KR20240087343A - Surface treatment composition for plated steel sheet, plated steel sheet using same and method for manufacturing thereof - Google Patents
Surface treatment composition for plated steel sheet, plated steel sheet using same and method for manufacturing thereof Download PDFInfo
- Publication number
- KR20240087343A KR20240087343A KR1020220172956A KR20220172956A KR20240087343A KR 20240087343 A KR20240087343 A KR 20240087343A KR 1020220172956 A KR1020220172956 A KR 1020220172956A KR 20220172956 A KR20220172956 A KR 20220172956A KR 20240087343 A KR20240087343 A KR 20240087343A
- Authority
- KR
- South Korea
- Prior art keywords
- steel sheet
- corrosion resistance
- plated steel
- solution composition
- surface treatment
- Prior art date
Links
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 91
- 239000010959 steel Substances 0.000 title claims abstract description 91
- 239000000203 mixture Substances 0.000 title claims abstract description 77
- 238000004381 surface treatment Methods 0.000 title claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 238000000034 method Methods 0.000 title claims description 16
- 230000007797 corrosion Effects 0.000 claims abstract description 151
- 238000005260 corrosion Methods 0.000 claims abstract description 151
- 239000011701 zinc Substances 0.000 claims abstract description 7
- 230000007774 longterm Effects 0.000 claims description 39
- 238000007747 plating Methods 0.000 claims description 31
- 239000010410 layer Substances 0.000 claims description 26
- 238000000576 coating method Methods 0.000 claims description 21
- 239000011248 coating agent Substances 0.000 claims description 19
- 150000001845 chromium compounds Chemical class 0.000 claims description 15
- 239000011247 coating layer Substances 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- 239000000314 lubricant Substances 0.000 claims description 14
- 239000011777 magnesium Substances 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- -1 chromium chloride anhydride Chemical class 0.000 claims description 9
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 8
- 239000006184 cosolvent Substances 0.000 claims description 8
- 229910000077 silane Inorganic materials 0.000 claims description 8
- 229910017706 MgZn Inorganic materials 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 239000004698 Polyethylene Substances 0.000 claims description 6
- 229910001297 Zn alloy Inorganic materials 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 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 claims description 6
- 239000013078 crystal Substances 0.000 claims description 6
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims description 6
- 229920000573 polyethylene Polymers 0.000 claims description 6
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 4
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 4
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 4
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 claims description 4
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 4
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 4
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 4
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 4
- 239000007921 spray Substances 0.000 claims description 4
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 claims description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- FSJSYDFBTIVUFD-SUKNRPLKSA-N (z)-4-hydroxypent-3-en-2-one;oxovanadium Chemical compound [V]=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FSJSYDFBTIVUFD-SUKNRPLKSA-N 0.000 claims description 2
- PAJMKGZZBBTTOY-UHFFFAOYSA-N 2-[[2-hydroxy-1-(3-hydroxyoctyl)-2,3,3a,4,9,9a-hexahydro-1h-cyclopenta[g]naphthalen-5-yl]oxy]acetic acid Chemical compound C1=CC=C(OCC(O)=O)C2=C1CC1C(CCC(O)CCCCC)C(O)CC1C2 PAJMKGZZBBTTOY-UHFFFAOYSA-N 0.000 claims description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 2
- LVACOMKKELLCHJ-UHFFFAOYSA-N 3-trimethoxysilylpropylurea Chemical compound CO[Si](OC)(OC)CCCNC(N)=O LVACOMKKELLCHJ-UHFFFAOYSA-N 0.000 claims description 2
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 claims description 2
- 229910021555 Chromium Chloride Inorganic materials 0.000 claims description 2
- 235000010919 Copernicia prunifera Nutrition 0.000 claims description 2
- 244000180278 Copernicia prunifera Species 0.000 claims description 2
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims description 2
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims description 2
- 238000002441 X-ray diffraction Methods 0.000 claims description 2
- QUEDYRXQWSDKKG-UHFFFAOYSA-M [O-2].[O-2].[V+5].[OH-] Chemical compound [O-2].[O-2].[V+5].[OH-] QUEDYRXQWSDKKG-UHFFFAOYSA-M 0.000 claims description 2
- YZETUZZBXNVESH-UHFFFAOYSA-I [V+5].CC(=O)CC([O-])=O.CC(=O)CC([O-])=O.CC(=O)CC([O-])=O.CC(=O)CC([O-])=O.CC(=O)CC([O-])=O Chemical compound [V+5].CC(=O)CC([O-])=O.CC(=O)CC([O-])=O.CC(=O)CC([O-])=O.CC(=O)CC([O-])=O.CC(=O)CC([O-])=O YZETUZZBXNVESH-UHFFFAOYSA-I 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- 235000004279 alanine Nutrition 0.000 claims description 2
- 229910021563 chromium fluoride Inorganic materials 0.000 claims description 2
- LJAOOBNHPFKCDR-UHFFFAOYSA-K chromium(3+) trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[Cr+3] LJAOOBNHPFKCDR-UHFFFAOYSA-K 0.000 claims description 2
