likely to occur.
- the group 4A metal compound improves the film adhesion, water resistance and discoloration resistance of the chemical conversion film.
- a chemical conversion treatment film is formed on the surface of an Al-containing Zn-based alloy-plated steel sheet with an aqueous treatment solution containing a 4A group metal compound
- the decrease in film adhesion due to the strong Al oxide present on the surface of the plated steel sheet is suppressed. can do.
- a chemical conversion treatment film is formed on the surface of an Al-containing Zn-based alloy-plated steel sheet with an aqueous processing solution containing a 4A group metal compound
- Al ions eluted by an etching reaction or the like react with the 4A group metal compound.
- the reaction product is concentrated at the interface between the plating layer and the chemical conversion film, thereby improving the initial corrosion resistance and discoloration resistance of the plated steel sheet.
- the metal-converted content of the group 4A metal compound in the aqueous treatment liquid can be, for example, 0.5 g / L, but the viewpoint of further improving the adhesion of the chemical conversion coating by sufficiently crosslinking the aqueous fluororesin. Is preferably 2 g / L or more. From the above viewpoint, the content of the group 4A metal compound is more preferably 1 g / L or more, and further preferably 2 g / L or more. In addition, from the viewpoint of suppressing deterioration of workability and weather resistance of the chemical conversion coating due to the chemical conversion coating becoming porous, the content of the group 4A metal compound in the aqueous processing solution is 30 g / L or less. It is preferable that The content of the 4A group metal compound in the aqueous treatment liquid in terms of metal can be measured using a fluorescent X-ray analyzer.
- the bond promoter can soften the fluororesin present in the aqueous processing solution.
- the fluororesin that has been softened by the above-mentioned bond promoter makes it easier for the particles constituting the emulsion to be more closely fused together, and forms a chemical conversion film that is less likely to penetrate water. Therefore, it is considered that the chemical conversion treatment film formed from the aqueous treatment liquid containing the binding accelerator is less likely to generate red rust, and the corrosion resistance of the chemical conversion treatment film is further increased.
- the above-mentioned bond promoter can fuse the fluororesin well even at about room temperature due to the above-described action. For this reason, the aqueous processing liquid containing the above-mentioned bond promoter can be easily used without heating at the processing site to the exposed portion of the base steel plate generated by cutting the steel plate or the plated steel plate at the processing site or forming the plated steel plate. A chemical conversion treatment film can be formed.
- dimethyl adipate, diethyl adipate, di (iso) propyl adipate, di (iso) butyl adipate, dimethyl phthalate, diethyl phthalate, di (iso) propyl phthalate, di (iso) butyl phthalate, etc. may be used. it can.
- dimethyl adipate, diethyl adipate, di (iso) propyl adipate and di (iso) butyl adipate are preferred from the viewpoint of corrosion resistance and treated appearance.
- the content of the binding accelerator in the aqueous treatment liquid can be set to, for example, 0.1 g / L or more and 50 g / L or less. From the viewpoint of further improving the corrosion resistance, it is preferably 0.5 g / L or more and 50 g / L or less, more preferably 0.7 g / L or more and 30 g / L or less, and 1 g / L or more and 15 g / L or less. More preferably it is.
- Etching agent makes the surface of a base-material steel plate uniform and activates, improves the adhesiveness of a chemical conversion treatment film, and suppresses the water penetration from a chemical conversion treatment film to a steel plate or a plated steel plate. Therefore, it is considered that the chemical conversion treatment film formed from the aqueous treatment liquid containing the binding accelerator is less likely to generate red rust, and the corrosion resistance of the chemical conversion treatment film is further increased.
- the etching agent dissolves metal components such as Zn and Al contained in the plating layer and Fe contained in the base steel plate, and takes the dissolved metal component into the chemical treatment film, thereby converting the chemical treatment film. Increases the corrosion resistance of the steel sheet or plated steel sheet on which is formed.
- the incorporated metal component is incorporated into the emulsion-like fluororesin by the above-described binding accelerator, and as a result, the adhesion of the chemical conversion film is further improved. It is considered that the corrosion resistance of the formed steel sheet or plated steel sheet is further increased.
