WO2022138005A1 - 表面処理鋼板およびその製造方法 - Google Patents
表面処理鋼板およびその製造方法 Download PDFInfo
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- WO2022138005A1 WO2022138005A1 PCT/JP2021/043710 JP2021043710W WO2022138005A1 WO 2022138005 A1 WO2022138005 A1 WO 2022138005A1 JP 2021043710 W JP2021043710 W JP 2021043710W WO 2022138005 A1 WO2022138005 A1 WO 2022138005A1
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- Prior art keywords
- steel sheet
- layer
- metal
- treated steel
- less
- Prior art date
Links
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 171
- 239000010959 steel Substances 0.000 title claims abstract description 171
- 238000004519 manufacturing process Methods 0.000 title claims description 19
- 239000011651 chromium Substances 0.000 claims abstract description 205
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 99
- 229910052751 metal Inorganic materials 0.000 claims abstract description 84
- 239000002184 metal Substances 0.000 claims abstract description 84
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 19
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 18
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 18
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 18
- 238000005868 electrolysis reaction Methods 0.000 claims description 61
- 239000008151 electrolyte solution Substances 0.000 claims description 60
- 238000000034 method Methods 0.000 claims description 55
- 238000011282 treatment Methods 0.000 claims description 55
- 238000005406 washing Methods 0.000 claims description 50
- -1 carboxylic acid compound Chemical class 0.000 claims description 16
- 229910001430 chromium ion Inorganic materials 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 8
- 230000007797 corrosion Effects 0.000 abstract description 45
- 238000005260 corrosion Methods 0.000 abstract description 45
- 239000003973 paint Substances 0.000 abstract description 22
- 239000011248 coating agent Substances 0.000 abstract description 16
- 238000000576 coating method Methods 0.000 abstract description 16
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 abstract description 15
- 239000010410 layer Substances 0.000 description 129
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 30
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 17
- 239000007864 aqueous solution Substances 0.000 description 17
- 238000012360 testing method Methods 0.000 description 14
- 229910052804 chromium Inorganic materials 0.000 description 12
- 229910000576 Laminated steel Inorganic materials 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 9
- 238000001228 spectrum Methods 0.000 description 9
- 239000005029 tin-free steel Substances 0.000 description 9
- 239000011347 resin Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 238000005554 pickling Methods 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 238000005238 degreasing Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical group [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 230000007246 mechanism Effects 0.000 description 5
- 230000035945 sensitivity Effects 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000004544 sputter deposition Methods 0.000 description 4
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 230000003746 surface roughness Effects 0.000 description 3
- 239000002335 surface treatment layer Substances 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 238000000441 X-ray spectroscopy Methods 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 235000013361 beverage Nutrition 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- 239000010960 cold rolled steel Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000002788 crimping Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 229910000457 iridium oxide Inorganic materials 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000000851 scanning transmission electron micrograph Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000012085 test solution Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001734 carboxylic acid salts Chemical class 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- DSHWASKZZBZKOE-UHFFFAOYSA-K chromium(3+);hydroxide;sulfate Chemical compound [OH-].[Cr+3].[O-]S([O-])(=O)=O DSHWASKZZBZKOE-UHFFFAOYSA-K 0.000 description 1
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 description 1
- 229910000356 chromium(III) sulfate Inorganic materials 0.000 description 1
- 235000015217 chromium(III) sulphate Nutrition 0.000 description 1
- 239000011696 chromium(III) sulphate Substances 0.000 description 1
- 238000007621 cluster analysis Methods 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 201000003373 familial cold autoinflammatory syndrome 3 Diseases 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 235000009973 maize Nutrition 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N perisophthalic acid Natural products OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000010731 rolling oil Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/38—Chromatising
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/04—Electroplating: Baths therefor from solutions of chromium
- C25D3/06—Electroplating: Baths therefor from solutions of chromium from solutions of trivalent chromium
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- 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
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
- C25D5/36—Pretreatment of metallic surfaces to be electroplated of iron or steel
Definitions
- the present invention relates to a surface-treated steel sheet, and more particularly to a surface-treated steel sheet which is excellent in corrosion resistance in a laminated state and a coated state of a resin film and also has excellent adhesion to a resin film and a coating film in a wet environment.
- the surface-treated steel sheet of the present invention can be suitably used for containers such as cans.
- the present invention also relates to a method for manufacturing the surface-treated steel sheet.
- Sn-plated steel plate (buriki) has excellent corrosion resistance, weldability, workability, and is easy to manufacture, so it has been used as a material for various metal cans such as beverage cans, food cans, pail cans, and 18-liter cans for 200 years. It has been used over the above.
- tin-free steel sheet which is a surface-treated steel sheet that does not use Sn
- the tin-free steel sheet is a surface-treated steel sheet in which a metal Cr layer and an oxide Cr layer are formed on the surface of the steel sheet, and is usually manufactured by electrolytically treating the steel sheet in an electrolytic solution containing hexavalent Cr (Patent Document). 1-3). Tin-free steel sheets are now very commonly used as container steel sheets to replace tinplate because they have excellent corrosion resistance and paint adhesion.
- the methods proposed in Patent Documents 4 and 5 are known.
- the surface treatment layer is formed by performing an electrolytic treatment in an electrolytic solution containing a trivalent chromium compound such as basic chromium sulfate.
- the surface treatment layer can be formed without using hexavalent chromium.
- film wet adhesion the adhesion to the resin film in a wet environment
- paint 2 the adhesion to the paint in a wet environment
- the surface-treated steel sheet obtained by the conventional method as proposed in Patent Documents 4 and 5 is excellent in film wet adhesion and paint secondary adhesion, but has corrosion resistance in a state of being coated with a resin film ( Hereinafter, it is inferior in corrosion resistance in a coated state (hereinafter referred to as "coating corrosion resistance”) and "film corrosion resistance”), and can be used as a substitute for a tin-free steel sheet manufactured by a method using hexavalent chromium. The performance was not enough.
- the present invention has been made in view of the above circumstances, and an object thereof is that it can be produced without using hexavalent chromium, and has excellent film wet adhesion and paint secondary adhesion. It is an object of the present invention to provide a surface-treated steel sheet having both film corrosion resistance and coating corrosion resistance.
- the surface-treated steel sheet is subjected to cathodic electrolytic treatment using an electrolytic solution containing trivalent chromium ions prepared by a specific method, and then finalized with water having an electric conductivity of a predetermined value or less. It can be manufactured by washing with water.
- the present invention has been completed based on the above findings.
- the gist of the present invention is as follows.
- a surface-treated steel sheet having a steel sheet, a metal Cr layer arranged on at least one surface of the steel sheet, and an oxide Cr layer arranged on the metal Cr layer.
- the water contact angle is 50 ° or less
- a surface-treated steel sheet having a total atomic ratio of K, Na, Mg, and Ca adsorbed on the surface to Cr of 5% or less.
- the electrolytic solution preparation step Mix trivalent chromium ion source, carboxylic acid compound, and water, The electrolytic solution was prepared by adjusting the pH to 4.0 to 7.0 and the temperature to 40 to 70 ° C.
- the washing step A method for producing a surface-treated steel sheet, which uses water having an electric conductivity of 100 ⁇ S / m or less at least in the final washing with water.
- the present invention it is possible to provide a surface-treated steel sheet having excellent film wet adhesion and paint secondary adhesion, and high film corrosion resistance and coating corrosion resistance.
- the surface-treated steel sheet of the present invention can be suitably used as a material for containers and the like.
- the surface-treated steel sheet according to the embodiment of the present invention is a surface-treated steel sheet having a steel sheet, a metal Cr layer arranged on at least one surface of the steel sheet, and an oxide Cr layer arranged on the metal Cr layer.