- ONVSPUZIHWFQDG-UHFFFAOYSA-K chromium(3+);trichloride;pentahydrate Chemical compound O.O.O.O.O.[Cl-].[Cl-].[Cl-].[Cr+3] ONVSPUZIHWFQDG-UHFFFAOYSA-K 0.000 claims description 2
- 229910000151 chromium(III) phosphate Inorganic materials 0.000 claims description 2
- 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 claims description 2
- IKZBVTPSNGOVRJ-UHFFFAOYSA-K chromium(iii) phosphate Chemical compound [Cr+3].[O-]P([O-])([O-])=O IKZBVTPSNGOVRJ-UHFFFAOYSA-K 0.000 claims description 2
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 claims description 2
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 claims description 2
- 229940043279 diisopropylamine Drugs 0.000 claims description 2
- PKTOVQRKCNPVKY-UHFFFAOYSA-N dimethoxy(methyl)silicon Chemical compound CO[Si](C)OC PKTOVQRKCNPVKY-UHFFFAOYSA-N 0.000 claims description 2
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 claims description 2
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 claims description 2
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical compound NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 claims description 2
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 claims description 2
- 239000004310 lactic acid Substances 0.000 claims description 2
- 235000014655 lactic acid Nutrition 0.000 claims description 2
- NHBRUUFBSBSTHM-UHFFFAOYSA-N n'-[2-(3-trimethoxysilylpropylamino)ethyl]ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCNCCN NHBRUUFBSBSTHM-UHFFFAOYSA-N 0.000 claims description 2
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 claims description 2
- 235000002949 phytic acid Nutrition 0.000 claims description 2
- 229940068041 phytic acid Drugs 0.000 claims description 2
- 239000000467 phytic acid Substances 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 239000003760 tallow Substances 0.000 claims description 2
- 150000004992 toluidines Chemical class 0.000 claims description 2
- UDUKMRHNZZLJRB-UHFFFAOYSA-N triethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OCC)(OCC)OCC)CCC2OC21 UDUKMRHNZZLJRB-UHFFFAOYSA-N 0.000 claims description 2
- FTBATIJJKIIOTP-UHFFFAOYSA-K trifluorochromium Chemical compound F[Cr](F)F FTBATIJJKIIOTP-UHFFFAOYSA-K 0.000 claims description 2
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims 2
- 229920002554 vinyl polymer Polymers 0.000 claims 2
- MTEZSDOQASFMDI-UHFFFAOYSA-N 1-trimethoxysilylpropan-1-ol Chemical compound CCC(O)[Si](OC)(OC)OC MTEZSDOQASFMDI-UHFFFAOYSA-N 0.000 claims 1
- 239000004593 Epoxy Substances 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- IBKNSIPMTGYUNZ-UHFFFAOYSA-N ethenyl(methoxy)silane Chemical compound CO[SiH2]C=C IBKNSIPMTGYUNZ-UHFFFAOYSA-N 0.000 claims 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052725 zinc Inorganic materials 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 50
- 230000007547 defect Effects 0.000 description 24
- 238000011156 evaluation Methods 0.000 description 12
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 11
- 239000010779 crude oil Substances 0.000 description 10
- 229910003023 Mg-Al Inorganic materials 0.000 description 9
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 9
- 239000003513 alkali Substances 0.000 description 7
- 239000011651 chromium Substances 0.000 description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 6
- 229910052804 chromium Inorganic materials 0.000 description 6
- 238000003754 machining Methods 0.000 description 6
- 230000035515 penetration Effects 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 229910001335 Galvanized steel Inorganic materials 0.000 description 5
- 239000008397 galvanized steel Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005238 degreasing Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 229910002058 ternary alloy Inorganic materials 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000002542 deteriorative effect Effects 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 description 1
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000003666 anti-fingerprint Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 239000003256 environmental substance Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- ALTWGIIQPLQAAM-UHFFFAOYSA-N metavanadate Chemical compound [O-][V](=O)=O ALTWGIIQPLQAAM-UHFFFAOYSA-N 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- BYOIQYHAYWYSCZ-UHFFFAOYSA-N prop-2-enoxysilane Chemical compound [SiH3]OCC=C BYOIQYHAYWYSCZ-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
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
-
- 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
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
- C23C2/06—Zinc or cadmium or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/26—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/321—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/10—Use of solutions containing trivalent chromium but free of hexavalent chromium
Abstract
본 발명은 아연합금 도금강판의 내식성, 윤활성 등을 향상시킬 수 있는 표면처리 용액 조성물과, 이를 이용하여 표면처리된 도금강판 및 상기 도금강판을 제조하는 방법에 관한 것이다. The present invention relates to a surface treatment solution composition that can improve the corrosion resistance, lubricity, etc. of zinc alloy-plated steel sheets, a surface-treated plated steel sheet using the same, and a method of manufacturing the plated steel sheets.
