CN1745196A - 黑色镀锌系钢板 - Google Patents
黑色镀锌系钢板 Download PDFInfo
- Publication number
- CN1745196A CN1745196A CNA2004800031343A CN200480003134A CN1745196A CN 1745196 A CN1745196 A CN 1745196A CN A2004800031343 A CNA2004800031343 A CN A2004800031343A CN 200480003134 A CN200480003134 A CN 200480003134A CN 1745196 A CN1745196 A CN 1745196A
- Authority
- CN
- China
- Prior art keywords
- black
- steel sheet
- ion
- zinc
- tunicle
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910000831 Steel Inorganic materials 0.000 title claims description 79
- 239000010959 steel Substances 0.000 title claims description 79
- 239000011347 resin Substances 0.000 claims abstract description 68
- 229920005989 resin Polymers 0.000 claims abstract description 68
- -1 vanadate ion Chemical class 0.000 claims abstract description 48
- VPVSTMAPERLKKM-UHFFFAOYSA-N glycoluril Chemical compound N1C(=O)NC2NC(=O)NC21 VPVSTMAPERLKKM-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 27
- 150000001875 compounds Chemical class 0.000 claims description 50
- 239000011701 zinc Substances 0.000 claims description 40
- 229910052751 metal Inorganic materials 0.000 claims description 34
- 239000002184 metal Substances 0.000 claims description 34
- 229910052725 zinc Inorganic materials 0.000 claims description 32
- 238000000576 coating method Methods 0.000 claims description 30
- 239000011248 coating agent Substances 0.000 claims description 29
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 28
- 229910019142 PO4 Inorganic materials 0.000 claims description 25
- 239000010452 phosphate Substances 0.000 claims description 25
- 150000002500 ions Chemical class 0.000 claims description 19
- 238000012545 processing Methods 0.000 claims description 18
- 239000003973 paint Substances 0.000 claims description 10
- 239000004925 Acrylic resin Substances 0.000 claims description 7
- 229920000178 Acrylic resin Polymers 0.000 claims description 7
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 5
- 229920001225 polyester resin Polymers 0.000 claims description 5
- 239000004645 polyester resin Substances 0.000 claims description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 3
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 150000003751 zinc Chemical class 0.000 claims description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 7
- 230000007797 corrosion Effects 0.000 abstract description 5
- 238000005260 corrosion Methods 0.000 abstract description 5
- 239000002131 composite material Substances 0.000 abstract description 3
- 229910001335 Galvanized steel Inorganic materials 0.000 abstract 4
- 239000008397 galvanized steel Substances 0.000 abstract 4
- 239000011247 coating layer Substances 0.000 abstract 2
- 238000010521 absorption reaction Methods 0.000 abstract 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 abstract 1
- 230000017525 heat dissipation Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 abstract 1
- 229940085991 phosphate ion Drugs 0.000 abstract 1
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 49
- 230000003628 erosive effect Effects 0.000 description 35
- 230000000052 comparative effect Effects 0.000 description 28
- 239000000523 sample Substances 0.000 description 22
- 150000001735 carboxylic acids Chemical class 0.000 description 19
- 238000000034 method Methods 0.000 description 18
- 238000005452 bending Methods 0.000 description 17
- 238000003754 machining Methods 0.000 description 16