- the etching agent is preferably phosphoric acid or phosphate, and ammonia or ammonium salt from the viewpoint of activating the exposed portion of the base steel sheet.
- Phosphoric acid or phosphate homogenizes and activates iron (Fe) in the exposed portion of the base steel sheet and zinc (Zn) contained in the Zn-based plating. Therefore, phosphoric acid or phosphate is particularly useful for steel plates and Zn-based plated steel plates.
- the phosphoric acid or phosphate may be any water-soluble compound having a phosphate anion (PO 4 3 ⁇ ).
- phosphates include sodium phosphate, ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, magnesium phosphate, potassium phosphate, manganese phosphate, zinc phosphate, orthophosphoric acid, metaphosphoric acid, pyrroline Acids, triphosphates, tetraphosphates and the like are included. These phosphoric acids or phosphates may be used alone or in combination of two or more.
- Ammonia acid or ammonium salt homogenizes and activates iron (Fe) in the exposed portion of the base steel sheet and aluminum (Al) contained in the Al-based plating or Zn-Al-based plating. Therefore, phosphoric acid or phosphate is particularly useful for steel plates and Zn—Al-based plated steel plates.
- ammonium salts include phosphates, fluorides and metal salts of quaternary ammonium cations (NH 4 + ). Among these, it is preferable to include a phosphate of a quaternary ammonium cation, and it is more preferable to include ammonium phosphate, ammonium hydrogen phosphate, and ammonium dihydrogen phosphate.
- the etching agent is preferably a phosphate of a quaternary ammonium cation, and more preferably ammonium phosphate, ammonium hydrogen phosphate and ammonium dihydrogen phosphate.
- the content of the etching agent in the aqueous processing liquid is such that the content of phosphate anion (PO 4 3 ⁇ ) is preferably 1 g / L or more, preferably 2 g / L or more in terms of phosphate anion. Further preferred.
- the content of the etching agent in the aqueous processing solution is preferably such that the content of the quaternary ammonium cation (NH 4 + ) is 1 g / L or more in terms of quaternary ammonium cation, 2 g / L. More preferably, it is the above.
- the content of the etching agent in the aqueous processing solution is determined based on phosphate anion (PO 4 3- ) and quaternary ammonium cation (
- the content of (NH 4 + ) is preferably 1 g / L or more and more preferably 2 g / L or more in terms of phosphate anion and quaternary ammonium cation, respectively.
- Water-based treatment liquids may contain other components such as inorganic compounds other than those mentioned above, organic lubricants such as silane coupling agents, inorganic lubricants, inorganic pigments, organic pigments, and dyes as necessary. Also good. Inorganic compounds (oxides, phosphates, etc.) such as Mg, Ca, Sr, V, W, Mn, B, Si, and Sn improve the water resistance by densifying the chemical conversion film. Organic lubricants such as fluorine, polyethylene, and styrene, and inorganic lubricants such as molybdenum disulfide and talc improve the lubricity of the chemical conversion coating. Moreover, predetermined
- content of a vanadium (V) ion and a titanium (Ti) ion is 500 ppm or less in conversion of a metal in an aqueous processing liquid.
- a compound containing V or Ti may be used as a rust preventive, but by reducing the content of these ions, the deterioration of the weather resistance of the chemical conversion coating due to the photocatalytic action of V or Ti is suppressed. be able to.
- the content of chromium (Cr), particularly hexavalent chromium, in the aqueous processing solution is preferably 100 ppm or less in terms of metal.
- the aqueous treatment liquid does not substantially contain an inorganic pigment, an organic pigment, a dye, or the like from the viewpoint of forming a clear film.
- the water-based treatment liquid is mainly composed of fluororesin, phosphate treatment (parkerizing) that forms a phosphate film with a salt such as manganese phosphate or iron phosphate, and a sacrificial anticorrosive layer with a large amount of zinc powder are formed. Unlike zinc rich paint, it can form a clear film.
- content of the silane coupling agent in an aqueous processing liquid is 0.5 mass part or more and 5 mass parts or less with respect to 100 mass parts of fluororesins. It is preferable.
- the adhesiveness of a chemical conversion treatment film can be improved more as content of a silane coupling agent is 0.5 mass part or more.