Description
본 발명은 건자재 용도 등으로 사용되는 도금강판의 윤활성, 내식성 등을 향상시킬 수 있는 표면처리용 용액 조성물 이를 이용하여 표면처리된 도금강판과 상기 도금강판을 제조하는 방법에 관한 것이다.The present invention relates to a solution composition for surface treatment that can improve the lubricity and corrosion resistance of plated steel sheets used for construction materials, etc., a surface-treated plated steel sheet using the same, and a method of manufacturing the plated steel sheets.
건자재 등으로 사용되는 도금강판은 고내식이 요구되며, 일예로 아연(Zn), 마그네슘(Mg) 및 알루미늄(Al)을 함유하는 도금층이 형성된 고내식 용융도금강판이 많이 사용된다. 이러한 고내식 용융도금강판은 적청(red rust) 내식성이 우수한 것으로 알려져 있다.Coated steel sheets used as building materials, etc. require high corrosion resistance. For example, highly corrosion-resistant hot-dip galvanized steel sheets formed with a plating layer containing zinc (Zn), magnesium (Mg), and aluminum (Al) are widely used. These highly corrosion-resistant hot-dip galvanized steel sheets are known to have excellent red rust corrosion resistance.
그러나, 이러한 고내식 용융도금강판은 노출면이 대부분 아연 또는 아연합금으로 이루어져 있어, 일반 환경 일반 환경 특히, 습윤 분위기에 노출되었을 때 표면에 점상의 부식성 결함이 쉽게 발생하여 외관이 나빠지는 문제가 있다. However, since most of the exposed surfaces of these highly corrosion-resistant hot-dip galvanized steel sheets are made of zinc or zinc alloy, there is a problem in that point-like corrosive defects easily occur on the surface when exposed to the general environment, especially a humid atmosphere, deteriorating the appearance. .
이러한 문제를 해결하기 위해서, 대부분의 도금강판은 표면에 표면처리 용액을 적용하여 도금층이 부식되어 발생하는 백청 생성을 억제하고 있다. 종래에는 도금처리된 강판에 6가 크롬 또는 크로메이트 처리를 행함으로써 내식성 및 내흑변성을 확보하여 왔다. 그러나, 6가 크롬이 유해 환경물질로 지정되면서 현재에는 6가 크롬 사용에 대한 규제가 강화되고 있는 실정이다. 더욱이, 6가 크롬을 도금강판의 표면처리제로 사용시 강판 표면이 흑색으로 변하거나 흑점이 발생하는 결함의 문제가 있다.To solve this problem, most coated steel sheets apply a surface treatment solution to the surface to suppress the formation of white rust caused by corrosion of the plating layer. Conventionally, corrosion resistance and blackening resistance have been secured by performing hexavalent chromium or chromate treatment on plated steel sheets. However, as hexavalent chromium has been designated as a hazardous environmental substance, regulations on the use of hexavalent chromium are currently being strengthened. Moreover, when hexavalent chromium is used as a surface treatment agent for plated steel sheets, there is a problem of defects such as the surface of the steel sheet turning black or black spots occurring.
따라서, 현재에는 3가 크롬을 함유하는 표면처리 용액 조성물을 도금강판 상에 코팅하여 도금강판의 내식성 및 내흑변성을 확보하는 방법이 적용되고 있다. 예를 들어, 특허문헌 1 내지 3은 3가 크롬을 함유한 조성물에 강판을 침적시켜 화성 처리하는 방식으로 내식성 및 흑변성을 확보하고 있으나, 철강사의 연속공정에 적용하기에는 침적시간이 길고, 화성 처리 방법은 내지문성 저하 등의 문제가 있다.Therefore, a method of securing corrosion resistance and blackening resistance of the plated steel sheet by coating a surface treatment solution composition containing trivalent chromium on the plated steel sheet is currently being applied. For example, Patent Documents 1 to 3 secure corrosion resistance and blackening by immersing a steel sheet in a composition containing trivalent chromium and chemical treatment, but the immersion time is long and the chemical treatment is too long to be applied to the continuous process of steelmaking. This method has problems such as reduced fingerprint resistance.