- 238000012360 testing method Methods 0.000 description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 15
- 230000006978 adaptation Effects 0.000 description 13
- 229910052782 aluminium Inorganic materials 0.000 description 13
- 239000000463 material Substances 0.000 description 12
- 239000003513 alkali Substances 0.000 description 11
- 239000004411 aluminium Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 229910052759 nickel Inorganic materials 0.000 description 9
- 239000000049 pigment Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000003153 chemical reaction reagent Substances 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 6
- 229910000990 Ni alloy Inorganic materials 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 5
- 229910052804 chromium Inorganic materials 0.000 description 5
- 239000011651 chromium Substances 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 241000282994 Cervidae Species 0.000 description 4
- 206010038743 Restlessness Diseases 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 4
- 229940040145 liniment Drugs 0.000 description 4
- 239000000865 liniment Substances 0.000 description 4
- 150000003016 phosphoric acids Chemical class 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000012267 brine Substances 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000005246 galvanizing Methods 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000003595 mist Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- 239000011135 tin Substances 0.000 description 3
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical compound O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- 230000000007 visual effect Effects 0.000 description 3
- UUGLSEIATNSHRI-UHFFFAOYSA-N 1,3,4,6-tetrakis(hydroxymethyl)-3a,6a-dihydroimidazo[4,5-d]imidazole-2,5-dione Chemical compound OCN1C(=O)N(CO)C2C1N(CO)C(=O)N2CO UUGLSEIATNSHRI-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 238000007743 anodising Methods 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 238000007429 general method Methods 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 238000010884 ion-beam technique Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000007761 roller coating Methods 0.000 description 2
- 229920002379 silicone rubber Polymers 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 230000006208 butylation Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- ONIOAEVPMYCHKX-UHFFFAOYSA-N carbonic acid;zinc Chemical compound [Zn].OC(O)=O ONIOAEVPMYCHKX-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000011086 glassine Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910001867 inorganic solvent Inorganic materials 0.000 description 1
- 239000003049 inorganic solvent Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000021715 photosynthesis, light harvesting Effects 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- BQFYGYJPBUKISI-UHFFFAOYSA-N potassium;oxido(dioxo)vanadium Chemical compound [K+].[O-][V](=O)=O BQFYGYJPBUKISI-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000002813 thiocarbonyl group Chemical group *C(*)=S 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
- C23C22/42—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates containing also phosphates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/52—Two layers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
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Abstract