- the water contact angle of the surface-treated steel sheet is 50 ° or less, and the total atomic ratio of K, Na, Mg, and Ca adsorbed on the surface to Cr is 5% or less. is important.
- each of the constituent requirements of the surface-treated steel sheet will be described.
- any steel plate can be used without particular limitation, but it is preferable to use a steel plate for cans.
- a steel plate for example, an ultra-low carbon steel sheet or a low carbon steel sheet can be used.
- the method for manufacturing the steel sheet is not particularly limited, and a steel sheet manufactured by any method can be used, but usually a cold-rolled steel sheet may be used.
- the cold-rolled steel sheet can be manufactured by, for example, a general manufacturing process of hot rolling, pickling, cold rolling, annealing, and temper rolling.
- the composition of the steel sheet is not particularly limited, but the Cr content is preferably 0.10% by mass or less, and more preferably 0.08% by mass or less.
- the Cr content of the can steel sheet is within the above range, Cr is not excessively concentrated on the surface of the steel sheet, and as a result, the atomic ratio of Fe to Cr on the surface of the finally obtained surface-treated steel sheet. Can be 15% or less.
- the steel sheet may contain C, Mn, P, S, Si, Cu, Ni, Mo, Al and unavoidable impurities as long as the effects of the range of the present invention are not impaired.
- a steel sheet having a component composition specified in ASTM A623M-09 can be preferably used as the steel sheet.
- in% by weight C: 0.0001 to 0.13%, Si: 0 to 0.020%, Mn: 0.01-0.60% P: 0 to 0.020%, S: 0 to 0.030%, Al: 0 to 0.20%, N: 0 to 0.040%, Cu: 0 to 0.20%, Ni: 0 to 0.15%, Cr: 0 to 0.10%, Mo: 0-0.05%, Ti: 0 to 0.020%, Nb: 0 to 0.020%, B: 0 to 0.020%, Ca: 0 to 0.020%, Sn: 0 to 0.020%, Sb: 0 to 0.020%, It is preferable to use a steel sheet having a component composition consisting of the remaining Fe and unavoidable impurities. Of the above component compositions, Si, P, S, Al, and N are preferable components as the content is lower, and Cu, Ni, Cr, Mo, Ti, Nb, B, Ca, Sn, and Sb are optional. It is an ingredient
- the thickness of the steel sheet is not particularly limited, but is preferably 0.60 mm or less.
- “steel plate” is defined to include “steel strip”.
- Metal Cr layer A metal Cr layer is present on the surface of the steel sheet.
- the metal Cr layer may be arranged on at least one surface of the steel sheet, and may be arranged on both surfaces. That is, the metal Cr layer is directly formed on the surface of the steel sheet.
- the thickness of the metal Cr layer is not particularly limited, but from the viewpoint of further improving the corrosion resistance, the thickness of the metal Cr layer is preferably 3 nm or more, more preferably 4 nm or more, and more preferably 5 nm or more. Is even more preferable.
- the upper limit of the thickness of the metal Cr layer is not particularly limited, but if the metal Cr layer is excessively thick, the water contact angle described later may become large and the adhesion may be impaired. Therefore, from the viewpoint of ensuring more stable adhesion, the thickness of the metal Cr layer is preferably 100 nm or less, more preferably 90 nm or less, and further preferably 80 nm or less.
- the thickness of the metal Cr layer can be measured by the method described in Examples using X-ray photoelectron spectroscopy (XPS).
- the metal Cr constituting the metal Cr layer may be an amorphous Cr or a crystalline Cr. That is, the metal Cr layer can contain one or both of amorphous Cr and crystalline Cr.
- the metal Cr layer produced by the method described later generally contains amorphous Cr, and may further contain crystalline Cr. Although the formation mechanism of the metal Cr layer is not clear, it is considered that the metal Cr layer containing both the amorphous and the crystalline phase is formed by partially crystallization when the amorphous Cr is formed.
- the ratio of crystalline Cr to the total of amorphous Cr and crystalline Cr contained in the metal Cr layer is preferably 0% or more and 80% or less, and more preferably 0% or more and 50% or less.
- the ratio of the crystalline Cr can be measured by observing the metal Cr layer with a scanning transmission electron microscope (STEM). Specifically, first, an STEM image is acquired at a magnification of about 2 million times to 10 million times with a beam diameter that can obtain a resolution of 1 nm or less. In the obtained STEM image, the area where the plaid can be confirmed is defined as the crystal phase, and the region where the maize pattern can be confirmed is defined as amorphous, and the areas of both are determined. From the result, the ratio of the area of crystalline Cr to the total area of amorphous Cr and crystalline Cr is calculated.
- Cr oxide layer An oxidized Cr layer is present on the metal Cr layer.
- the thickness of the Cr oxide layer is not particularly limited, but is preferably 0.5 nm or more.
- the thickness of the Cr oxide layer is preferably 15 nm or less.
- the thickness of the Cr oxide layer can be measured by the method described in Examples using XPS.
- the C may be contained in one or both of the metal Cr layer and the oxidized Cr layer.
- the upper limit of the C content in the metal Cr layer is not particularly limited, but the atomic ratio to Cr is preferably 50% or less, and more preferably 45% or less.
- the upper limit of the C content in the Cr oxide layer is not particularly limited, but the element ratio to Cr is preferably 50% or less, and more preferably 45% or less.
- the metal Cr layer and the oxide Cr layer do not have to contain C. Therefore, the lower limit of the atomic ratio of C contained in the metal Cr layer and the oxide Cr layer to Cr is not particularly limited and may be 0%. ..
- the content of C in the metal Cr layer and the oxidized Cr layer is not particularly limited, but can be measured by, for example, XPS. That is, the content of C in the metal Cr layer is sputtered from the outermost surface to a value obtained by adding 1/2 the thickness of the metal Cr layer and the thickness of the oxidized Cr layer, and the integrated intensity of the narrow spectra of Cr2p and C1s is integrated.
- the atomic ratio may be quantified by the relative sensitivity coefficient method, and the C atomic ratio / Cr atomic ratio may be calculated.
- the C content in the Cr oxide layer is sputtered from the outermost surface to a value of 1/2 of the thickness of the Cr oxide layer, and the integrated intensity of the narrow spectra of Cr2p and C1s is quantified by the relative sensitivity coefficient method.
- the C atomic ratio / Cr atomic ratio may be calculated.
- a scanning X-ray photoelectron spectroscopy analyzer PHI X-tool manufactured by ULVAC-PHI can be used.
- the X-ray source is monochrome AlK ⁇ ray, the voltage is 15 kV, the beam diameter is 100 ⁇ m ⁇ , the extraction angle is 45 °, the sputtering conditions are Ar ion acceleration voltage 1 kV, and the sputtering rate is 1.50 nm / min in terms of SiO 2 . ..
- the form of existence of C in the metal Cr layer and the oxidized Cr layer is not particularly limited, but if it exists as a precipitate, the corrosion resistance may decrease due to the formation of a local battery. Therefore, the sum of the volume fractions of carbides and clusters having a clear crystal structure is preferably 10% or less, and more preferably not contained at all (0%).
- the presence or absence of charcoal can be confirmed, for example, by composition analysis using energy dispersion type X-ray spectroscopy (EDS) or wavelength dispersion type X-ray spectroscopy (WDS) attached to a scanning electron microscope (SEM) or transmission electron microscope (TEM). You can.
- the presence or absence of a cluster can be confirmed, for example, by performing a cluster analysis on the data after the three-dimensional composition analysis by the three-dimensional atom probe (3DAP).