또한, 특허문헌 4 및 5는 크롬을 함유한 조성물을 도금강판 상에 스프레이 또는 롤코터 방식으로 코팅함으로써, 철강사의 연속라인에 적용이 가능하고 내지문성을 확보할 수 있다고 개시하고 있다. 하지만, 이들 조성물에는 다공질의 실리카 성분이 함유됨에 따라 습윤한 분위기에서 변색 발생이 심한 Mg, Al계 합금에는 적합하지 않다. 뿐만 아니라, 다공질의 실리카는 흡습 성질이 강하여 Zn-Mg-Al계 합금 강판에서는 급격한 변색 발생을 유발시키는 문제가 있다.In addition, Patent Documents 4 and 5 disclose that by coating a composition containing chromium on a plated steel sheet using a spray or roll coater method, it can be applied to a continuous line of steel mills and anti-fingerprint properties can be secured. However, as these compositions contain porous silica components, they are not suitable for Mg- and Al-based alloys, which are prone to severe discoloration in a humid atmosphere. In addition, porous silica has strong moisture absorption properties, which causes rapid discoloration in Zn-Mg-Al alloy steel sheets.
본 발명의 일 측면은, 도금강판 바람직하게는 삼원계 합금도금강판의 표면에 적용되는 코팅 용액의 조성을 제어하여 부식 초기의 백청 발생을 억제할 뿐만 아니라, 궁극적으로 희생방식에 의한 도금층의 감소 속도를 늦추고 소지철의 부식속도를 늦추어 장기 내식성을 향상시킬 수 있는 용액 조성물을 제공하고, 이를 이용하여 표면처리된 도금강판 및 이의 제조방법을 제공하고자 하는 것이다.One aspect of the present invention is to control the composition of the coating solution applied to the surface of a plated steel sheet, preferably a ternary alloy plated steel sheet, to not only suppress the generation of white rust in the early stages of corrosion, but also ultimately reduce the rate of reduction of the plating layer by sacrificial method. The object is to provide a solution composition that can improve long-term corrosion resistance by slowing down the corrosion rate of base iron, and to provide a surface-treated plated steel sheet and a manufacturing method thereof using the same.
본 발명의 과제는 상술한 내용에 한정하지 않는다. 본 발명의 과제는 본 명세서의 내용 전반으로부터 이해될 수 있을 것이며, 본 발명이 속하는 기술분야에서 통상의 지식을 가지는 자라면 본 발명의 부가적인 과제를 이해하는데 아무런 어려움이 없을 것이다.The object of the present invention is not limited to the above-described content. The subject of the present invention can be understood from the overall content of the present specification, and those skilled in the art will have no difficulty in understanding the additional subject of the present invention.
본 발명의 일태양은 3가 크롬 화합물 1~10중량%, One aspect of the present invention is 1 to 10% by weight of a trivalent chromium compound,
산도 조절제 0.1~5중량%, Acidity regulator 0.1~5% by weight,
밀착성 향상제 1~20중량%, Adhesion improver 1-20% by weight,
내식성 개선제 1~20중량%, Corrosion resistance improver 1~20% by weight,
점상 부식 개선제 0.1~5.0중량%, Spot corrosion improver 0.1 to 5.0% by weight,
장기 내식성 향상제 1~10중량%, 1 to 10% by weight of long-term corrosion resistance improver,
윤활제 0.1~3.0중량%, Lubricant 0.1~3.0% by weight,
조용제 1~20중량% 및 잔량 용제를 포함하는 표면처리용 용액 조성물을 제공한다. A solution composition for surface treatment containing 1 to 20% by weight of a co-solvent and the remaining amount of solvent is provided.
본 발명의 다른 일태양은 강판;Another aspect of the present invention is a steel plate;
상기 강판의 적어도 일면에 형성된 도금층; 및 A plating layer formed on at least one surface of the steel sheet; and
상기 도금층 상에 형성된 표면처리 코팅층을 포함하며,It includes a surface treatment coating layer formed on the plating layer,
상기 표면처리 코팅층은 상기 용액 조성물로 형성된 것인 표면처리된 도금강판을 제공한다. The surface treatment coating layer provides a surface-treated plated steel sheet formed from the solution composition.