- the fall of the storage stability of an aqueous processing liquid can be suppressed as content of a silane coupling agent is 5 mass parts or less.
- the aqueous treatment liquid preferably has a solid content (solid content concentration) excluding a solvent such as water of 20% by mass or more based on the total mass of the aqueous treatment liquid. If the solid content is 20% by mass or more, a chemical conversion film having a sufficient film thickness and sufficient weather resistance can be formed. In addition, it is preferable that the upper limit of content of solid content is 40 mass% or less from the surface of process liquid stability.
- the aqueous processing solution preferably has a pH of 7.0 or more and 9.5 or less.
- the pH is 7.0 or more
- the etching amount of Zn can be adjusted moderately
- the pH is 9.5 or less
- the etching amount of Al can be adjusted appropriately. Therefore, when the pH is 7.0 or more and 9.5 or less, it is possible to suppress appearance defects or deterioration of corrosion resistance due to excessive etching.
- the aqueous treatment liquid may be a one-component type or a two-component mixed type in which a fluororesin emulsion and a solution (or dispersion) containing a binding accelerator are mixed at the time of use.
- the chemical treatment method of a steel plate or a plated steel plate The aqueous processing liquid mentioned above can be used for the chemical conversion treatment of a steel plate or a plated steel plate. Specifically, the above-mentioned aqueous treatment liquid can be applied to the surface of a steel plate or a plated steel plate and dried to form a chemical conversion treatment film.
- the type of steel plate is not particularly limited.
- the steel plate may be carbon steel including low carbon steel, medium carbon steel, high carbon steel, or the like, or may be alloy steel containing Mn, Cr, Si, Ni, or the like.
- the steel plate may be killed steel including Al killed steel or rimmed steel.
- a steel sheet for deep drawing including a low carbon Ti-added steel and a low carbon Nb-added steel is preferred as the steel sheet.
- the plated steel plate may be any steel plate with the above steel plate as a base steel plate and subjected to known plating.
- the plating may be hot dip plating or vapor deposition plating.
- the type of plating is not particularly limited, and Zn-based plating (such as Zn plating, Zn—Al plating, and Zn—Al—Mg plating), Al-based plating, and Ni-based plating can be used. Of these, Zn-based plating and Al-based plating are preferable, and Zn-based plating is more preferable.
- steel plates or plated steel plates may be formed products such as round tubes, square tubes, C channels, H-shaped steels, and L-shaped steels.
- the above-mentioned aqueous treatment liquid can form a chemical conversion treatment film having high adhesion on both the various plating layers and the base steel plate, it is applied to a portion of the plated steel plate where the base steel plate is exposed by forming or the like. It is preferable to dry and form a chemical conversion film. Examples of the forming process include drawing, bending, roll forming, shearing, welding, and thermal spraying.
- the plated steel sheet is formed into an open pipe shape by roll forming, and then the end in the width direction of the plated steel sheet is welded.
- a thermal spray repair layer may be formed on the bead cut weld.
- the kind of thermal spraying method and thermal spraying material is not specifically limited, For example, it can be set as the dual spray of Al and Zn, or the triple spray of Al, Zn, and Al.
- the base steel sheet In the welded portion where the plating layer is melted and welded, the base steel sheet is exposed in a relatively wide range, the sacrificial anticorrosive action by the plating layer is lowered, and the corrosion resistance is likely to be lowered.
- the above-described aqueous treatment liquid is applied to such a weld and dried to form a chemical conversion treatment film, the effect of improving corrosion resistance is noticeable.
- the steel sheet or the plated steel sheet may be subjected to a precoat foundation chemical conversion treatment by a known method.
- the method for applying the aqueous treatment liquid is not particularly limited, and may be appropriately selected depending on the shape of the steel plate or the plated steel plate.
- the coating method include a roll coating method, a curtain flow method, a spin coating method, a spray method, a dip-up method, and a dropping method.
- the thickness of the liquid film of the aqueous processing liquid can be adjusted by a felt throttle or an air wiper.
- the coating amount of the aqueous treatment liquid is not particularly limited, but it is preferably adjusted so that the film thickness of the chemical conversion treatment film is 0.5 ⁇ m or more and 10 ⁇ m or less.