- Fe may be contained in one or both of the metal Cr layer and the oxidized Cr layer.
- the Fe content in each layer is not particularly limited, but the atomic ratio to Cr is preferably less than 100%.
- the metal Cr layer and the oxidized Cr layer do not have to contain Fe, and therefore, the lower limit of the atomic ratio of Fe to Cr in each layer is not particularly limited and may be 0%.
- the Fe content on the surface of the surface-treated steel sheet is not particularly limited, but the lower the value, the better the adhesion and corrosion resistance. Therefore, the atomic ratio of Fe to Cr on the surface of the surface-treated steel sheet is preferably 15% or less, and more preferably 10% or less. The lower the atomic ratio, the better, so the lower limit may be 0%, and the atomic ratio is most preferably 0%.
- the content of Fe in the metal Cr layer and the oxidized Cr layer can be measured by XPS as well as the content of C. Further, the atomic ratio of Fe to Cr on the surface of the surface-treated steel sheet, that is, the surface of the Cr oxide layer, can be measured by XPS on the surface of the surface-treated steel sheet. Narrow spectra of Cr2p and Fe2p may be used to calculate the atomic ratio.
- Fe contained in the metal Cr layer and the oxide Cr layer is not clear, but in the process of forming the metal Cr layer and the oxide Cr layer on the steel plate, Fe contained in the steel plate is slightly dissolved in the electrolytic solution and Fe. Is considered to be incorporated into the film.
- O may be contained in the metal Cr layer.
- the upper limit of the O content in the metal Cr layer is not particularly limited, but when the O content is high, Cr oxide may precipitate and the corrosion resistance may decrease due to the formation of the local battery. Therefore, the O content in the metal Cr layer is preferably 30% or less, and more preferably 25% or less as the atomic ratio with respect to Cr.
- the metal Cr layer does not have to contain O, and therefore, the lower limit for Cr contained in the metal Cr layer is not particularly limited and may be 0%.
- the content of O in the metal Cr layer can be measured by composition analysis such as EDS and WDS attached to SEM or TEM, or 3DAP.
- the metal Cr layer and the oxidized Cr layer include metal impurities such as Cu, Zn, and Ni contained in the aqueous solution, and S. N, Cl, Br and the like may be included.
- the presence of these elements may reduce corrosion resistance and adhesion. Therefore, the total amount of elements other than Cr, O, Fe, C, K, Na, Mg, and Ca is preferably 3% or less as the atomic ratio with respect to Cr, and more preferably not contained at all (0%). ..
- the content of the above element is not particularly limited, but can be measured by XPS in the same manner as the content of C, for example.
- the metal Cr layer and the oxidized Cr layer are preferably crack-free.
- the presence or absence of cracks can be confirmed, for example, by cutting out the cross section of the film with a focused ion beam (FIB) or the like and directly observing it with a transmission electron microscope (TEM).
- FIB focused ion beam
- TEM transmission electron microscope
- the surface roughness of the surface-treated steel sheet of the present invention does not change significantly with the formation of the metal Cr layer and the oxide Cr layer, and is almost the same as the surface roughness of the base steel sheet normally used.
- the surface roughness of the surface-treated steel sheet is not particularly limited, but it is preferable that the arithmetic average roughness Ra is 0.1 ⁇ m or more and 4 ⁇ m or less. Further, the ten-point average roughness Rz is preferably 0.2 ⁇ m or more and 6 ⁇ m or less.
- the water contact angle of the surface-treated steel sheet is 50 ° or less.
- the water contact angle is preferably 48 ° or less, and more preferably 45 ° or less.
- the temperature may be 5 ° or more, and may be 8 ° or more.
- the water contact angle can be measured by the method described in the examples.
- the mechanism by which the surface of the surface-treated steel plate becomes hydrophilic is not clear, but when the metal Cr layer and the oxide Cr layer are formed by cathode electrolysis in the electrolytic solution, the carboxylic acid or carboxylate contained in the electrolytic solution is present. It is considered that this is because hydrophilic functional groups such as carboxyl groups are imparted to the surface by being decomposed and incorporated into the film. However, when the electrolytic solution is not prepared under specific conditions as described later, the surface of the surface-treated steel sheet is not hydrophilized even if the electrolytic solution contains a carboxylic acid or a carboxylate.
- the composition of the chromium hydrated oxide layer existing on the surface layer is in a wet environment. It has been reported to significantly affect the adhesion to paints or films. In a moist environment, the water that has permeated the coating film or film inhibits the adhesion of the interface between the coating film or film and the chromium hydrated oxide layer. Therefore, it has been considered that when a large amount of hydrophilic OH groups are present in the chromium hydrated oxide layer, the expanded wetting of water at the interface is promoted and the adhesive strength is lowered.
- the adhesion to the paint or the film in a moist environment is improved by reducing the OH groups due to the progress of the oxoification of the chromium hydrated oxide, that is, by making the surface hydrophobic.
- the surface-treated steel sheet of the present invention has high hydrophilicity with a water contact angle of 50 ° or less, and its surface is chemically active. Therefore, cations of elements such as K, Na, Mg, and Ca are easily adsorbed on the surface of the surface-treated steel sheet.
- the present inventors have found that simply setting the water contact angle to 50 ° or less does not exhibit the original adhesion due to the influence of the adsorbed cations.
- the adhesion to the resin is improved by reducing the amount of the cation adsorbed on the surface of the surface-treated steel sheet, and as a result, excellent film wet adhesion and paint secondary adhesion and high film corrosion resistance are achieved. And both paint corrosion resistance can be achieved.
- the total atomic ratio of K, Na, Mg, and Ca adsorbed on the surface of the surface-treated steel sheet to Cr is 5% or less, preferably 3% or less, and more preferably 1% or less.
- the total atomic ratio can be measured by the method described in the examples.
- a surface-treated steel sheet having the above characteristics can be manufactured by the method described below.
- the method for manufacturing a surface-treated steel sheet according to an embodiment of the present invention includes a steel sheet, a metal Cr layer arranged on at least one surface of the steel sheet, and an oxidized Cr layer arranged on the metal Cr layer. It is a method for manufacturing a surface-treated steel sheet, and includes the following steps (1) to (3). Hereinafter, each step will be described.
- Electrolyte preparation step of preparing an electrolytic solution containing trivalent chromium ion (2)
- Electrolytic solution preparation process (I) Mixing In the above electrolytic solution preparation step, first, a trivalent chromium ion source, a carboxylic acid compound, and water are mixed to prepare an aqueous solution.
- trivalent chromium ion source any compound that can supply trivalent chromium ions can be used.
- the trivalent chromium ion source for example, at least one selected from the group consisting of chromium chloride, chromium sulfate, and chromium nitrate can be used.
- the content of the trivalent chromium ion-containing source in the aqueous solution is not particularly limited, but is preferably 3 g / L or more and 50 g / L or less in terms of trivalent chromium ions, and is preferably 5 g / L or more and 40 g / L or less. More preferred.
- the trivalent chromium ion source Atotech's BluCr® TFS A can be used.
- the carboxylic acid compound is not particularly limited, and any carboxylic acid compound can be used.
- the carboxylic acid compound may be at least one of a carboxylic acid and a carboxylic acid salt, and preferably at least one of an aliphatic carboxylic acid and a salt of the aliphatic carboxylic acid.
- the aliphatic carboxylic acid preferably has 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms.
- the carbon number of the aliphatic carboxylate is preferably 1 to 10, and preferably 1 to 5.
- the content of the carboxylic acid compound is not particularly limited, but is preferably 0.1 mol / L or more and 5.5 mol / L or less, and more preferably 0.15 mol / L or more and 5.3 mol / L or less.