一种黑色镀锌系钢板，其特征在于，在黑色化处理的镀锌系钢板表面，具有涂敷添加有磷酸根离子、钒酸根离子、金属离子、α，β－不饱和羧酸及甘脲树脂的处理液形成的复合被膜，而且在该复合被膜的表面具有有机树脂层。上述黑色镀锌系钢板具有优良的吸放热性，而且还具有优良的导电性及加工部耐腐蚀性，不含有6价铬。
Description
技术领域
本发明涉及黑色镀锌系钢板，特别涉及具有优良的吸放热性、导电性、电磁波屏蔽性、平板部耐腐蚀性及加工部耐腐蚀性，作为使用时发热的电子仪器的框体材料等可以无涂饰使用，同时不含有害的6价铬的黑色镀锌系钢板。
背景技术
近年来，随着电子仪器性能的提高，CPU(中央处理器)等的发热量倾向于增大，其热的扩散正在成为大课题。例如，个人电脑、特别是台式个人电脑的情况，通常使用风扇排放热，当提高转数增大风量时，将出现噪音大的问题。另外，有的仪器如汽车音响部分内部等难安装风扇。这种情况下，如果能够增大框体扩散的传热量，则可以没有风扇或不增大风扇的转数，而将仪器内部发出的热快速扩散到仪器外部。
从上述观点出发，进行了赋予钢板吸放热性的试验。例如有方案(例如，特开2002-226783号公报)提出，具有含有作为颜料的碳黑和二氧化钛的涂膜的钢板。该发明根据各个颜料成分的最大热辐射率的红外线波长区域不同，通过组合这些颜料，在钢板表面上形成在宽波长区域范围显示高热辐射率的涂膜。如果使用这样的钢板作为框体材料，可以将仪器内部发出的热通过框体有效地发散到外部。
但是，为了得到充足的效果，必须使其含有大量的颜料，必须为此加厚膜厚，使成本变高。另外，也存在随着膜厚的增大，钢板表面的电阻增加的问题。为了防止电子仪器发生的电磁波泄漏，必须确实地保证框体地线，为此，钢板表面的的导电性良好是重要的。因为对电子仪器来说防止电磁波泄漏是必须的，故为了赋予吸放热性，在使用含有大量高热辐射率颜料的涂料时存在限制。
另外，众所周知，以前用于复印机内部部件等的黑色镀锌系钢板呈现黑色外观，除具有对可见光的反射率低的特性外，还有比通常的镀锌系钢板高的热辐射率。
一般在钢板上形成黑色被膜的方法大致分为以下几种。
(a)将含有碳黑等黑色颜料的涂料，利用喷雾或辊涂等涂敷，形成数十μm厚的黑色被膜的方法。
(b)通过使预先形成的镀层本身反应或电解，形成黑色被膜的方法。
但是，在(a)法得到的黑色钢板中，存在上述的普通钢板上形成含有颜料的涂饰膜时导电性低下问题。
在(b)法分类中有各种各样的方法，但近年来从环境保护的观点考虑，正在关注不含6价铬的黑色被膜的形成方法。例如，有方案提出(例如，特开2000-290783号公报)可以焊接的非铬型黑色处理镀锌系钢板，其以镀锌系钢板为基材，在镀锌系镀层的表面上，形成含有镍及锌的金属、和镍及锌的氧化物、甚至任意地含有氢氧化物的金属/氧化物复合黑色被膜，而且，在其上层，形成非铬型防锈被膜层，其含有树脂、和至少含有硫代羰基的化合物和/或钒酸化合物，而且任意地含有磷酸化合物和/或微粒氧化硅，根据需要，再作为其上层，具有任意地含有黑色颜料和/或防锈颜料的有机树脂层。
另外，有方案(例如，特开2002-47579号公报)提出具有优良的黑色外观的表面处理金属材料，其特征在于，在表面存在着Zn的金属基材上，选自Ni、Co及Fe中的一种以上的金属置换析出30～200mg/m2，形成这些金属氧化物层。
(b)法得到的黑色钢板，其目的都是提供进行取代铬酸盐处理的耐腐蚀性处理的黑色镀锌系钢板，在平板部，虽然具有大致的耐腐蚀性，但是存在加工部耐腐蚀性不足的问题。
发明内容
本发明的目的在于提供黑色镀锌系钢板，其经济且具有优良的吸放热性，并且具有优良的导电性和电磁波屏蔽性及平板部耐腐蚀性以及加工部耐腐蚀性，作为内部发热的电子仪器的框体材料等，可以无涂饰地使用，同时不含有6价铬。
为了实现上述目的，本发明提供一种黑色镀锌系钢板，其包括：镀锌系钢板；形成在该镀锌系钢板上的黑色被膜；形成在该黑色被膜上的含有磷酸根离子、钒酸根离子、金属离子、α，β-不饱和羧酸及甘脲树脂的复合被膜；和形成在该复合被膜上的有机树脂层。
上述黑色被膜优选黑色化处理上述镀锌系钢板的表面而得到的被膜。黑色被膜的膜厚优选0.01～0.5μm。
上述复合被膜优选具有0.02～1mg/m2的附着量。
上述复合被膜中的金属离子优选选自Mg离子、Zn离子、Mn离子、Al离子中的至少一种。
上述复合被膜是将含有磷酸根离子、钒酸根离子、金属离子、α，β-不饱和羧酸及甘脲树脂的处理液，涂敷在上述黑色被膜上形成的。
上述处理液中的金属离子优选选自Mg离子、Zn离子、Mn离子、Al离子中的至少一种。
上述处理液优选具有下述添加量。磷酸根离子：20～85质量％、钒酸根离子：0.5～20质量％、金属离子：5～20质量％、α，β-不饱和羧酸：2～60质量％、甘脲树脂：1～20质量％。
优选通过涂敷选自聚酯类树脂涂料、氟树脂涂料、氯乙烯溶胶涂料、丙烯酸树脂涂料中的一种涂料，形成上述有机树脂层。
上述有机树脂层优选具有0.1～4μm的膜厚。
附图说明
图1是吸放热性试验装置的示意图。
图2是表示使用参考例的电镀锌钢板、和实施例1的具有复合被膜及有机树脂层的黑色镀锌系钢板时的吸放热性的图。
图3是表示平板状的电磁波屏蔽材料的泄漏噪声测定用的框图。
图4是在图3所示的装置的Al框体上不装载试样，在开口状态下测定的噪声实例。
图5是以实用化的材料的电镀锡铁皮为试样的情况下，电磁波屏蔽性试验测定例。
图6是实施例1的电磁波屏蔽性试验测定例。
图7是图3所示装置的Al框体上不装载试样，在开口状态下，并且不振动输出高频，而测定外来噪声的实例。
具体实施方式
本发明的黑色镀锌系钢板，在黑色化处理的镀锌系钢板表面上，具有复合被膜，该复合被膜是涂敷添加有磷酸根离子(PO4 3-)、钒酸根离子(VO3 -)、金属离子、α，β-不饱和羧酸及甘脲树脂的处理液而形成的；进而，通过在该复合被膜的表面具有有机树脂层，除得到优良的吸放热性、导电性及电磁波屏蔽性外，在平板部具有优良的耐腐蚀性的基础上，加工该钢板时的加工部也具有优良的耐腐蚀性，其在广泛应用中可以具有充分的实用性。
作为本发明基材的黑色化处理的镀锌系钢板，是镀锌系钢板或镀锌合金钢板，例如熔融镀锌系钢板、熔融镀锌-铝(Zn-5质量％Al)钢板、熔融镀锌-铝(Zn-55质量％Al)钢板等镀锌系钢板被黑色化处理形成的。因为利用黑色化处理形成的黑色被膜具有优良的密合性，批量生产质量稳定，故特别优选黑色化处理后的镀锌-镍合金类钢板。黑色化处理优选在镀锌系钢板经热水洗、碱脱脂等通常的处理之后进行。
作为本发明的基材的黑色处理的镀锌系钢板，首先将镀锌系层的表面进行黑色化处理，形成黑色被膜。黑色被膜的厚度优选0.01～0.5μm，特别优选0.05～0.2μm。当小于0.01μm时，不仅黑色化不足，而且将不能得到足够的吸放热性。当超过0.5μm时，有时相对黑色被膜的镀锌系钢板的密合性变差。黑色被膜的厚度可以通过FIB(集束离子束加工装置)加工等制成薄膜后，用TEM(透射电子显微镜)观察剖面等确认。
黑色化处理方法没有特别限定，可以使用一般的方法，如阳极电解、阴极电解、交替电解等电化学处理方法，及使镍、钴、铁等金属与其金属氧化物同时置换析出的处理方法等。通过利用这些方法，形成以氧化物为主成分的黑色被膜，可以使镀锌系钢板的表面黑色化。
从其稳定性观点考虑，推荐如下黑色化处理方法：即将具有锌-镍合金层的电镀锌-镍合金钢板，例如在含有5～100g/l的氯酸根离子(ClO3 -)、10～300g/l的硫酸根离子(SO4 2-)的水溶液中，在pH0.5以上小于3.0，温度30～75℃、电量10～300C/dm2的条件下进行阳极电解。镀锌系钢板的表面形成的黑色被膜包括至少含有锌的金属和这些金属的氧化物，进而也可以含有这些金属的氢氧化物。如果列举这些金属，则为锌、镍等。
本发明的复合被膜按如下形成，即，在黑色化处理的镀锌系钢板表面，涂敷添加有磷酸根离子、钒酸根离子、金属离子、α，β-不饱和羧酸及甘脲树脂的处理液而形成，例如在磷酸水溶液中，添加钒酸化合物、金属离子、α，β-不饱和羧酸及甘脲树脂后，将形成的处理液涂敷在黑色化处理的镀锌系钢板表面，干燥。