- the film thickness of the chemical conversion film is 0.5 ⁇ m or more, weather resistance, corrosion resistance, discoloration resistance, and the like can be sufficiently imparted to the chemical conversion film.
- the film thickness exceeds 10 ⁇ m, it cannot be expected to improve the performance with the increase in film thickness.
- the applied aqueous treatment liquid can be dried at room temperature to form a chemical conversion treatment film.
- the applied aqueous treatment liquid may be dried by heating (for example, heating to 50 ° C. or more), but at this time, from the viewpoint of suppressing the performance deterioration of the chemical conversion film due to thermal decomposition of the organic component, drying is performed.
- the temperature is preferably 300 ° C. or lower.
- from the viewpoint of more easily forming a chemical conversion coating on the exposed part of the base steel sheet which is generated by cutting steel sheets or plated steel sheets, forming steel sheets, etc. Is preferred.
- Chemical conversion treatment steel plate which has a chemical conversion treatment film formed from the above-mentioned aqueous processing liquid has the above-mentioned steel plate or plating steel plate, and the above-mentioned chemical conversion treatment film formed on the surface of the above-mentioned steel plate or plating steel plate.
- the chemical conversion treatment film includes an organic resin containing the above-described fluororesin, the above-described group 4A metal compound, dimethyl adipate, diethyl adipate, di (iso) propyl adipate, di (iso) butyl adipate, And one or more bond promoters selected from the group consisting of dimethyl phthalate, diethyl phthalate, di (iso) propyl phthalate and di (iso) butyl phthalate.
- the content ratio of these components is the same as that described above for the aqueous treatment liquid.
- the film thickness of the chemical conversion coating is preferably 0.5 ⁇ m or more and 10 ⁇ m or less.
- the film thickness is 0.5 ⁇ m or more, weather resistance, corrosion resistance, discoloration resistance, and the like can be sufficiently imparted to the chemical conversion coating.
- the film thickness exceeds 10 ⁇ m, it cannot be expected to improve the performance with the increase in film thickness.
- This chemical conversion treated steel sheet has excellent weather resistance, particularly long-term weather resistance.
- the chemical conversion treatment steel sheet having the chemical conversion treatment film on the exposed portion of the base steel plate caused by the forming process of the plated steel plate, etc. It is preferable because of excellent weather resistance.
- the chemical conversion treated steel sheet having the chemical conversion coating on the welded portion that has been welded by melting the plating layer has a remarkable effect of increasing the corrosion resistance of the welded portion.
- FR fluororesin
- Tg ⁇ 35 to 25 ° C., minimum film forming temperature (MFT): 10 ° C., FR
- MFT minimum film forming temperature
- the acrylic resin (AR) was an acrylic resin emulsion, “Patera Coal” manufactured by DIC Corporation (“Patela Coal” is a registered trademark of the company).
- the solid content concentration of “Pateracol” was 40% by mass, and the average particle size of the emulsion seemed to be about 10 to 100 nm.
- Urethane resin (PU) used was “Hydran” manufactured by DIC Corporation, which is a urethane resin emulsion.
- the solid content concentration of “Hydran” was 35% by mass, and the average particle size of the emulsion seemed to be about 10 to 100 nm.
- the amount of phosphoric acid is adjusted by the total amount of phosphoric acid, diammonium hydrogen phosphate and ammonium dihydrogen phosphate.
- the amount of ammonium is ammonia (aqueous solution), ammonium zirconium carbonate, ammonium ammonium fluoride, phosphoric acid.
- the total amount of diammonium hydrogen, ammonium dihydrogen phosphate and ammonium carbonate was adjusted.
- F amount “F amount”, “Zr amount”, “addition amount”, “phosphoric acid amount”, and “ammonium amount” are the amount of fluorine atom (% by mass) and the metal conversion of the group 4A metal compound, respectively.
- Amount (g / L) addition amount of binding accelerator (g / L), phosphoric acid or phosphate content in terms of phosphate anion (g / L), and ammonia or ammonium salt fourth
- the content (g / L) in terms of quaternary ammonium cation is shown.
- the metal plate a was a steel plate made of plain steel having a thickness of 0.8 mm. A film was formed on the surface of the steel sheet using the aqueous processing solution.