- the carboxylic acid compound Atotech's BluCr® TFS B can be used.
- water is used as a solvent for preparing the electrolytic solution.
- the water it is preferable to use ion-exchanged water from which cations have been removed in advance with an ion-exchange resin or the like, or water having high purity such as distilled water.
- water having an electric conductivity of 30 ⁇ S / m or less it is preferable to use water having an electric conductivity of 30 ⁇ S / m or less.
- K, Na, Mg, and Ca adsorbed on the surface of the surface-treated steel sheet it is preferable that K, Na, Mg, and Ca are not intentionally contained in the above-mentioned aqueous solution. Therefore, it is preferable that K, Na, Mg, and Ca are not contained in the components added to the aqueous solution such as the above-mentioned trivalent chromium ion source, the carboxylic acid compound, and the pH adjuster described in detail below.
- the pH adjuster it is preferable to use hydrochloric acid, sulfuric acid, nitric acid or the like for lowering the pH, and ammonia water or the like for raising the pH.
- K, Na, Mg, and Ca inevitably mixed in an aqueous solution or an electrolytic solution are acceptable, but the total of K, Na, Mg, and Ca is preferably 2.0 mol / L or less. It is more preferably 5 mol / L or less, and further preferably 1.0 mol / L or less.
- At least one halide ion may be further contained in the above-mentioned aqueous solution.
- the content of the halide ion is not particularly limited, but is preferably 0.05 mol / L or more and 3.0 mol / L or less, and more preferably 0.10 mol / L or more and 2.5 mol / L or less.
- Atotech's BluCr® TFS C1 and BluCr® TFS C2 can be used.
- Hexavalent chromium is not contained in the above-mentioned electrolytic solution except for a very small amount of hexavalent chromium formed at the anode in the cathode electrolysis treatment step. Since a very small amount of hexavalent chromium formed at the anode in the cathode electrolysis treatment step is reduced to trivalent chromium, the hexavalent chromium concentration in the electrolytic solution does not increase.
- the above-mentioned aqueous solution does not intentionally add metal ions other than trivalent chromium ions.
- the metal ion is not limited, but examples thereof include Cu ion, Zn ion, Ni ion and the like, each of which is preferably 0 mg / L or more and 40 mg / L or less, and further preferably 0 mg / L or more and 20 mg / L or less. It is preferably 0 mg / L or more and 10 mg / L or less.
- Fe ions may be dissolved in the electrolytic solution by immersing the steel plate in the electrolytic solution described above in the cathode electrolysis treatment step and coagulate in the film, but the film corrosion resistance and coating corrosion resistance It does not affect the wet adhesion of the film and the secondary adhesion of the paint.
- Fe ions are preferably 0 mg / L or more and 40 mg / L or less, more preferably 0 mg / L or more and 20 mg / L or less, and most preferably 0 mg / L or more and 10 mg / L or less.
- the Fe ion concentration is preferably in the above range at the time of building bath, but it is preferable to maintain the Fe ion concentration in the electrolytic solution in the above range even in the cathode electrolysis treatment step.
- the electrolytic solution is prepared by adjusting the pH of the aqueous solution to 4.0 to 7.0 and the temperature of the aqueous solution to 40 to 70 ° C.
- the pH of the aqueous solution it is not enough to simply dissolve the trivalent chromium ion source and the carboxylic acid compound in water, and it is important to properly control the pH and temperature as described above. ..
- the pH of the mixed aqueous solution is adjusted to 4.0 to 7.0.
- the pH is less than 4.0 or more than 7.0, the water contact angle of the surface-treated steel sheet manufactured by using the obtained electrolytic solution is higher than 50 °.
- the pH is preferably 4.5 to 6.5.
- the temperature of the mixed aqueous solution is adjusted to 40 to 70 ° C.
- the temperature is less than 40 ° C. or higher than 70 ° C.
- the water contact angle of the surface-treated steel sheet manufactured by using the obtained electrolytic solution becomes larger than 50 ° C.
- the holding time in the temperature range of 40 to 70 ° C. is not particularly limited.
- the electrolytic solution to be used in the next cathode electrolysis treatment step can be obtained.
- the electrolytic solution produced by the above procedure can be stored at room temperature.
- the temperature of the electrolytic solution during the cathode electrolysis treatment is not particularly limited, but is preferably set to a temperature range of 40 ° C. or higher and 70 ° C. or lower in order to efficiently form the metal Cr layer and the oxidized Cr layer. From the viewpoint of stably producing the above-mentioned surface-treated steel sheet, it is preferable to monitor the temperature of the electrolytic solution and maintain it in the above-mentioned temperature range in the cathode electrolysis treatment step.
- the pH of the electrolytic solution when performing the cathode electrolysis treatment is not particularly limited, but is preferably 4.0 or higher, and more preferably 4.5 or higher.
- the pH is preferably 7.0 or less, more preferably 6.5 or less. From the viewpoint of stably producing the above-mentioned surface-treated steel sheet, it is preferable to monitor the pH of the electrolytic solution and maintain it in the above-mentioned pH range in the cathode electrolysis treatment step.
- the current density in the cathode electrolysis treatment is not particularly limited, and may be appropriately adjusted so that a desired surface treatment layer is formed. However, if the current density is excessively high, the load on the cathode electrolysis treatment device becomes excessive. Therefore, the current density is preferably 200.0 A / dm 2 or less, and more preferably 100 A / dm 2 or less. Further, the lower limit of the current density is not particularly limited, but if the current density is excessively low, hexavalent Cr may be generated in the electrolytic solution, and the stability of the bath may be deteriorated. Therefore, the current density is preferably 5.0 A / dm 2 or more, and more preferably 10.0 A / dm 2 or more.
- the number of times the cathode electrolysis treatment is applied to the steel sheet is not particularly limited, and can be any number of times.
- the cathode electrolysis treatment can be performed using an electrolysis treatment device having one or more and any number of passes.
- the electrolysis time per pass is not particularly limited. However, if the electrolysis time per pass is too long, the transfer speed (line speed) of the steel sheet is lowered, and the productivity is lowered. Therefore, the electrolysis time per pass is preferably 5 seconds or less, and more preferably 3 seconds or less.
- the lower limit of the electrolysis time per pass is not particularly limited, but if the electrolysis time is excessively shortened, it becomes necessary to increase the line speed accordingly, which makes control difficult. Therefore, the electrolysis time per pass is preferably 0.005 seconds or longer, more preferably 0.01 seconds or longer.
- the thickness of the metal Cr layer formed by the cathode electrolysis treatment can be controlled by the total electric quantity density expressed by the product of the current density, the electrolysis time and the number of passes. As described above, if the metal Cr layer is excessively thick, the water contact angle may increase and the adhesion may be impaired. Therefore, from the viewpoint of ensuring more stable adhesion, the thickness of the metal Cr layer It is preferable to control the total electric quantity density so that the thickness is 100 nm or less. However, since the relationship between the thickness of the metal Cr layer and the total electric energy density changes depending on the configuration of the device used in the cathode electrolysis treatment step, the actual electrolysis treatment conditions may be adjusted according to the device.
- the type of anode used when performing cathode electrolysis treatment is not particularly limited, and any anode can be used.
- the anode it is preferable to use an insoluble anode.
- the insoluble anode it is preferable to use at least one selected from the group consisting of an anode in which Ti is coated with one or both of a platinum group metal and an oxide of a platinum group metal, and a graphite anode. More specifically, examples of the insoluble anode include an anode in which the surface of Ti as a substrate is coated with platinum, iridium oxide, or ruthenium oxide.
