JP2006225737A - 耐食性及び耐黒変性に優れたリン酸塩処理亜鉛めっき鋼板 - Google Patents
耐食性及び耐黒変性に優れたリン酸塩処理亜鉛めっき鋼板 Download PDFInfo
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- 229910001335 Galvanized steel Inorganic materials 0.000 title claims abstract description 39
- 239000008397 galvanized steel Substances 0.000 title claims abstract description 39
- 238000005260 corrosion Methods 0.000 title claims abstract description 34
- 230000007797 corrosion Effects 0.000 title claims abstract description 34
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 38
- 239000010959 steel Substances 0.000 claims abstract description 38
- 229910019142 PO4 Inorganic materials 0.000 claims description 73
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 73
- 239000010452 phosphate Substances 0.000 claims description 73
- 238000005246 galvanizing Methods 0.000 abstract description 19
- 239000010410 layer Substances 0.000 description 116
- 238000011282 treatment Methods 0.000 description 83
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 61
- 238000000034 method Methods 0.000 description 41
- 239000000243 solution Substances 0.000 description 29
- 238000012360 testing method Methods 0.000 description 29
- 239000011701 zinc Substances 0.000 description 28
- 238000007747 plating Methods 0.000 description 21
- 238000007789 sealing Methods 0.000 description 18
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 15
- 229910052725 zinc Inorganic materials 0.000 description 15
- 239000007864 aqueous solution Substances 0.000 description 13
- 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 9
- 229910000165 zinc phosphate Inorganic materials 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 229910001425 magnesium ion Inorganic materials 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000007598 dipping method Methods 0.000 description 5
- 239000003973 paint Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 238000005238 degreasing Methods 0.000 description 4
- 238000009713 electroplating Methods 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- -1 zircon compound Chemical class 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 3
- 239000004566 building material Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- JOSWYUNQBRPBDN-UHFFFAOYSA-P ammonium dichromate Chemical compound [NH4+].[NH4+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O JOSWYUNQBRPBDN-UHFFFAOYSA-P 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000003750 conditioning effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 229910000457 iridium oxide Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007739 conversion coating Methods 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- RZLVQBNCHSJZPX-UHFFFAOYSA-L zinc sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Zn+2].[O-]S([O-])(=O)=O RZLVQBNCHSJZPX-UHFFFAOYSA-L 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