- the metal plate b is a welded plated steel plate in which plated steel plates in which a molten Zn-0.18 mass% Al plating layer (plating adhesion amount 60 g / m 2 ) is formed on the surface of plain steel having a thickness of 0.8 mm are welded together. there were. A film was formed on the exposed portion of the base steel plate in the weld using the aqueous processing solution.
- the metal plate c is made of plated steel plates in which a molten Zn-6.0 mass% Al-3.0 mass% Mg plating layer (plating adhesion amount 60 g / m 2 ) is formed on the surface of plain steel having a thickness of 0.8 mm. It was a welded and plated steel sheet. After welding, a sprayed repaired part was formed on the welded part by double spraying of Al—Zn, and a coating was formed on the sprayed repaired part using the aqueous processing solution.
- a molten Zn-6.0 mass% Al-3.0 mass% Mg plating layer plating adhesion amount 60 g / m 2
- the metal plate d is composed of plated steel plates in which a molten Zn-6.0 mass% Al-3.0 mass% Mg plating layer (plating adhesion amount 60 g / m 2 ) is formed on the surface of plain steel having a thickness of 0.8 mm. It was a work-plated steel sheet that was bent. In the processed portion of the metal plate d, the plating layer was cracked by the processing, and the steel plate was partially exposed. For the straight region arbitrarily provided in this processed part, the steel base length after bending is Y, and the total length of the steel plate parts exposed by bending is X, and the steel sheet exposure is (X / Y) ⁇ 100. When the rate was calculated, the steel plate exposure rate was 20%. A film was formed on the processed part using the aqueous processing solution.
- the metal plate e was a plated steel plate in which a molten Zn-6.0 mass% Al-3.0 mass% Mg plating layer (plating adhesion amount 60 g / m 2 ) was formed on the surface of plain steel with a thickness of 0.8 mm. .
- a film was formed on the end face of the plated steel sheet on the exposed part of the base steel sheet using the aqueous processing solution.
- Aqueous treatment liquid 1 to aqueous treatment liquid 19 were applied to the above-described evaluation sites of metal plate a to metal plate e, and the aqueous treatment liquid applied at the temperatures shown in the following table was dried to form a film. .
- Evaluation-1 A test piece including the evaluation part was cut out from the metal plate a, and the adhesion, weather resistance, and corrosion resistance of the film formed on the test piece were evaluated according to the following criteria.
- the film peeling area ratio (PA) of the cellophane tape peeling test was measured, and the adhesiveness was evaluated according to the following criteria.
- a The film peeling area rate was 5% or less
- B The film peeling area rate was more than 5% and 10% or less
- D The film peeling area rate was more than 10
- Aqueous treatment solutions 1 to 19 were stored at room temperature for 180 days.
- the amount of change in viscosity before and after storage of each aqueous processing solution (the value obtained by subtracting the viscosity before storage from the viscosity after storage) was measured by Ford Cup No. 4, and the storage stability was evaluated according to the following criteria.
- a Change in viscosity was less than 10 seconds
- B Change in viscosity was more than 10 seconds, but there was no problem in use
- Table 3 shows the drying temperature, the film thickness, and the adhesion, weather resistance, and corrosion resistance when the aqueous treatment liquid 1 to the aqueous treatment liquid 19 are applied.
- the weather resistance is further improved. There was a trend of higher corrosion resistance.
- an aqueous treatment liquid 1 to an aqueous treatment liquid 3 an aqueous treatment liquid 5 to an aqueous treatment liquid 14 and an aqueous treatment liquid 19 in which the content in terms of metal of the group 4A metal compound in the aqueous treatment liquid is 2 g / L or more.
- the chemical conversion treatment film was formed using the adhesive, the adhesion became higher.
- the chemical conversion treatment is performed using the aqueous treatment liquid 1 to the aqueous treatment liquid 4, the aqueous treatment liquid 6 to the aqueous treatment liquid 14, and the aqueous treatment liquid 19 in which the content of the binding accelerator is 0.5 g / L or more and 50 g / L or less.
- the corrosion resistance became higher.