- the concentration of the electrolytic solution constantly changes due to the influence of the formation of the metal Cr layer and the oxide Cr layer on the steel sheet, the carry-out and carry-in of the liquid, the evaporation of water, and the like. Since the change in the concentration of the electrolytic solution in the cathode electrolysis process changes depending on the configuration of the device and the manufacturing conditions, from the viewpoint of more stable production of the surface-treated steel plate, the concentration of the components contained in the electrolytic solution in the cathode electrolysis process. Is preferably monitored and maintained within the concentration range described above.
- the steel sheet Prior to the cathode electrolysis treatment, the steel sheet can be arbitrarily pretreated.
- any treatment can be performed, but it is preferable to perform at least one of degreasing, pickling, and washing with water.
- degreasing rolling oil, rust preventive oil, etc. adhering to the steel sheet can be removed.
- the degreasing is not particularly limited and can be performed by any method. After degreasing, it is preferable to perform washing with water in order to remove the degreasing treatment liquid adhering to the surface of the steel sheet.
- the natural oxide film existing on the surface of the steel sheet can be removed and the surface can be activated.
- the pickling is not particularly limited and can be carried out by any method. After pickling, it is preferable to wash with water in order to remove the pickling treatment liquid adhering to the surface of the steel sheet.
- the steel sheet after the cathode electrolysis treatment is washed with water at least once.
- the washing with water can be performed by any method without particular limitation.
- a water washing tank can be provided downstream of the electrolytic cell for performing the cathode electrolysis treatment, and the steel sheet after the cathode electrolysis treatment can be continuously immersed in water. Further, the steel sheet after the cathode electrolysis treatment may be washed with water by spraying water.
- the number of times of washing with water is not particularly limited, and may be once or twice or more. However, in order to prevent the number of washing tanks from becoming excessively large, it is preferable that the number of washings is 5 or less. Further, when the water washing treatment is performed twice or more, each water washing may be performed by the same method or may be performed by different methods.
- water having an electric conductivity of 100 ⁇ S / m or less in at least the final water washing in the water washing treatment step.
- the amount of K, Na, Mg, and Ca adsorbed on the surface of the surface-treated steel sheet can be reduced, and as a result, the adhesion can be improved.
- Water having an electric conductivity of 100 ⁇ S / m or less can be produced by any method.
- the water having an electric conductivity of 100 ⁇ S / m or less may be, for example, ion-exchanged water or distilled water.
- the above-mentioned effect can be obtained by using water having an electric conductivity of 100 ⁇ S / m or less for the final water washing.
- Any water can be used.
- Water with an electric conductivity of 100 ⁇ S / m or less may be used for water washing other than the final washing, but from the viewpoint of cost reduction, water with an electric conductivity of 100 ⁇ S / m or less is used only for the final washing.
- the electric conductivity of the water used for the final washing with water is preferably 50 ⁇ S / m or less, preferably 30 ⁇ S. It is more preferable to set it to / m or less.
- the temperature of the water used for the water washing treatment is not particularly limited and may be any temperature. However, if the temperature is excessively high, the washing equipment is overloaded, so the temperature of the water used for washing is preferably 95 ° C. or lower. On the other hand, the lower limit of the temperature of the water used for washing with water is not particularly limited, but it is preferably 0 ° C. or higher. The temperature of the water used for washing with water may be room temperature.
- the water washing time per water washing treatment is not particularly limited, but is preferably 0.1 seconds or more, and more preferably 0.2 seconds or more from the viewpoint of enhancing the effect of the water washing treatment. Further, the upper limit of the washing time per washing treatment is not particularly limited, but in the case of manufacturing on a continuous line, 10 seconds or less is preferable because the line speed is lowered and the productivity is lowered. Seconds or less is more preferable.
- drying may be performed arbitrarily.
- the drying method is not particularly limited, and for example, a normal dryer or an electric furnace drying method can be applied.
- the temperature during the drying treatment is preferably 100 ° C. or lower. Within the above range, deterioration of the surface treatment film can be suppressed.
- the lower limit is not particularly limited, but is usually about room temperature.
- the use of the surface-treated steel sheet of the present invention is not particularly limited, but it is particularly suitable as a surface-treated steel sheet for containers used for manufacturing various containers such as food cans, beverage cans, pail cans, and 18-liter cans.
- a surface-treated steel sheet was manufactured by the procedure described below and its characteristics were evaluated.
- electrolytic solution preparation process First, electrolytic solutions having compositions A to G shown in Table 1 were prepared under the conditions shown in Table 1. That is, each component shown in Table 1 was mixed with water to form an aqueous solution, and then the aqueous solution was adjusted to the pH and temperature shown in Table 1.
- the electrolytic solution G corresponds to the electrolytic solution used in the examples of Patent Document 4. Ammonia water was used for raising the pH, sulfuric acid was used for the electrolytic solutions A, B and G, hydrochloric acid was used for the electrolytic solutions C and D, and nitric acid was used for the electrolytic solutions E and F to lower the pH.
- the steel sheet Prior to the next cathode electrolysis treatment step, the steel sheet was pretreated. As the pretreatment, electrolytic degreasing, washing with water, pickling by immersion in dilute sulfuric acid, and washing with water were sequentially performed. As the steel sheet, a steel sheet for cans (T4 original plate) having a Cr content mass% of the values shown in Tables 2 and 4 and a plate thickness of 0.22 mm was used.
- the pretreated steel sheet was subjected to cathode electrolysis under the conditions shown in Tables 2 and 4.
- the electrolytic solution during the cathode electrolysis treatment was maintained at the pH and temperature shown in Table 1.
- the electric energy density during the cathode electrolysis treatment was 40 A / dm 2 , and the electrolysis time and the number of passes were appropriately changed.
- As the anode during the cathode electrolysis treatment an insoluble anode in which Ti as a substrate was coated with iridium oxide was used. After the cathode electrolysis treatment, it was washed with water and dried at room temperature using a blower.
- the thickness of the Cr oxide layer, the thickness of the metallic Cr layer, the water contact angle, the atomic ratio of the adsorbed element, and the Fe atomic ratio were measured by the following procedure. The measurement results are shown in Tables 3 and 5.
- the thickness of the Cr oxide layer was measured by XPS. Specifically, the narrow spectrum of Cr2p was separated into three peaks corresponding to the metal Cr, the oxide Cr, and the hydroxide Cr, respectively, from the one with the lower binding energy, and the integrated intensity ratio was calculated. The measurement was performed every 2 nm from the outermost layer until the sum of the integrated intensities of the Cr oxide peak and the Cr hydroxide peak became smaller than the integrated intensity of the metal Cr peak.
- the relationship of the metal Cr peak integral strength / integral strength of the oxide Cr peak + the integral strength of the hydroxylated Cr peak) with respect to the depth from the outermost layer is linearly approximated by the minimum square method, and the metal Cr peak integral strength / (Cr oxide). The depth from the outermost layer where the integrated intensity of the peak + the integrated intensity of the Cr hydroxide peak) was 1 was defined as the thickness of the Cr oxide layer.
- the Cr2p narrow spectrum may include a peak corresponding to the bond energy between C and Cr evaporating in the metal Cr layer or the oxide Cr layer, but the thickness of the metal Cr layer or the oxide Cr layer may be included. In the calculation, there is no problem even if the peaks corresponding to the coupling energies of C and Cr are ignored and separated by the above three peaks.