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- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/26—After-treatment
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- 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
- C23C22/07—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 phosphates
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—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 phosphates
- C23C22/08—Orthophosphates
- C23C22/12—Orthophosphates containing zinc cations
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- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/78—Pretreatment of the material to be coated
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- 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
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- 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
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- 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
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
- C23C28/3225—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only with at least one zinc-based layer
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- 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
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
- C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
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Abstract
【解決手段】 鋼板表面に、亜鉛めっき層と、亜鉛めっき層の上層としてりん酸塩処理層とを有し、さらに亜鉛めっき層とりん酸塩処理層との中間に0.1〜500 mg/m2のNi付着部を介在させためっき層構造とする。これにより、耐食性及び耐黒変性に優れたリン酸塩処理亜鉛めっき鋼板となる。なお、リン酸塩処理層はMgを0.1質量%以上2.0質量%未満含有することが好ましい。
【選択図】 なし
Description
リン酸塩処理は、リン酸イオンを含有した酸性溶液と亜鉛系めっき鋼板とを接触させ、反応させてリン酸亜鉛を主成分とする結晶性皮膜をめっき表面に形成させる処理であり、塗膜との密着性を向上させ、各種塗装に対して安定した塗装下地性能を有する。このため、リン酸塩処理を施された亜鉛系めっき鋼板は、建材用、家電用等の塗装用下地鋼板として幅広く使用されてきた。
また、特許文献4には、リン酸亜鉛皮膜が、Mgを2%以上、Ni、Co、Cuから選ばれた1種以上の元素を0.01〜1%含有し,付着量が0.7g/m2以上である耐食性および色調に優れたリン酸亜鉛処理亜鉛系めっき鋼板が提案されている。
また、リン酸塩処理層の付着量は、耐食性及び十分な塗料密着性を確保するために、0.2g/m2以上とすることが好ましく、より好ましくは1.0g/m2以上、さらに好ましくは1.5g/m2以上である。なお、付着量の増加による上記した効果は、3g/m2以上では飽和するために、3g/m2を上限とすることが好ましい。
本発明では、基板とする鋼板に、鋼板の少なくとも一方の面に亜鉛めっき層を形成する亜鉛めっき処理工程と、前記亜鉛めっき層の表面に微量のNi付着部を形成するNi付着部形成処理工程と、前記亜鉛めっき層の上層として、該Ni付着部のうえにリン酸塩処理層を形成するリン酸塩処理工程と、を順次施す。
亜鉛めっき処理工程における亜鉛めっき層の形成手段としては、真空蒸着法、溶融めっき法及び電気めっき法などが例示できるが、本発明の亜鉛めっき処理工程においては、電気めっき法もしくは溶融めっき法を用いて、電気亜鉛めっき処理工程もしくは溶融亜鉛めっき処理工程とすることが好ましい。以下、電気めっき法を用いる場合を例として説明する。
亜鉛めっき浴としては、通常の純亜鉛めっき層を形成する亜鉛めっき浴である、硫酸亜鉛溶液、塩化亜鉛溶液等が、いずれも好適に利用でき、とくに限定する必要はない。また、亜鉛めっき層の付着量に応じ、電流密度等の通電条件を調整することはいうまでもない。なお、亜鉛めっき層の付着量は、1〜100g/m2の範囲とすることが耐食性、耐めっき剥離性の観点から好ましい。