从该处理液的涂敷容易度及干燥容易度考虑，优选设定该处理液的磷酸根离子、钒酸根离子、金属离子、α，β-不饱和羧酸及甘脲树脂的总添加浓度为10～30质量％。溶剂使用水、或水和可以与水混合的有机溶剂或无机溶剂的混合介质。
该处理液添加有磷酸根离子且为酸性，因此通过涂敷该处理液，一部分锌从镀锌系层溶解析出，该处理液中的锌离子活度增加。然后在干燥中，该处理液中的各种成分变浓，析出在黑色被膜的表面，形成含有磷酸根离子、钒酸根离子、金属离子、α，β-不饱和羧酸及甘脲树脂的复合被膜。
上述处理液的pH优选1.5～4，更优选2.5～3.5。例如pH通过适当添加氨进行调节。当pH小于1.5时，在该处理液从涂敷到干燥期间，锌类镀层剧烈溶解，镀锌系层及黑色被膜会受损。当pH超过4时，添加在该处理液的各种金属离子不能稳定存在，作为氢氧化物沉淀，有时涂敷困难。该处理液利用通常的方法，例如辊涂法、喷涂法、杆涂法等进行涂敷。
该处理液涂敷后，优选设定最高到达板温为80～250℃下进行干燥，更优选100～180℃。当小于80℃时，干燥时间过长，不适合连续生产线涂敷干燥。如果干燥温度为250℃，则足够，再提高超过需要量，则形成能源浪费。
本发明的复合被膜的附着量优选0.02～1g/m2。更优选0.05～0.5g/m2。当小于0.02g/m2时，耐腐蚀性不够，当超过1g/m2时，则表面电阻增加，有时不能得到必要的导电性及电磁波屏蔽性。
上述处理液中的磷酸根离子，在干燥时作为磷酸盐析出在黑色被膜上，使耐腐蚀性提高，同时在该处理液中具有使该处理液中的各种金属离子成分稳定化的效果。该处理液中的主要成分磷酸根离子PO4 3-向该处理液中的添加量，优选相对磷酸根离子、钒酸根离子、金属离子、α，β-不饱和羧酸及甘脲树脂向该处理液中的添加量的总量，为20～85质量％，更优选50～80质量％。当小于20质量％时，上述复合被膜中形成的磷酸盐的包敷不够，耐腐蚀性会变差。当超过85质量％时，上述复合被膜中的游离磷酸增加，耐腐蚀性仍然变差。另外，这意味着该处理液中的磷酸根离子浓度形成过剩，不经济。
上述处理液中的钒酸根离子，具有使上述复合被膜的耐腐蚀性提高的效果。钒酸根离子VO3 -向该处理液的添加量，优选相对磷酸根离子、钒酸根离子、金属离子、α，β-不饱和羧酸及甘脲树脂向该处理液中的添加的总量，为0.5～20质量％，更优选4～8质量％。当小于0.5质量％时，耐腐蚀性不够；当超过20质量％时，耐腐蚀性仍然变差。另外，这意味着使该处理液中的磷酸根离子浓度增大，有时导致该处理液中不稳定，在保存该处理液过程中生成沉淀。钒酸优选以钒酸钠、钒酸钾、钒酸铵等钒酸盐的形式添加在该处理液中。
上述处理液中的α，β-不饱和羧酸，具有提高上述复合被膜与黑色被膜的密合性的效果。α，β-不饱和羧酸向该处理液中的添加量，优选相对磷酸根离子、钒酸根离子、金属离子、α，β-不饱和羧酸及甘脲树脂向该处理液中的添加的总量，为2～60质量％，更优选10～30质量％。当小于2质量％时，与上述黑色被膜的密合性改善效果不够，结果有时加工部耐腐蚀性不够。当超过60质量％时，导电性及电磁波屏蔽性有时变差。α，β-不饱和羧酸例如有丙烯酸、甲基丙烯酸、巴豆酸、衣康酸、马来酸、富马酸等。
上述处理液中的甘脲树脂具有明显提高后述的与上述复合被膜表面设有的有机树脂层、例如聚酯类树脂层的密合性的效果。甘脲树脂向上述处理液中的添加量，优选相对磷酸根离子、钒酸根离子、金属离子、α，β-不饱和羧酸及甘脲树脂向该处理液中添加的总量，为1～20质量％，更优选5～15质量％。当小于1质量％时，与有机树脂层的密合性改善效果不够，结果有时加工部耐腐蚀性不够。当超过20质量％时，导电性及电磁波屏蔽性有时变差。
甘脲树脂是下述结构式所示的单体、或者该单体的聚合物、或者该单体的缩合物、或该单体和该单体的聚合物和该单体的缩合物的混合物。
(式中，R1～R4表示H、或CnH2n+1表示的烷基、或者CnH2nOH、或者CnH2nOCmH2m+1，m、n是1～4的整数。另外，R1～R4可以相同也可以不同。)
该单体例如有甘脲的1-，3-，4-，6-氨基的全部或一部分中加成羟甲基、羟丁基等的衍生物，使该衍生物再甲基化、甲基/乙基化、丁基化等的烷基醚化衍生物等。
该单体的缩合物，例如有通过羟甲基等缩合形成的低聚物。
优选的物质是水溶性好，在上述处理液中的稳定性良好的四羟甲基化甘脲及其低聚物。
上述处理液中的金属离子，具有提高上述复合被膜的致密性，提高耐腐蚀性的效果。金属离子优选以下述金属化合物的形态添加，即，选自Al、Mg、Mn、Zn、Co、Ti、Sn、Ni、Fe、Zr、Sr、Y、Nb、Cu、Ca、V、Ba、Na中的一种或两种以上的金属的氧化物、碳酸盐、磷酸盐、硝酸盐、醋酸盐、氢氧化物、羧酸盐、硼酸盐、氟化物等金属化合物。更优选磷酸盐、氢氧化物、氧化物、碳酸盐、硝酸盐或乙酸盐。特别优选选自Mg离子、Zn离子、Mn离子、Al离子中的一种或两种以上的磷酸盐、氢氧化物、氧化物、碳酸盐、硝酸盐或乙酸盐。
从耐腐蚀性提高的观点出发，选自Al、Mg、Mn、Zn、Co、Ti、Sn、Ni、Fe、Zr、Sr、Y、Nb、Cu、Ca、V、Ba、Na中的一种或两种以上物质向该处理液的添加量，相对磷酸根离子、钒酸根离子、金属离子、α，β-不饱和羧酸及甘脲树脂向该处理液中添加的总量，优选为5～20质量％，更优选8～15质量％。通过添加这些金属离子，可以进一步提高上述复合被膜的致密性，得到高的耐腐蚀性。当小于5质量％时，该复合被膜的耐腐蚀性提高不够，超过20质量％时，该复合被膜的析出物粗大化，反而影响耐腐蚀性。
本发明的黑色镀锌系钢板中，在上述黑色被膜、上述复合被膜的表面进一步形成有机树脂层。通过形成有机树脂层，可以提高加工部耐腐蚀性。该有机树脂层也可以应用于金属预涂的涂料而形成。具体适合应用聚酯类树脂涂料、氟树脂涂料、氯乙烯溶胶涂料、丙烯酸树脂涂料等。其中，优选多用作加工性好的家电制品的预涂钢板用涂料的聚酯类树脂涂料。
另外需要说明的是，一般的预涂钢板的情况下，有机树脂层的膜厚为10μm以上，本发明的黑色镀锌系钢板中的该有机树脂层的膜厚优选0.1～4μm以上，特别优选0.5～2μm以上。当小于0.1μm时，耐碱性不够，当超过4μm时，导电性及电磁波屏蔽性有时变差。
本发明的该有机树脂层，通过在上述复合被膜的表面，利用辊涂、喷涂涂饰、刷涂、浸渍涂敷、幕涂等方式进行涂敷，用挤干辊挤压，烧结而形成。
烧结温度优选最高达到板温为150～200℃。低于150℃时，该有机树脂层的固化略微不足，因为溶剂残存在该有机树脂层中，故有时腐蚀性稍差。另外，当超过200℃的情况下，没有特别的问题，但有时该有机树脂层成分部分分解，可见变黄。
实施例
以下，根据实施例更详细地说明本发明。但本发明不限于这些实施例。
实施例1～25、比较例1～7
在实施例1～25、比较例1～7中，在镀锌系钢板上，利用下述方法形成黑色被膜、复合被膜及有机树脂层，制造黑色镀锌系钢板。另外，作为参考例使用不进行黑色化处理，不形成复合被膜及有机树脂层的电镀锌系钢板(镀敷附着量20g/m2)。
黑色被膜的形成
在电镀生产线中，钢带宽1200mm、钢带厚0.8mm的冷轧钢板的两面上，进行镀锌-镍合金(镀敷附着量20g/m2，镍含量15质量％)后，在含有氯酸钠和硫酸钠的溶液(氯酸根离子浓度80g/l、硫酸根离子浓度100g/l、pH1.0、温度50℃)中，以镍电极为反电极，在电流密度40A/dm2的条件下进行阳极处理，在两面形成黑色被膜。该黑色被膜膜厚通过控制阳极处理时间进行调整。该黑色被膜的厚度示于表1、2。使用FIB(集束离子束加工装置)加工制成的薄膜，TEM(透射电子显微镜)观察剖面测定该黑色被膜的厚度。
复合被膜的形成
原磷酸水溶液(使用试剂特级磷酸)中，分别按形成表1、2所示的处理液中的添加量(固体成分量)，添加钒酸钠(试剂特级)、衣康酸(试剂鹿特级)、碱性碳酸锌(试剂鹿特级)、氢氧化铝(试剂鹿特级)、氢氧化锰(试剂鹿一级)、氧化镁(试剂特级)及四羟甲基化甘脲树脂(“サイメル1172”，三井サイテツク株式会社制)，配制处理液(总固体成分浓度：20质量％)。pH使用氨水(试剂特级)调整为2.9。