- the thickness of the metallic Cr layer was also measured by XPS in the same manner as the oxidized Cr layer. Specifically, the integral intensity of the narrow spectra of Cr2p and Fe2p was quantified by the relative sensitivity coefficient method, and measured every 2 nm from the outermost layer until the Cr atomic ratio became smaller than the Fe atomic ratio. The relationship between the Fe atomic ratio / Cr atomic ratio with respect to the depth from the outermost layer is approximated by a cubic equation using the minimum square method, and the Cr oxide is obtained from the depth from the outermost layer where the Fe atomic ratio / Cr atomic ratio is 1. The value obtained by subtracting the thickness of the layer was taken as the thickness of the metal Cr layer. If the depth from the outermost layer where the Fe atom ratio / Cr atom ratio is 1 is smaller than the thickness of the oxidized Cr layer, it means that the metal Cr layer does not exist, and in that case, sufficient. Corrosion resistance cannot be obtained.
- a scanning X-ray photoelectron spectroscopy analyzer PHI X-tool manufactured by ULVAC-PHI is used to measure the thickness of the Cr oxide layer and the thickness of the metal Cr layer.
- the X-ray source is monochrome AlK ⁇ ray, the voltage is 15 kV, and the beam.
- the diameter was 100 ⁇ m ⁇ and the extraction angle was 45 °.
- the sputtering conditions are Ar ion with an acceleration voltage of 1 kV, and the sputtering rate is 1.50 nm / min in terms of SiO 2 .
- the water contact angle was measured using an automatic contact angle meter CA-VP manufactured by Kyowa Interface Science Co., Ltd.
- the surface temperature of the surface-treated steel plate is set to 20 ° C ⁇ 1 ° C, distilled water of 20 ⁇ 1 ° C is used as water, and distilled water is dropped on the surface of the surface-treated steel plate with a droplet volume of 2 ⁇ l, and ⁇ / 1 second later.
- the contact angle was measured by two methods, and the additive average value of the contact angles for 5 drops was taken as the water contact angle.
- the total atomic ratio of K, Na, Mg, and Ca adsorbed on the surface of the surface-treated steel sheet to Cr was measured by XPS. No spatter was performed in the measurement. From the integrated intensity of the narrow spectra of K2p, Na1s, Ca2p, Mg1s, and Cr2p on the outermost surface of the sample, the atomic ratio is quantified by the relative sensitivity coefficient method, and (K atomic ratio + Na atomic ratio + Ca atomic ratio + Mg atomic ratio) / Cr atom. The ratio was calculated.
- a scanning X-ray photoelectron spectroscopy analyzer PHI X-tool manufactured by ULVAC-PHI was used, the X-ray source was monochrome AlK ⁇ ray, the voltage was 15 kV, the beam diameter was 100 ⁇ m ⁇ , and the extraction angle was 45 °.
- Fe atom ratio The atomic ratio of Fe to Cr on the surface of the surface-treated steel sheet was measured by XPS. No spatter was performed in the measurement. From the integrated intensities of the narrow spectra of Fe2p and Cr2p on the sample surface, the atomic ratio was quantified by the relative sensitivity coefficient method, and the Fe atomic ratio / Cr atomic ratio was calculated.
- a scanning X-ray photoelectron spectroscopy analyzer PHI X-tool manufactured by ULVAC-PHI was used for XPS measurement, the X-ray source was monochrome AlK ⁇ ray, the voltage was 15 kV, the beam diameter was 100 ⁇ m ⁇ , and the extraction angle was 45 °.
- the obtained surface-treated steel sheet was evaluated for film corrosion resistance, coating corrosion resistance, film wet adhesion, and paint secondary adhesion by the following methods. The evaluation results are also shown in Tables 3 and 5.
- the laminating was carried out under the condition that the crystallinity of the resin film was 10% or less, specifically, the feed rate of the steel plate was 40 m / min, the nip length of the rubber roll was 17 mm, and the time until water cooling after crimping was 1 sec. ..
- the crystallinity of the resin film was determined by the density gradient tube method based on JIS K7112.
- the nip length is the length of the portion where the rubber roll and the steel plate are in contact with each other in the transport direction.
- a coated steel sheet as a sample used for evaluation of coating corrosion resistance and secondary paint adhesion was produced by the following procedure.
- An epoxyphenol-based paint was applied to the surface of the obtained surface-treated steel sheet and baked at 210 ° C. for 10 minutes to prepare a coated steel sheet.
- the amount of paint adhered was 50 mg / dm 2 .
- a cross cut having a depth reaching the base iron (steel plate) was made on the film surface of the produced laminated steel plate and the coated surface of the painted steel plate using a cutter.
- the cross-cut laminated steel sheet and coated steel sheet were immersed in a test solution at 55 ° C. consisting of a mixed aqueous solution containing 1.5% by mass citric acid and 1.5% by mass of salt for 96 hours. After dipping, washing and drying, cellophane adhesive tape was attached to the film surface of the laminated steel sheet and the coated surface of the painted steel sheet, and the tape was peeled off.
- the film peeling width (total width on the left and right extending from the cut portion) was measured at any four locations of the cross-cut portion of the laminated steel sheet, and the average value of the four locations was calculated and regarded as the corrosion width.
- the coating peeling width (total width on the left and right spreading from the cut portion) was measured at any four locations of the cross-cut portion of the coated steel sheet, and the average value of the four locations was calculated and regarded as the corrosion width.
- the film corrosion resistance and the coating corrosion resistance were evaluated according to the following criteria. Practically, if the result is ⁇ , ⁇ or ⁇ , it can be evaluated as having excellent corrosion resistance.
- Corrosion width less than 0.3 mm ⁇ Corrosion width 0.3 mm or more and less than 0.5 mm ⁇ : Corrosion width 0.5 mm or more and less than 1.0 mm ⁇ : Corrosion width 1.0 mm or more
- test pieces were cut out from each of the above laminated steel sheets, 3 test pieces having the front surface as the target surface and 3 test pieces having the back surface as the target surface.
- the size of each test piece was 30 mm in width and 100 mm in length.
- the film on the target surface was left at a position 15 mm from the upper part in the length direction of each test piece, and the film on the surface opposite to the target surface and the steel plate were cut.
- the part of the test piece after cutting is fixed from the bottom to 15 mm in the length direction of the test piece so that the steel plate is perpendicular to the ground, and the part with a width of 30 mm and a length of 15 mm above the cutting position is the target. I made it hang down while being connected by the film on the surface.
- a weight of 100 g was attached to the hanging portion having a width of 30 mm and a length of 15 mm.
- the test piece in this state was left in a retort atmosphere at a temperature of 130 ° C. and a relative humidity of 100% for 30 minutes, and then opened to the atmosphere.
- the length at which the film on the target surface was peeled off from the surface-treated steel sheet was defined as the film peeling length, and the average value of the film peeling lengths of the six test pieces was obtained for each laminated steel sheet.
- the film wet adhesion was evaluated according to the following evaluation criteria. Practically, if the result is ⁇ , ⁇ or ⁇ , it can be said that the film has excellent wet adhesion.
- ⁇ Peeling length less than 20 mm ⁇ : Peeling length 20 mm or more and less than 40 mm
- ⁇ Peeling length 40 mm or more and less than 60 mm
- the surface-treated steel sheets satisfying the conditions of the present invention are all excellent in film wet adhesion and paint 2 even though they are manufactured without using hexavalent chromium. It has both high adhesion and high film corrosion resistance and coating corrosion resistance.