- the aqueous treatment liquid 1 to the aqueous treatment liquid 4, the aqueous treatment liquid 6 to the aqueous treatment liquid 13 and the aqueous treatment liquid 19 in which the content of the binding accelerator is 20 g / L or less is stored stably even when the one-component type is used. The nature was high.
- Evaluation-2 A test piece including the above-mentioned evaluation part was cut out from the metal plate b to the metal plate e, and the corrosion resistance of the film formed on the test piece was evaluated according to the following criteria.
- Corrosion resistance 2 An accelerated weather resistance test (xenon lamp method) was performed in accordance with JIS K 5600-7-7: 2008. In this test method, the process of spraying water for 18 minutes while irradiating light from a xenon arc lamp for 120 minutes was defined as one cycle (2 hours). After 100 cycles of the accelerated weathering test, the sample was exposed to the atmosphere for 1 month. The area ratio of red rust generated on the surface of the test piece was measured, the red rust generation area ratio (WR) was determined, and the corrosion resistance was evaluated according to the following criteria.
- the area ratio of red rust was 10% or less B + The area ratio of red rust was more than 10% and less than 20% B- The area ratio of red rust was more than 20% and less than 30% C The area ratio of red rust was more than 30% 50 D Red rust area ratio was over 50%
- Table 4 shows the drying temperature, film thickness, and corrosion resistance when the aqueous treatment liquid 1 to the aqueous treatment liquid 18 were applied.
- the chemical conversion coating produced by the aqueous treatment liquid of the present invention can further improve the corrosion resistance of the steel plate and the plated steel plate, particularly the plated steel plate, where the base steel plate is exposed by forming or the like.
- the water-based treatment liquid of the present invention includes: 1) steel pipes for steelhouses, agricultural houses, columns, columns, beams, conveying members, 2) sound insulation walls, sound insulation walls, sound absorption walls, snow walls, guardrails, railings, protection Fences, pillars, 3) Railcar members, overhead wire members, electrical equipment members, safety environment members, structural members, chemical conversion coatings by post-coating on steel plates or plated steel plates used for solar mounts, etc. It can be used suitably for formation of.