另外，作为比较例7，配制涂敷剂，在去离子水中添加水溶性丙烯酸树脂(关东化学株式会社制、聚丙烯酸)100.0质量份、含硫代羰基化合物(关东化学株式会社制、硫尿素)2.5质量份、磷酸化合物(关东化学株式会社制、磷酸铵)1.0质量份、及微粉氧化硅(日产化学工业株式会社制スノ一テツクス-N)10.0质量份，使总固体成分浓度为20.0质量％。
将该处理液使用辊涂机涂敷在上述镀锌-镍合金钢板的两面的上述黑色被膜的表面上，在最高到达板温以15秒达到120℃的条件下干燥，形成复合被膜。
另外，将比较例7的涂敷剂，使用杆涂机涂敷在上述镀锌-镍合金钢板的两面的上述黑色被膜的表面上，加热使最高到达板温以20秒达到120℃，形成被膜。
该复合被膜及上述被膜的附着量和该复合被膜中的磷酸根离子、钒酸根离子、金属(锌、铝、锰、镁、钠)离子、α，β-不饱和羧酸及甘脲树脂的添加量示于表1、2中。预先将该处理液中的磷酸浓度设为一定，利用形成复合被膜后的标准试样得到检测线，利用X射线荧光分析求得其附着量。
有机树脂层的形成
在聚酯-密胺树脂类PCM涂料(“Vニツト#9900”，大日本涂料株式会社制)中混合稀释剂(“Vニツト稀释剂”、大日本涂料株式会社制)，将粘度调整为福特杯(フオ一ドカツプ)#4-20s(25℃)，得到涂料溶液，将该涂料溶液用辊涂机涂敷在上述复合被膜的两表面，加热使最高到达板温以20秒达到200℃，形成有机树脂层。表1、2表示该有机树脂的膜厚。用SEM(扫描电子显微镜)观察剖面而测定膜厚。
对上述的方法得到的黑色镀锌系钢板，利用以下方法评价上述有机树脂层的密合性、吸放热性、耐腐蚀性(平板部和弯曲加工部)、耐碱性、导电性及电磁波屏蔽性。
密合性试验
将上述黑色镀锌系钢板切成纵100mm、横50mm大小的试样，将该试样以外R1.5mm弯曲90℃，设置弯曲加工部。沿该弯曲加工部的外侧的弯曲线粘贴粘结带(商品名：玻璃纸粘接带、ニチバン株式会社制)后，拉开，通过外观的变色目视判定该复合被膜和/或该有机树脂层有无剥离。完全不变色为○，变色面积率小于5％的为△，变色面积率在5％以上的为×，将其结果示于表3，4。这里所述的变色面积率是指该复合被膜和/或该有机树脂剥离外观变色的面积的总和，相对粘贴粘结带的弯曲加工部总面积的百分率。
吸放热性试验
制作图1所示的试验装置，进行吸放热性试验。用丙烯酸树脂板(板后2mm)组装框体1(内尺寸：纵280mm、横280mm、高110mm、上面完全开口)，在框体1的内面(侧面和底面)粘贴铝圈(アルミホイル)2(商品名：アルミホイル、株式会社武田コ一ポレ一シヨン社制)，完全覆盖框体1的内面(侧面和底面)。设置在框体1的内部底面中央的铝架台3上，设置硅橡胶加热器4(シリコンラバ一ヒ一タ一、アズワン株式会社制、纵150mm、横150mm、电力密度0.6w/cm2-100V加压时)，使其位于比底面高10mm的位置，从直流稳定电源5(最大70V、1A)供给电压，使其发热(输入65V×705mA＝45.8W)。在框体1上，作为顶板6，装载、密封从上述黑色镀锌系钢板上，切成纵300mm、横300mm大小的试样，使涂敷上述有机树脂层的面与设置在框体1的上面开口部(侧面上端部)的衬垫7相接。下述的铠装型铂电阻测温体10和加热器4之间的空间上，用于防止该加热器4向该铠装型铂电阻测温体10直接辐射的铝圈8(纵200mm、横200mm)，位于硅橡胶加热器4的正上方，且与底面平行地设置在自底面35mm的规定位置，为了维持其位置用钢丝9支撑铝圈8的4角。
在自顶板6垂直向下的方向离开35mm，且自铝圈8垂直向上方向离开40mm的框体1内部，插入铠装型铂电阻测温体10(直径1.6mm、长度150mm)，使其自框体1的侧面保持水平，在框体1内部的水平方向的中央部分、自顶板6垂直向下方向可以测定35mm附近的温度。将框体1内部温度的变化记录在数据记录器11上，从框体1的内部温度到达常规状态时的温度判定顶板吸放热性。判定标准是，框体1内部温度与使用参考例所示的电镀锌系钢板为顶板6的情况相比，降低幅度5℃以上时为○，小于5℃时为×。判定结果示于表3、4。
图2是表示顶板6使用参考例的电镀锌钢板和实施例1的黑色电镀锌类钢板的情况下，框体1的内部温度随加热时间的变化的曲线图。可知后者情况下，框体1的内部温度与前者相比低，吸放热性良好。
耐腐蚀性试验
将上述黑色镀锌系钢板切成和密合性试验相同的大小，同样设置有弯曲加工部的试样上，进行3循环的循环盐水喷雾试验(根据JIS Z2371-2000中性盐水喷雾试验的盐水喷雾进行8h，喷雾停止16h，将其作为1循环的试验的重复试验)，目测观察弯曲加工部和未弯曲加工的平面且涂敷上述有机树脂层的面的平板部各自白锈发生状况。设完全没有发生白锈为○，白锈发生面积率小于5％的为△，白锈发生面积率为5％以上的为×。在表3、4中表示判定结果。这里所述的白锈发生面积率是指白锈面积相对弯曲加工部和平板部分别观测的总面积的百分率。
耐碱试验
将从上述黑色镀锌系钢板切成纵100mm、横50mm大小的试样，在脱脂液(“パルクリ一ンN364S”、日本帕卡濑精株式会社制)2g/l中60℃下浸渍2min，取出后通过外观变色目测观察复合被膜和/或有机树脂层的剥落。完全没有变色的为○，变色面积率小于5％的为△，变色面积率为5％以上的为×，将结果示于表3、4。这里所述的变色面积率是指变色面积的总和相对观测总面积的百分率。
导电性试验
使用表面电阻计(“ロレスタGP”、三菱化学株式会社制)，用4探针ESP探针，在240g/探针的荷重下，将自上述黑色镀锌系钢板切成纵200mm、横100mm大小的试样，在10个位置测定涂敷有上述有机树脂层的表面电阻。10个位置的配置是：试样的一半的纵200、横50mm的区域上，主要纵方向位置不同的任意5个位置，另外一半的区域，主要是纵方向位置不同的任意5个位置。
设定10个位置电阻值都小于1mΩ的情况为○，电阻值1mΩ以上的位置有1～2个的情况为△，电阻值为1mΩ以上的位置有3个以上的情况为×。判定结果如表3、4所示。
电磁波屏蔽性试验
利用图3所示的泄漏噪声的测定评价本发明的电磁波屏蔽性。
在板厚2mm的铝板成型的外形100mm×100mm×100mm的Al制框体23中，作为振源设置20MHz的时钟脉冲(クロツク)24，每20MHz输出20～1000MHz的高频。
Al制框体23上面形成100mm×100mm的开口，在侧面侧突出20mm的边框25，与试样的评价面接触的Al制框体的上面形成外形140mm×140mm、宽20mm的前边缘状。自上述黑色镀锌系钢板切成140mm×140mm大小的试样21(板厚约0.8mm)，将其评价面22作为下表面与Al制框体23的上表面连接载置。然后，对试样21向垂直向下方向施加1kg的荷重。这里评价面22是试样21的单面的表面。
如上所述，从Al制框体23和试样21接触的前缘状接缝泄漏的电磁波，利用直径30mm的环形天线26，从边框25到50mm的位置接受信息，利用25dB的前置放大器27增幅后，使用光谱分析仪(アドバンテスト(株)制R3162)28进行分析。
电磁波屏蔽性，使用图3所示的装置，用光谱分析仪测定试样的评价面的泄漏噪声，得到图4～图6所示的图。
实施例和比较例的评价按如下进行：从频率20MHz到1000MHz每20MHz，读取自背景噪声有3dB以上差的峰值，利用下式1换算的值设定为噪声评价值(I)。
I＝10log(100.1d1+100.1d2+...100.1dn) ...式1
N：峰值自背景噪声存在3dB以上差的峰数。
d1、d2...dn：峰值和背景噪声的差(限于有3dB以上的)。
作为评价基准，考虑最适用于现时要求具有高度电磁波屏蔽性的情况，在图5中表示以实用的材料电镀锡铁皮(锡附着量2.8g/m2)为试样情况下的测定例，在图6表示实施例1的测定例，在图4中表示在无试样的状态下测定的例子。另外，在图7中表示不发振输出高频率，无试样的状态下的测定例。图7表示外来噪声。从图5、图6读取的峰值和背景噪声(28dB。图4～图7中用箭头表示)的差(限于3dB以上的)，代入上述式1，设计算结果为I0和I。另外，图5、图6中标×的位置的峰来自图7表示的外来噪声，故作为上述式1的对象以外。