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Abstract
Description
水接触角が50°以下であり、
表面に吸着したK、Na、Mg、およびCaの、Crに対する原子比率の合計が、5%以下である、表面処理鋼板。
3価クロムイオンを含有する電解液を調製する電解液調製工程と、
前記電解液中で鋼板を陰極電解処理する陰極電解処理工程と、
前記陰極電解処理後の鋼板を少なくとも1回水洗する水洗工程とを含み、
前記電解液調製工程では、
3価クロムイオン源、カルボン酸化合物、および水を混合し、
pHを4.0~7.0に調整するとともに、温度を40~70℃に調整することによって前記電解液が調製され、
前記水洗工程では、
少なくとも最後の水洗において、電気伝導度100μS/m以下の水を使用する、表面処理鋼板の製造方法。
前記鋼板としては、とくに限定されることなく任意の鋼板を用いることができるが、缶用鋼板を用いることが好ましい。前記鋼板としては、例えば、極低炭素鋼板または低炭素鋼板を用いることができる。前記鋼板の製造方法についてもとくに限定されず、任意の方法で製造された鋼板を用いることができるが、通常は冷延鋼板を使用すればよい。前記冷延鋼板は、例えば、熱間圧延、酸洗、冷間圧延、焼鈍、および調質圧延を行う、一般的な製造工程により製造することができる。
C :0.0001~0.13%、
Si:0~0.020%、
Mn:0.01~0.60%
P :0~0.020%、
S :0~0.030%、
Al:0~0.20%、
N :0~0.040%、
Cu:0~0.20%、
Ni:0~0.15%、
Cr:0~0.10%、
Mo:0~0.05%、
Ti:0~0.020%、
Nb:0~0.020%、
B :0~0.020%、
Ca:0~0.020%、
Sn:0~0.020%、
Sb:0~0.020%、
および残部のFeおよび不可避的不純物からなる成分組成を有する鋼板を用いることが好ましい。上記成分組成のうち、Si、P、S、Al、およびNは含有量が低いほど好ましい成分であり、Cu、Ni、Cr、Mo、Ti、Nb、B、Ca、SnおよびSbは、任意に添加し得る成分である。
前記鋼板の表面には金属Cr層が存在する。前記金属Cr層は、前記鋼板の少なくとも一方の表面上に配置されていればよく、両側の表面上に配置されていてもよい。すなわち、前記金属Cr層は、鋼板の表面に直接形成されている。
前記金属Cr層上には酸化Cr層が存在する。前記酸化Cr層の厚さは特に限定されないが、0.5nm以上であることが好ましい。また、前記酸化Cr層の厚さは、15nm以下であることが好ましい。前記酸化Cr層の厚さは、XPSを用いて、実施例に記載した方法で測定することができる。
本発明においては、表面処理鋼板の水接触角が50°以下であることが重要である。水接触角が50°以下となるよう表面処理鋼板の表面を高度に親水化することにより、フィルムまたは塗料に含まれる樹脂と表面処理鋼板との間に強固な水素結合が形成され、その結果、湿潤環境下においても高い密着性を得ることができる。密着性をさらに向上させるという観点からは、水接触角を48°以下とすることが好ましく、45°以下とすることがより好ましい。前記水接触角は、密着性向上の観点からは低ければ低いほど好ましいため、その下限はとくに限定されず、0°であってもよい。しかし、製造しやすさなどの観点からは、5°以上であってよく、8°以上であってもよい。なお、前記水接触角は、実施例に記載した方法で測定することができる。
上述したように、本発明の表面処理鋼板は水接触角が50°以下という高い親水性を有しており、その表面は化学的に活性である。そのため、前記表面処理鋼板の表面には、K、Na、Mg、およびCaなどの元素のカチオンが吸着しやすい。本発明者らは、単純に水接触角を50°以下とするのみでは、吸着した前記カチオンの影響のため、本来の密着性が発揮されないことを見出した。本発明では、表面処理鋼板の表面に吸着した前記カチオンの量を低減することにより、樹脂に対する密着性を向上させ、その結果、優れたフィルム湿潤密着性および塗料2次密着性と、高いフィルム耐食性および塗装耐食性の両者を実現することができる。
本発明の一実施形態における表面処理鋼板の製造方法では、以下に説明する方法で、上記特性を備えた表面処理鋼板を製造することができる。
(1)3価クロムイオンを含有する電解液を調製する電解液調製工程
(2)前記電解液中で鋼板を陰極電解処理する陰極電解処理工程
(3)前記陰極電解処理後の鋼板を少なくとも1回水洗する水洗工程
(i)混合
上記電解液調製工程では、まず、3価クロムイオン源、カルボン酸化合物、および水を混合して水溶液とする。
次に、前記水溶液のpHを4.0~7.0に調整するとともに、前記水溶液の温度を40~70℃に調整することによって前記電解液を調製する。上述した表面処理鋼板を製造するためには、単に3価クロムイオン源とカルボン酸化合物を水に溶解させるだけでは不十分であり、上記のとおりpHと温度を適正に制御することが重要である。
前記電解液調製工程においては、混合後の水溶液のpHを4.0~7.0に調整する。pHが4.0未満または7.0超であると、得られた電解液を用いて製造した表面処理鋼板の水接触角は50°より高くなる。pHは、4.5~6.5とすることが好ましい。
前記電解液調製工程では、混合後の水溶液の温度を40~70℃に調整する。温度が40℃未満、あるいは70℃超であると、得られた電解液を用いて製造した表面処理鋼板の水接触角が50°より大きくなる。なお、40~70℃の温度域での保持時間は特に限定されない。
次に、上記電解液調製工程で得られた電解液中で鋼板を陰極電解処理する。前記陰極電解処理により、下地鋼板の少なくとも一方の表面上に金属Cr層と酸化Cr層とを形成することができる。
次に、上記陰極電解処理後の鋼板を少なくとも1回水洗する。水洗を行うことにより、鋼板の表面に残留している電解液を除去することができる。前記水洗は、特に限定されることなく任意の方法で行うことができる。例えば、陰極電解処理を行うための電解槽の下流に水洗タンクを設け、陰極電解処理後の鋼板を連続的に水に浸漬することができる。また、陰極電解処理後の鋼板にスプレーで水を吹き付けることによって水洗を行ってもよい。
まず、表1に示す組成A~Gを有する電解液を、表1に示した各条件で調製した。すなわち、表1に示した各成分を水と混合して水溶液とし、次いで前記水溶液を表1に示したpHおよび温度に調整した。なお、電解液Gは、特許文献4の実施例で使用されている電解液に相当する。pHの上昇にはいずれもアンモニア水を使用し、pHの低下には電解液A、B、Gには硫酸、電解液C、Dには塩酸、電解液E、Fには硝酸を使用した。
次の陰極電解処理工程に先だって、鋼板に前処理を施した。前記前処理としては、電解脱脂、水洗、希硫酸への浸漬による酸洗、および水洗を順次行った。なお、前記鋼板としては、Cr含有量質量%が表2、4に示す値であり、板厚が0.22mmである缶用鋼板(T4原板)を使用した。
その後、前記前処理後の鋼板に対して、表2および表4に示す条件で陰極電解処理を施した。なお、陰極電解処理の際の電解液は表1に示したpHと温度に保持した。陰極電解処理時の電気量密度は40A/dm2とし、電解時間とパス数は適宜変化させた。陰極電解処理時の陽極としては、基体としてのTiに酸化イリジウムをコーティングした不溶性陽極を使用した。陰極電解処理を行った後は、水洗処理を行い、ブロアを用いて室温で乾燥を行った。
次いで、上記陰極電解処理後の鋼板に水洗処理を施した。前記水洗処理は、表2および表4に示した条件で1~5回行った。各回の水洗の方法と、使用した水の電気伝導度は表2および表4に示したとおりとした。