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Abstract
Description
上記水系処理液は、フッ素樹脂を含む有機樹脂、4A族金属化合物および上記結合促進剤を含む。上記水系処理液は、エッチング剤などのその他の成分をさらに含んでもよい。
有機樹脂は、フッ素樹脂を含む有機樹脂である。フッ素樹脂は、化成処理皮膜の耐候性(耐紫外線性および耐光性など)および耐食性(赤錆の防止など)を高めることができる。なお、有機樹脂は、化成処理皮膜の耐候性および耐食性を顕著に低下させない限りにおいて、フッ素樹脂以外の樹脂を含んでもよい。
4A族金属化合物は、フッ素樹脂、特には水系フッ素樹脂中のカルボキシル基やスルホン酸基などの官能基と反応しやすく、水系フッ素樹脂の硬化または架橋反応を促進する。そのため、4A族金属化合物は、低温乾燥でも化成処理皮膜の耐水性を向上させることができる。
結合促進剤は、水系処理液中に存在するフッ素樹脂を軟質化することができる。上記結合促進剤によって軟質化したフッ素樹脂は、エマルションを構成する粒子同士がより密に融着しやすくなり、より水を浸透しにくい化成処理皮膜を形成する。そのため、結合促進剤を含む上記水系処理液から形成された化成処理皮膜は赤錆を発生させにくくなり、化成処理皮膜の耐食性がより高まると考えられる。
エッチング剤は、基材鋼板の表面を均一化および活性化して、化成処理皮膜の密着性をより高め、化成処理皮膜から鋼板またはめっき鋼板への水の浸透を抑制する。そのため、結合促進剤を含む上記水系処理液から形成された化成処理皮膜は赤錆を発生させにくくなり、化成処理皮膜の耐食性がより高まると考えられる。
水系処理液は、その他の成分として、上述以外の無機化合物、シランカップリング剤などの有機潤滑剤、無機潤滑剤、無機顔料、有機顔料、および染料などを必要に応じて添加してもよい。Mg、Ca、Sr、V、W、Mn、B、Si、Snなどの無機化合物(酸化物、リン酸塩など)は、化成処理皮膜を緻密化して耐水性を向上させる。フッ素系、ポリエチレン系、およびスチレン系などの有機潤滑剤、ならびに二硫化モリブデンおよびタルクなどの無機潤滑剤は、化成処理皮膜の潤滑性を向上させる。また、無機顔料、有機顔料、および染料などを配合することで、化成処理皮膜に所定の色調を付与することができる。
水系処理液は、水などの溶媒を除く固形分の含有量(固形分濃度)が、水系処理液の全質量に対して20質量%以上であることが好ましい。固形分の含有量が20質量%以上であると、十分な膜厚を有し、十分な耐候性を有する化成処理皮膜を形成できる。なお、固形分の含有量の上限は処理液安定性の面から、40質量%以下であることが好ましい。
上述した水系処理液は、鋼板またはめっき鋼板の化成処理に用いることができる。具体的には、上述した水系処理液を、鋼板またはめっき鋼板の表面に付与し、乾燥させて、化成処理皮膜を形成することができる。
上述の水系処理液から形成された化成処理皮膜を有する化成処理鋼板は、上述の鋼板またはめっき鋼板と、上記鋼板またはめっき鋼板の表面に形成された上記化成処理皮膜と、を有する。
各成分を混合して、表1に示す水系処理液1~水系処理液19を調製した。
表2に示す金属板a~金属板eを用意した。
金属板a~金属板eの上述した評価部位に、水系処理液1~水系処理液19を塗布し、以下の表に示す温度で塗布した水系処理液を乾燥させて皮膜を形成した。
金属板aから上記評価部位を含む試験片を切り出して、試験片に形成した皮膜の密着性、耐候性および耐食性を以下の基準で評価した。
試験片を4t曲げした後、セロハンテープ剥離試験の皮膜剥離面積率(PA)を測定し、以下の基準で密着性を評価した。
A 皮膜剥離面積率は5%以下だった
B 皮膜剥離面積率は5%超10%以下だった
C 皮膜剥離面積率は10超50%以下だった
D 皮膜剥離面積率は50%超だった
JIS K 5600-7-7:2008に準拠して促進耐候性試験(キセノンランプ法)を実施した。本試験法では、キセノンアーク灯の光を120分間照射する間に18分間水を噴霧する工程を1サイクル(2時間)とした。100サイクルの試験後に光沢度を測定し、試験後の測定を試験前の光沢度と比較して光沢保持率(RG60)を算出して、以下の基準で耐候性を評価した。
A 光沢保持率は90%以上だった
B 光沢保持率は80%以上90%未満だった
C 光沢保持率は60%以上80%未満だった
D 光沢保持率は60%未満だった
試験片の端面をシールし、上記促進耐候性試験400サイクルの試験後に、大気に1ヶ月間暴露した。試験片表面に発生している赤錆の面積率を測定し、赤錆発生面積率(WR)を求めて、以下の基準で耐食性を評価した。
A 赤錆発生面積率は10%以下だった
B+ 赤錆発生面積率は10%超20%以下だった
B- 赤錆発生面積率は20%超30%以下だった
C 赤錆発生面積率は30%超50%以下だった
D 赤錆発生面積率は50%超だった
水系処理液1~水系処理液19を常温で180日間保管した。各水系処理液の保管前後の粘度変化量(保管後粘度から保管前粘度を差し引いた値)をフォードカップNo.4により測定し、以下の基準で保存安定性を評価した。