对于实施例和比较例的试验材料，分别测定泄漏噪声，设I/I0≤1.2的为○，1.2＜I/I0≤1.4为△，I/I0＞1.4为×，将其结果示于表3、4。
实施例1～25中任一个密合性、吸放热性、平板部耐腐蚀性、弯曲加工部耐腐蚀性、耐碱性、导电性和电磁波屏蔽性都优良。相反，不具有黑色被膜的比较例1的吸放热性差，没有有机树脂层的比较例2的弯曲加工部耐腐蚀性和耐碱性差；没有复合被膜的比较例3和比较例6的密合性、平板部耐腐蚀性、弯曲加工部耐腐蚀性、耐碱性差，特别是有机树脂层为10.0μm厚的比较例6，其导电性和电磁波屏蔽性更差。
另外，不使用添加钒的处理液的比较例4的平板部耐腐蚀性、弯曲加工部耐腐蚀性差，不使用甘脲树脂的比较例5的密合性、弯曲加工部耐腐蚀性、耐碱性差。使用水溶性丙烯酸树脂、含硫代羰基的化合物、磷酸化合物、微粉氧化硅构成的涂敷剂的比较例7的密合性、弯曲加工部耐腐蚀性、耐碱性差，导电性和电磁波屏蔽性差。
表1
| 黑色被膜 | 复合被膜 | 有机树脂层 | |||||||||||
| 附着量(g/m2) | PO4 3-(质量％) | VO3 -(质量％) | 金属离子(质量％) | α，β-不饱和羧酸及甘脲树脂(质量％) | 甘脲树脂(质量％) | ||||||||
| 膜厚(μm) | Zn | Al | Mn | Mg | Na | 合计 | 膜厚(μm) | ||||||
| 实施例1 | 0.15 | 0.10 | 69.0 | 6.8 | 4.8 | 0.5 | 3.4 | 2.0 | 1.6 | 12.3 | 6.7 | 5.2 | 1.0 |
| 实施例2 | 0.05 | 0.10 | 69.0 | 6.8 | 4.8 | 0.5 | 3.4 | 2.0 | 1.6 | 12.3 | 6.7 | 5.2 | 1.0 |
| 实施例3 | 0.08 | 0.10 | 69.0 | 6.8 | 4.8 | 0.5 | 3.4 | 2.0 | 1.6 | 12.3 | 6.7 | 5.2 | 1.0 |
| 实施例4 | 0.50 | 0.10 | 69.0 | 6.8 | 4.8 | 0.5 | 3.4 | 2.0 | 1.6 | 12.3 | 6.7 | 5.2 | 1.0 |
| 实施例5 | 0.15 | 0.40 | 69.0 | 6.8 | 4.8 | 0.5 | 3.4 | 2.0 | 1.6 | 12.3 | 6.7 | 5.2 | 1.0 |
| 实施例6 | 0.20 | 0.20 | 69.0 | 6.8 | 4.8 | 0.5 | 3.4 | 2.0 | 1.6 | 12.3 | 6.7 | 5.2 | 1.0 |
| 实施例7 | 0.15 | 0.30 | 69.0 | 6.8 | 4.8 | 0.5 | 3.4 | 2.0 | 1.6 | 12.3 | 6.7 | 5.2 | 1.0 |
| 实施例8 | 0.15 | 0.05 | 69.0 | 6.8 | 4.8 | 0.5 | 3.4 | 2.0 | 1.6 | 12.3 | 6.7 | 5.2 | 1.0 |
| 实施例9 | 0.15 | 0.10 | 21.0 | 19.0 | 3.0 | 0.5 | 2.0 | 2.0 | 4.4 | 11.9 | 28.1 | 20.0 | 1.0 |
| 实施例10 | 0.15 | 0.10 | 40.0 | 12.0 | 4.8 | 0.5 | 3.4 | 2.0 | 2.8 | 13.5 | 19.5 | 15.0 | 1.0 |
| 实施例11 | 0.15 | 0.10 | 60.0 | 7.0 | 6.0 | 2.0 | 5.0 | 5.0 | 1.6 | 19.6 | 7.4 | 6.0 | 1.0 |
| 实施例12 | 0.15 | 0.10 | 79.0 | 3.5 | 4.8 | 0.5 | 2.0 | 2.0 | 0.8 | 10.1 | 4.4 | 3.0 | 1.0 |
| 实施例13 | 0.15 | 0.10 | 84.0 | 2.2 | 4.8 | 0.5 | 2.0 | 2.0 | 0.5 | 9.8 | 2.0 | 2.0 | 1.0 |
| 实施例14 | 0.15 | 0.10 | 69.0 | 0.6 | 4.8 | 0.5 | 3.4 | 2.0 | 0.1 | 10.8 | 11.6 | 8.0 | 1.0 |
| 实施例15 | 0.15 | 0.10 | 69.0 | 4.2 | 4.0 | 0.8 | 1.0 | 0.1 | 1.0 | 6.9 | 12.9 | 7.0 | 1.0 |
| 实施例16 | 0.15 | 0.10 | 69.0 | 6.8 | 4.8 | 0.5 | 3.4 | 2.0 | 1.6 | 12.3 | 6.7 | 5.2 | 0.2 |
| 实施例17 | 0.15 | 0.10 | 69.0 | 6.8 | 4.8 | 0.5 | 3.4 | 2.0 | 1.6 | 12.3 | 6.7 | 5.2 | 0.5 |
| 实施例18 | 0.15 | 0.10 | 69.0 | 6.8 | 4.8 | 0.5 | 3.4 | 2.0 | 1.6 | 12.3 | 6.7 | 5.2 | 2.0 |
表2
| 黑色被膜 | 复合被膜 | 有机树脂层 | |||||||||||
| 附着量(g/m2) | PO4 3(质量％) | VO3 -(质量％) | 金属离子(质量％) | α，β-不饱和羧酸及甘脲树脂(质量％) | 甘脲树脂(质量％) | ||||||||
| 膜厚(μm) | Zn | Al | Mn | Mg | Na | 合计 | 膜厚(μm) | ||||||
| 实施例19 | 0.20 | 0.3 | 69.0 | 6.8 | 4.8 | 0.5 | 3.4 | 2.0 | 1.6 | 12.3 | 6.7 | 5.2 | 0.05 |
| 实施例20 | 0.15 | 0.3 | 69.0 | 6.8 | 4.8 | 0.5 | 3.4 | 2.0 | 1.6 | 12.3 | 6.7 | 5.2 | 4.00 |
| 实施例21 | 0.15 | 1.2 | 69.0 | 6.8 | 4.8 | 0.5 | 3.4 | 2.0 | 1.6 | 12.3 | 6.7 | 5.2 | 1.00 |
| 实施例22 | 0.15 | 0.3 | 19.0 | 10.0 | 4.8 | 0.5 | 3.4 | 2.0 | 2.3 | 13.0 | 35.0 | 23.0 | 1.00 |
| 实施例23 | 0.15 | 0.3 | 86.0 | 1.0 | 3.5 | 0.5 | 2.9 | 2.0 | 0.2 | 9.1 | 1.9 | 2.0 | 1.00 |
| 实施例24 | 0.15 | 0.3 | 69.0 | 6.8 | 1.0 | 0.0 | 0.0 | 2.0 | 1.6 | 4.6 | 11.6 | 8.0 | 1.00 |
| 实施例25 | 0.15 | 0.3 | 62.0 | 6.8 | 6.0 | 6.0 | 5.0 | 2.5 | 1.6 | 21.1 | 5.1 | 5.0 | 1.00 |
| 比较例1 | 0.00 | 0.3 | 69.0 | 6.8 | 4.8 | 0.5 | 3.4 | 2.0 | 1.6 | 12.3 | 6.7 | 5.2 | 1.00 |
| 比较例2 | 0.15 | 0.3 | 69.0 | 6.8 | 4.8 | 0.5 | 3.4 | 2.0 | 1.6 | 12.3 | 6.7 | 5.2 | 0.00 |
| 比较例3 | 0.15 | 0.0 | - | - | - | - | - | - | - | - | - | - | 1.00 |
| 比较例4 | 0.15 | 0.3 | 75.0 | 0.0 | 4.8 | 0.5 | 3.4 | 2.0 | 0.1 | 10.8 | 8.2 | 6.0 | 1.00 |