酸化Cr層の厚さは、XPSにより測定した。具体的には、Cr2pのナロースペクトルを、結合エネルギーの低い方から、それぞれ金属Cr、酸化Cr、水酸化Crに対応する3つのピークに分離し、積分強度比を算出した。酸化Crピークと水酸化Crピークの積分強度の和が金属Crピークの積分強度より小さくなるまで、最表層から2nmごとに測定した。最表層からの深さに対する、金属Crピーク積分強度/(酸化Crピークの積分強度+水酸化Crピークの積分強度)の関係を最小二乗法で線形近似し、金属Crピーク積分強度/(酸化Crピークの積分強度+水酸化Crピークの積分強度)が1となる最表層からの深さを、酸化Cr層の厚さとした。
金属Cr層の厚さについても、酸化Cr層と同様にXPSにより測定した。具体的には、Cr2pとFe2pのナロースペクトルの積分強度を相対感度係数法で原子比率を定量化し、Cr原子比率がFe原子比率より小さくなるまで、最表層から2nmごとに測定した。最表層からの深さに対する、Fe原子比率/Cr原子比率の関係を、最小二乗法で3次式近似し、Fe原子比率/Cr原子比率が1となる最表層からの深さから、酸化Cr層の厚さを差し引いた値を、金属Cr層の厚さとした。なお、上記のFe原子比率/Cr原子比率が1となる最表層からの深さが、上記酸化Cr層の厚さより小さい場合は、金属Cr層が存在しないことを意味し、その場合、十分な耐食性が得ることができない。
水接触角は、協和界面科学社製の自動接触角計CA-VP型を用いて測定した。表面処理鋼板の表面温度を20℃±1℃とし、水は20±1℃の蒸留水を使用し、2μlの液滴量で蒸留水を表面処理鋼板の表面に滴下し、1秒後にθ/2法によって接触角を測定し、5滴分の接触角の相加平均値を水接触角とした。
表面処理鋼板の表面に吸着したK、Na、Mg、およびCaの、Crに対する原子比率の合計を、XPSにより測定した。測定においては、スパッタは行わなかった。試料最表面のK2p、Na1s、Ca2p、Mg1s、およびCr2pのナロースペクトルの積分強度から、相対感度係数法により原子比率を定量化し、(K原子比率+Na原子比率+Ca原子比率+Mg原子比率)/Cr原子比率を算出した。XPSの測定には、アルバックファイ社製走査型X線光電子分光分析装置PHI X-toolを用い、X線源はモノクロAlKα線、電圧は15kV、ビーム径は100μmφ、取出角は45°とした。
表面処理鋼板の表面におけるFeの、Crに対する原子比率を、XPSにより測定した。測定においては、スパッタは行わなかった。試料表面のFe2pおよびCr2pのナロースペクトルの積分強度から、相対感度係数法により原子比率を定量化し、Fe原子比率/Cr原子比率を算出した。XPSの測定には、アルバックファイ社製走査型X線光電子分光分析装置PHI X-toolを用い、X線源はモノクロAlKα線、電圧は15kV、ビーム径は100μmφ、取出角は45°とした。
フィルム耐食性およびフィルム湿潤密着性の評価に使用するサンプルとしてのラミネート鋼板を、以下の手順で作製した。
作製したラミネート鋼板のフィルム面および塗装鋼板の塗装面に、カッターを用いて地鉄(鋼板)に達する深さのクロスカットを入れた。クロスカットを入れたラミネート鋼板および塗装鋼板を、1.5質量%クエン酸と1.5質量%食塩とを含有する混合水溶液からなる55℃の試験液に、96時間浸漬した。浸漬後、洗浄および乾燥をした後、ラミネート鋼板のフィルム面、および塗装鋼板の塗装面にセロハン粘着テープを貼り付け、引き剥がすテープ剥離を行った。フィルム耐食性については、ラミネート鋼板のクロスカット部の任意の4箇所についてフィルム剥離幅(カット部から広がる左右の合計幅)を測定し、4箇所の平均値を求め、腐食幅とみなした。塗装耐食性については、塗装鋼板のクロスカット部の任意の4箇所について塗装剥離幅(カット部から広がる左右の合計幅)を測定し、4箇所の平均値を求め、腐食幅とみなした。フィルム耐食性および塗装耐食性は、下記基準で評価した。実用上、結果が◎、〇または△であれば、耐食性に優れるものとして評価できる。
◎:腐食幅0.3mm未満
○:腐食幅0.3mm以上0.5mm未満
△:腐食幅0.5mm以上1.0mm未満
×:腐食幅1.0mm以上
フィルム湿潤密着性は、上記ラミネート鋼板を使用して、温度130℃、相対湿度100%のレトルト雰囲気における180°ピール試験により評価した。具体的な手順は以下の通りとした。
◎:剥離長20mm未満
○:剥離長20mm以上40mm未満
△:剥離長40mm以上60mm未満
×:剥離長60mm以上
同じ条件で作製した塗装鋼板2枚を、ナイロン接着フィルムを挟んで塗装面が向かい合わせになるように積層した後、圧力2.94×105Pa、温度190℃、圧着時間30秒の圧着条件下で貼り合わせた。その後、これを5mm幅の試験片に分割した。分割した試験片は、1.5質量%クエン酸と1.5質量%食塩とを含有する混合水溶液からなる55℃の試験液に、168時間浸漬した。浸漬後、洗浄および乾燥をした後、分割した試験片の2枚の鋼板を引張試験機で引き剥がし、引き剥がしたときの引張強度を測定した。3つの試験片の平均値を下記基準で評価した。実用上、結果が◎、〇または△であれば、塗料2次密着性に優れるものとして評価できる。
◎:2.5kgf以上
○:2.0kgf以上2.5kgf未満
△:1.5kgf以上2.0kgf未満
×:1.5kgf未満
Claims (5)
- 鋼板と、前記鋼板の少なくとも一方の表面上に配置された金属Cr層と、前記金属Cr層上に配置された酸化Cr層とを有する表面処理鋼板であって、
水接触角が50°以下であり、
表面に吸着したK、Na、Mg、およびCaの、Crに対する原子比率の合計が、5%以下である、表面処理鋼板。 - 前記金属Cr層の厚さが、3~100nmである、請求項1に記載の表面処理鋼板。
- 前記酸化Cr層の厚さが、0.5~15nmである、請求項1または2に記載の表面処理鋼板。
- 前記表面処理鋼板の表面におけるFeの、Crに対する原子比率が、15%以下である、請求項1~3のいずれか一項に記載の表面処理鋼板。
- 鋼板と、前記鋼板の少なくとも一方の表面上に配置された金属Cr層と、前記金属Cr層上に配置された酸化Cr層とを有する表面処理鋼板の製造方法であって、
3価クロムイオンを含有する電解液を調製する電解液調製工程と、
前記電解液中で鋼板を陰極電解処理する陰極電解処理工程と、
前記陰極電解処理後の鋼板を少なくとも1回水洗する水洗工程とを含み、
前記電解液調製工程では、
3価クロムイオン源、カルボン酸化合物、および水を混合し、
pHを4.0~7.0に調整するとともに、温度を40~70℃に調整することによって前記電解液が調製され、
前記水洗工程では、
少なくとも最後の水洗において、電気伝導度100μS/m以下の水を使用する、表面処理鋼板の製造方法。
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JP2020109205A (ja) * | 2018-12-13 | 2020-07-16 | ティッセンクルップ ラッセルシュタイン ゲー エム ベー ハー | 三価クロム化合物を含む電解液を使用してクロムおよび酸化クロムのコーティングで被覆された金属ストリップの製造方法 |
JP2020117748A (ja) * | 2019-01-22 | 2020-08-06 | Jfeスチール株式会社 | 缶用鋼板およびその製造方法 |
JP2020200533A (ja) * | 2019-06-06 | 2020-12-17 | Jfeスチール株式会社 | 缶用鋼板およびその製造方法 |
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