A 粘度変化量は10秒未満だった
B 粘度変化量は10秒以上だったが、使用に問題はなかった
C 粘度変化量は30秒以上であり、増粘により塗布が困難だった
金属板b~金属板eから上記評価部位を含む試験片を切り出して、試験片に形成した皮膜の耐食性を以下の基準で評価した。
JIS K 5600-7-7:2008に準拠して促進耐候性試験(キセノンランプ法)を実施した。本試験法では、キセノンアーク灯の光を120分間照射する間に18分間水を噴霧する工程を1サイクル(2時間)とした。上記促進耐候性試験100サイクルの試験後に、大気に1ヶ月間暴露した。試験片表面に発生している赤錆の面積率を測定し、赤錆発生面積率(WR)を求めて、以下の基準で耐食性を評価した。
A 赤錆発生面積率は10%以下だった
B+ 赤錆発生面積率は10%超20%以下だった
B- 赤錆発生面積率は20%超30%以下だった
C 赤錆発生面積率は30%超50%以下だった
D 赤錆発生面積率は50%超だった
Claims (13)
- フッ素樹脂を含む有機樹脂と、
4A族金属化合物と、
ジメチルアジペート、ジエチルアジペート、ジ(イソ)プロピルアジペート、ジ(イソ)ブチルアジペート、ジメチルフタレート、ジエチルフタレート、ジ(イソ)プロピルフタレートおよびジ(イソ)ブチルフタレートからなる群から選択される1以上の結合促進剤と、
を含む、鋼板またはめっき鋼板の化成処理用の水系処理液。 - 前記フッ素樹脂は、前記フッ素樹脂の全質量に対して8質量%以上のフッ素原子を含む、請求項1に記載の水系処理液。
- 前記4A族金属化合物の含有量は、金属換算で2g/L以上である、請求項1または2に記載の水系処理液。
- 前記結合促進剤の含有量は0.5g/L以上50g/L以下である、請求項1~3のいずれか1項に記載の水系処理液。
- リン酸およびリン酸塩、ならびにアンモニアおよびアンモニウム塩、からなる群から選択されるエッチング剤をさらに含む、請求項1~4のいずれか1項に記載の水系処理液。
- 前記エッチング剤は、リン酸またはリン酸塩と、アンモニアまたはアンモニウム塩と、をいずれも含む、請求項5に記載の水系処理液。
- 前記リン酸またはリン酸塩の含有量は、リン酸アニオン(PO4 3-)換算で1g/L以上であり、かつ、前記アンモニアまたはアンモニウム塩の含有量は、第四級アンモニウムカチオン(NH4 +)換算で1g/L以上である、請求項6に記載の水系処理液。
- 固形分の含有量は20%以上である、請求項1~7のいずれか1項に記載の水系処理液。
- pHは7.0以上9.5以下である、請求項1~8のいずれか1項に記載の水系処理液。
- 鋼板またはめっき鋼板の表面に、請求項1~9のいずれか1項に記載の水系処理液を付与する工程を含む、
鋼板またはめっき鋼板の化成処理方法。 - 前記水系処理液は、めっき鋼板の、基材鋼板が露出した部位に付与される、請求項10に記載の化成処理方法。
- 鋼板またはめっき鋼板と、
前記鋼板またはめっき鋼板の表面に形成された化成処理皮膜と、を有する化成処理鋼板であって、
前記化成処理皮膜は、
フッ素樹脂を含む有機樹脂と、
4A族金属化合物と、
ジメチルアジペート、ジエチルアジペート、ジ(イソ)プロピルアジペート、ジ(イソ)ブチルアジペート、ジメチルフタレート、ジエチルフタレート、ジ(イソ)プロピルフタレートおよびジ(イソ)ブチルフタレートからなる群から選択される1以上の結合促進剤と、
を含む、化成処理鋼板。 - 前記化成処理皮膜は、めっき鋼板の、基材鋼板が露出した部位に形成された、請求項12に記載の化成処理鋼板。
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RU2019134310A (ru) | 2021-05-26 |
CN110621808A (zh) | 2019-12-27 |
CN110621808B (zh) | 2022-07-08 |
BR112019022366A2 (pt) | 2020-05-19 |
US11280004B2 (en) | 2022-03-22 |
US20200087792A1 (en) | 2020-03-19 |
CA3061033A1 (en) | 2019-10-22 |
KR20190139905A (ko) | 2019-12-18 |
TW201839075A (zh) | 2018-11-01 |
AU2017411563A1 (en) | 2019-11-07 |
EP3617345A4 (en) | 2020-04-29 |
AU2017411563B2 (en) | 2023-05-11 |
KR102363972B1 (ko) | 2022-02-15 |
TWI699407B (zh) | 2020-07-21 |
RU2019134310A3 (ja) | 2021-05-26 |
MX2019012828A (es) | 2020-02-03 |
JP6271062B1 (ja) | 2018-01-31 |
EP3617345A1 (en) | 2020-03-04 |
JP2018184638A (ja) | 2018-11-22 |
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