| 比较例5 | 0.15 | 0.3 | 77.0 | 8.0 | 6.0 | 0.7 | 4.0 | 2.0 | 1.9 | 14.6 | 0.4 | 0.0 | 1.00 |
| 比较例6 | 0.15 | 0.0 | - | - | - | - | - | - | - | - | - | - | 10.00 |
| 比较例7 | 0.15 | 3.0* | - | - | - | - | - | - | - | - | - | - | 0.0 |
*涂敷剂(水溶性丙烯酸树脂∶含硫代羰基化合物∶磷酸化合物∶微粉氧化硅固体成分质量比＝100.0∶2.5∶1.0∶10.0)
“-”表示不含有
表3
| 密合性 | 吸放热性 | 平板部耐腐蚀性 | 弯曲加工部耐腐蚀性 | 耐碱性 | 导电性 | 电磁波屏蔽性 | |
| 实施例1 | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| 实施例2 | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| 实施例3 | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| 实施例4 | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| 实施例5 | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| 实施例6 | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| 实施例7 | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| 实施例8 | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| 实施例9 | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| 实施例10 | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| 实施例11 | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| 实施例12 | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| 实施例13 | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| 实施例14 | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| 实施例15 | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| 实施例16 | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| 实施例17 | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| 实施例18 | ○ | ○ | ○ | ○ | ○ | △ | △ |
表4
| 密合性 | 吸放热性 | 平板部耐腐蚀性 | 弯曲加工部耐腐蚀性 | 耐碱性 | 导电性 | 电磁波屏蔽性 | |
| 实施例19 | △ | ○ | ○ | △ | △ | ○ | ○ |
| 实施例20 | ○ | ○ | ○ | ○ | ○ | △ | △ |
| 实施例21 | ○ | ○ | ○ | ○ | ○ | △ | △ |
| 实施例22 | ○ | ○ | ○ | △ | ○ | ○ | ○ |
| 实施例23 | ○ | ○ | △ | △ | ○ | ○ | ○ |
| 实施例24 | ○ | ○ | ○ | △ | ○ | ○ | ○ |
| 实施例25 | ○ | ○ | △ | △ | ○ | ○ | ○ |
| 比较例1 | ○ | × | ○ | ○ | ○ | ○ | ○ |
| 比较例2 | ○ | ○ | ○ | × | × | ○ | ○ |
| 比较例3 | × | ○ | × | × | × | ○ | ○ |
| 比较例4 | ○ | ○ | × | × | ○ | ○ | ○ |
| 比较例5 | × | ○ | ○ | × | × | ○ | ○ |
| 比较例6 | × | ○ | × | × | × | × | × |
| 比较例7 | × | ○ | △ | × | × | × | × |
Claims (10)
1.一种黑色镀锌系钢板，其包括：镀锌系钢板；形成在该镀锌系钢板上的黑色被膜；形成在该黑色被膜上的含有磷酸根离子、钒酸根离子、金属离子、α，β-不饱和羧酸及甘脲树脂的复合被膜；和形成在该复合被膜上的有机树脂层。
2.如权利要求1所述的黑色镀锌系钢板，所述黑色被膜是将上述镀锌系钢板的表面黑色化处理而得到的被膜。
3.如权利要求1所述的黑色镀锌系钢板，所述黑色被膜具有0.01～0.5μm的膜厚。
4.如权利要求1所述的黑色镀锌系钢板，所述复合被膜具有0.02～1mg/m2的附着量。
5.如权利要求1所述的黑色镀锌系钢板，所述复合被膜中的金属离子是选自Mg离子、Zn离子、Mn离子、Al离子中的至少一种。
6.如权利要求1所述的黑色镀锌系钢板，所述复合被膜是将含有磷酸根离子、钒酸根离子、金属离子、α，β-不饱和羧酸及甘脲树脂的处理液，涂敷在上述黑色被膜上形成的。
7.如权利要求1所述的黑色镀锌系钢板，所述处理液中的金属离子是选自Mg离子、Zn离子、Mn离子、Al离子中的至少一种。
8.如权利要求6所述的黑色镀锌系钢板，所述处理液具有下述添加量，磷酸根离子：20～85质量％、钒酸根离子：0.5～20质量％、金属离子：5～20质量％、α，β-不饱和羧酸：2～60质量％、甘脲树脂：1～20质量％。
9.如权利要求1所述的黑色镀锌系钢板，所述有机树脂层，是通过涂敷选自聚酯类树脂涂料、氟树脂涂料、氯乙烯溶胶涂料、丙烯酸树脂涂料中的一种涂料而形成的。
10.如权利要求1所述的黑色镀锌系钢板，所述有机树脂层具有0.1～4μm的膜厚。
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| JP023467/2003 | 2003-01-31 | ||
| JP2003023467 | 2003-01-31 |
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| Country | Link |
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| US (1) | US7186467B2 (zh) |
| KR (1) | KR100700436B1 (zh) |
| CN (1) | CN100497733C (zh) |
| WO (1) | WO2004067802A1 (zh) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101535529B (zh) * | 2006-12-13 | 2011-02-16 | 杰富意钢铁株式会社 | 平板部耐腐蚀性、耐黑变性及冲压成形后的外观和耐腐蚀性优良的表面处理镀锌系钢板以及镀锌系钢板用水系表面处理液 |
| CN102031510A (zh) * | 2010-12-30 | 2011-04-27 | 合肥华清金属表面处理有限责任公司 | 一种金属镀锌层发黑剂及其制备方法 |
| CN103108991A (zh) * | 2010-09-15 | 2013-05-15 | 杰富意钢铁株式会社 | 容器用钢板的制造方法 |