本発明では、亜鉛めっき処理工程後でリン酸塩処理工程前に、Ni付着部形成処理工程を施す。Ni付着部形成処理工程では、亜鉛めっき処理工程により表面に亜鉛めっき層を形成された鋼板をNiイオンを含有する水溶液に接触させて亜鉛めっき層の表面にNiを置換析出させるか、あるいはより積極的に、前記亜鉛めっき層を形成した鋼板を陰極としてNiイオンを含有する水溶液中で電解し亜鉛めっき層の表面にNiを置換析出させることにより、微量のNi付着部を形成することが好ましい。Ni付着部形成処理工程で使用するNiイオンを含有する水溶液としては、塩化ニッケルや硫酸ニッケルなどの水溶液が適用できる。なお、Ni付着量に応じて、適宜水溶液中のNi濃度や、液温、接触時間、あるいは電解条件等を変化させることが好ましい。
つぎに、実施例に基づき本発明をさらに詳細に説明する。
440 g/Lの硫酸亜鉛7水和物を添加した亜鉛めっき液を用いて亜鉛めっき浴とした。亜鉛めっき液は硫酸を添加してpH:1.5に調整した。なお、亜鉛めっき浴の浴温は50℃とした。上記した亜鉛めっき浴中で、酸化イリジウム被覆Ti板電極を対極とし、該対極を、試験板と極間距離10mmで平行に配置し、極間に流速1.5m/sでめっき液を循環させながら、電流密度70A/dm2で通電した。
Ni付着部形成処理はつぎのとおりとした。
表面に亜鉛めっき層を形成された試験片を、10g/Lの硫酸ニッケル水溶液(40℃)に1〜10秒間浸漬するか、もしくは、酸化イリジウム被覆Ti板電極を対極として、該対極と試験片を平行に配置し、電流密度:5A/dm2で通電し、電解して、所定量のNiを析出させNi付着部を形成した。なお、Ni付着量は、浸漬時間または電解時間を変化させて調整した。
リン酸塩処理は、亜鉛めっき層のうえにNi付着部を形成した鋼板に、リン酸亜鉛処理液(日本パーカライジング(株)製:商品名「PB3312M」に硝酸Mgを添加したもの;Zn濃度:3.5g/L、液温:60℃、pH:2.2)をスプレーして接触させ、水洗、乾燥して、リン酸塩処理層を形成し、亜鉛めっき層とリン酸塩処理層との中間にNi付着部を介在させてなるリン酸塩処理亜鉛めっき鋼板(試験板)とした。なお、リン酸塩処理液中に添加するMg源の添加量を変化して、リン酸塩処理層中のMg量を変化させた。また、リン酸塩処理層の付着量はリン酸塩処理液との接触時間を変えて変化させた。
(1)亜鉛めっき層、Ni付着部、及びりん酸塩処理層の付着量
亜鉛めっき層中のめっき付着量及び亜鉛めっき層の上に形成されたNi付着部の付着量は、亜鉛めっき処理後にNiを析出付着させ表面にNi付着部を形成された亜鉛めっき層について、JIS H 0401-1999に規定された付着量試験方法に準拠して、ヘキサメチレンテトラミン液に溶解させ、めっき層が溶解した液を、JIS K 0121-1993に規定された電気加熱方式原子吸光分析装置にて分析して求めた。リン酸塩処理層の付着量は重クロム酸アンモニウム水溶液で溶解して重量法で求めた。またリン酸塩処理層中のMg含有量は、リン酸塩処理層を重クロム酸アンモニウム水溶液で溶解し、その溶解液をICP分析(誘起結合プラズマ発光分析)により分析して求めた。
(2)耐食性
得られた試験板から、試験片(大きさ:100×50mm)を切り出し、試験片の端部及び裏面をテープシールした後、JIS Z 2371-2000の規定に準拠して塩水噴霧試験を実施した。試験中、定期的に試験片表面を観察し、試験片の全評価面積に対し白錆発生面積が5%になるまでの時間(白錆発生時間)を調べ、耐食性を評価した。白錆発生時間が、24時間以上である場合を◎、24時間未満8時間以上である場合を○、8時間未満4時間以上である場合を△、4時間未満である場合を×とした。
(3)耐黒変性
得られた試験板から、試験片(大きさ:100×50mm)を切り出し、分光式色差計SQ2000(日本電色製)を用いて、まず、試験片の初期のL値(明度)を測定した。ついで、試験片を、温度80℃、湿度95%RHの恒温恒湿槽中に24時間放置した。放置後、試験片のL値を同様に測定し、L値(初期値)からのL値の変化量ΔLを求めた。ΔLが、−1以上である場合を◎、−1未満−2以上である場合を○、−2未満−4以上である場合を△、−4未満である場合を×として耐黒変性を評価した。
Claims (2)
- 鋼板の少なくとも一方の面に亜鉛めっき層と該亜鉛めっき層の上層としてりん酸塩処理層を有するりん酸塩処理亜鉛めっき鋼板であって、前記亜鉛めっき層とりん酸塩処理層との中間に0.1〜500mg/m2のNi付着部を形成してなることを特徴とする耐食性及び耐黒変性に優れたりん酸塩処理亜鉛めっき鋼板。
- 前記りん酸塩処理層が、Mgを0.1質量%以上2.0質量%未満含有することを特徴とする請求項1に記載のりん酸塩処理亜鉛めっき鋼板。
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CN2006800013202A CN101068951B (zh) | 2005-02-18 | 2006-02-16 | 耐腐蚀性和耐黑变性优良的磷酸盐处理镀锌钢板 |
KR1020077008720A KR20070061880A (ko) | 2005-02-18 | 2006-02-16 | 내식성 및 내흑변성이 뛰어난 인산염처리 아연도금강판 |
PCT/JP2006/303204 WO2006088225A1 (ja) | 2005-02-18 | 2006-02-16 | 耐食性及び耐黒変性に優れたリン酸塩処理亜鉛めっき鋼板 |
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JPH01222065A (ja) * | 1988-03-02 | 1989-09-05 | Nisshin Steel Co Ltd | 溶融めっき鋼板の表面処理方法 |
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JPH01312081A (ja) * | 1988-06-09 | 1989-12-15 | Kobe Steel Ltd | 表面処理金属材料 |
JPH0813154A (ja) * | 1994-06-27 | 1996-01-16 | Nippon Parkerizing Co Ltd | 塗装性に優れた亜鉛含有金属めっき鋼板複合体、およびその製造方法 |
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