| CN104294348A (zh) * | 2013-07-16 | 2015-01-21 | 蒂森克虏拉塞斯坦有限公司 | 用于钝化带状的黑铁皮的方法 |
| TWI494215B (zh) * | 2012-03-01 | 2015-08-01 | Kobe Steel Ltd | 著色樹脂塗裝金屬板 |
| CN107532307A (zh) * | 2015-06-15 | 2018-01-02 | 杰富意钢铁株式会社 | 表面处理镀锌系钢板及其制造方法 |
| CN107541722A (zh) * | 2016-06-24 | 2018-01-05 | Posco公司 | 镀锌系钢板用磷酸盐溶液、磷酸盐处理镀锌系钢板及其制造方法 |
| CN113825640A (zh) * | 2019-05-24 | 2021-12-21 | 日本制铁株式会社 | 镀敷钢板 |
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| JP2010112667A (ja) * | 2008-11-10 | 2010-05-20 | Mitsubishi Electric Corp | 空気調和機 |
| MX343388B (es) | 2009-08-06 | 2016-11-04 | Nippon Steel & Sumitomo Metal Corp | Lámina de metal para calentamiento por radiación, proceso para producir la misma, y metal procesado que tiene una porción con resistencia diferente y proceso para producir el mismo. |
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| DE102011078258A1 (de) * | 2011-06-29 | 2013-01-03 | Henkel Ag & Co. Kgaa | Elektrolytische Vereisenung von Zinkoberflächen |
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| KR102390079B1 (ko) * | 2015-04-28 | 2022-04-25 | 스미토모 긴조쿠 고잔 가부시키가이샤 | 도전성 기판 |
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|---|---|---|---|---|
| JPS6270583A (ja) | 1986-09-16 | 1987-04-01 | Nippon Steel Corp | 黒色亜鉛合金メツキ鋼板の製造方法 |
| US5525431A (en) * | 1989-12-12 | 1996-06-11 | Nippon Steel Corporation | Zinc-base galvanized sheet steel excellent in press-formability, phosphatability, etc. and process for producing the same |
| JP2000290783A (ja) * | 1999-02-01 | 2000-10-17 | Nippon Steel Corp | 溶接可能な非クロム型黒色処理亜鉛系めっき鋼板 |
| JP2002047579A (ja) | 2000-07-31 | 2002-02-15 | Kobe Steel Ltd | 黒色外観に優れた表面処理金属材料 |
| JP3864705B2 (ja) | 2001-01-31 | 2007-01-10 | 住友金属工業株式会社 | 熱放射性表面処理材 |
-
2004
- 2004-01-30 WO PCT/JP2004/000951 patent/WO2004067802A1/ja active Application Filing
- 2004-01-30 CN CNB2004800031343A patent/CN100497733C/zh not_active Expired - Fee Related
- 2004-01-30 US US10/536,564 patent/US7186467B2/en not_active Expired - Lifetime
- 2004-01-30 KR KR1020057011959A patent/KR100700436B1/ko active IP Right Grant
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101535529B (zh) * | 2006-12-13 | 2011-02-16 | 杰富意钢铁株式会社 | 平板部耐腐蚀性、耐黑变性及冲压成形后的外观和耐腐蚀性优良的表面处理镀锌系钢板以及镀锌系钢板用水系表面处理液 |
| CN103108991A (zh) * | 2010-09-15 | 2013-05-15 | 杰富意钢铁株式会社 | 容器用钢板的制造方法 |
| CN103108991B (zh) * | 2010-09-15 | 2016-05-25 | 杰富意钢铁株式会社 | 容器用钢板的制造方法 |
| CN102031510A (zh) * | 2010-12-30 | 2011-04-27 | 合肥华清金属表面处理有限责任公司 | 一种金属镀锌层发黑剂及其制备方法 |
| CN102031510B (zh) * | 2010-12-30 | 2012-07-25 | 合肥华清金属表面处理有限责任公司 | 一种金属镀锌层发黑剂及其制备方法 |
| TWI494215B (zh) * | 2012-03-01 | 2015-08-01 | Kobe Steel Ltd | 著色樹脂塗裝金屬板 |
| CN104294348A (zh) * | 2013-07-16 | 2015-01-21 | 蒂森克虏拉塞斯坦有限公司 | 用于钝化带状的黑铁皮的方法 |
| CN107532307A (zh) * | 2015-06-15 | 2018-01-02 | 杰富意钢铁株式会社 | 表面处理镀锌系钢板及其制造方法 |
| CN107532307B (zh) * | 2015-06-15 | 2019-12-24 | 杰富意钢铁株式会社 | 表面处理镀锌系钢板及其制造方法 |
| CN107541722A (zh) * | 2016-06-24 | 2018-01-05 | Posco公司 | 镀锌系钢板用磷酸盐溶液、磷酸盐处理镀锌系钢板及其制造方法 |
| CN113825640A (zh) * | 2019-05-24 | 2021-12-21 | 日本制铁株式会社 | 镀敷钢板 |
| CN113825640B (zh) * | 2019-05-24 | 2023-09-15 | 日本制铁株式会社 | 镀敷钢板 |
Also Published As
| Publication number | Publication date |
|---|---|
| US20050282033A1 (en) | 2005-12-22 |
| CN100497733C (zh) | 2009-06-10 |
| KR100700436B1 (ko) | 2007-03-28 |
| WO2004067802A1 (ja) | 2004-08-12 |
| KR20050089076A (ko) | 2005-09-07 |
| US7186467B2 (en) | 2007-03-06 |
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