본 발명의 또다른 일태양은 적어도 일면에 도금층이 형성된 도금강판을 제공하는 단계;Another aspect of the present invention includes providing a plated steel sheet having a plating layer formed on at least one surface;
상기 도금층 상에 상기 용액 조성물을 코팅처리하는 단계; 및Coating the solution composition on the plating layer; and
상기 코팅처리된 강판을 건조처리하는 단계를 포함하는 표면처리된 도금강판의 제조방법을 제공한다. A method for manufacturing a surface-treated plated steel sheet is provided, including the step of drying the coated steel sheet.
본 발명에 의하면, 고내식 도금강판의 표면에 적용되는 코팅 용액의 조성을 조절하여 부식 초기의 백청 발생뿐만 아니라, 궁극적으로 희생방식에 의한 도금층의 감모속도를 늦추어 소지철의 부식속도를 늦추어 장기 내식성이 향상되는 효과를 갖는 표면처리용 용액 조성물을 제공할 수 있다.According to the present invention, by controlling the composition of the coating solution applied to the surface of the highly corrosion-resistant plated steel sheet, not only does white rust occur in the early stages of corrosion, but it ultimately slows down the corrosion rate of the base iron by slowing down the wear rate of the plating layer due to sacrificial corrosion, thereby improving long-term corrosion resistance. A solution composition for surface treatment with improved effectiveness can be provided.
또한, 본 발명에 의하면, 평판 내식성, 가공 내식성, 조관유 침해성, 내알칼리성, 점상 부식 내식성, 내흑변성 및 장기 내식성이 우수하며 이물결함이 발생하지 않는 고내식 도금강판을 제공할 수 있다.In addition, according to the present invention, it is possible to provide a highly corrosion-resistant plated steel sheet that is excellent in plate corrosion resistance, processing corrosion resistance, crude oil penetration, alkali resistance, pitting corrosion resistance, blackening resistance, and long-term corrosion resistance, and does not generate foreign material defects.
본 발명의 다양하면서도 유익한 장점과 효과는 상술한 내용에 한정되지 않고, 본 발명의 구체적인 실시 태양을 설명하는 과정에서 보다 쉽게 이해될 수 있을 것이다.The various and beneficial advantages and effects of the present invention are not limited to the above-described content, and may be more easily understood through description of specific embodiments of the present invention.
도 1은 본 발명의 실시예 중 장기 내식성 평가에서, 비교예 1에서 적청이 발생한 것을 나타낸 사진이다.
도 2는 본 발명의 실시예 중 장기 내식성 평가에서, 발명예 3에서 적청이 발생하지 않은 것을 나타낸 사진이다. Figure 1 is a photograph showing that red rust occurred in Comparative Example 1 in the long-term corrosion resistance evaluation among the examples of the present invention.
Figure 2 is a photograph showing that red rust did not occur in Inventive Example 3 in the long-term corrosion resistance evaluation among the Examples of the present invention.
본 명세서에서 사용되는 용어는 본 발명을 설명하기 위한 것이고, 본 발명을 한정하는 것을 의도하지 않는다. 또한, 본 명세서에서 사용되는 단수 형태들은 관련 정의가 이와 명백히 반대되는 의미를 나타내지 않는 한 복수 형태들도 포함한다. The terms used in this specification are for describing the present invention and are not intended to limit the present invention. Additionally, as used herein, singular forms include plural forms unless the relevant definition clearly indicates the contrary.
명세서에서 사용되는 "포함하는"의 의미는 구성을 구체화하고, 다른 구성의 존재나 부가를 제외하는 것은 아니다.The meaning of “including” used in the specification specifies a configuration and does not exclude the presence or addition of another configuration.
달리 정의하지 않는 한, 본 명세서에서 사용되는 기술 용어 및 과학 용어를 포함하는 모든 용어들은 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자가 일반적으로 이해하는 의미와 동일한 의미를 가진다. 사전에 정의된 용어들은 관련 기술문헌과 현재 개시된 내용에 부합하는 의미를 가지도록 해석된다.Unless otherwise defined, all terms, including technical and scientific terms, used in this specification have the same meaning as commonly understood by a person of ordinary skill in the technical field to which the present invention pertains. Terms defined in the dictionary are interpreted to have meanings consistent with related technical literature and current disclosure.
이하, 본 발명에 대하여 상세히 설명한다.Hereinafter, the present invention will be described in detail.
먼저, 본 발명의 일 측면에 따른 도금강판 표면처리용 용액 조성물에 대하여 구체적으로 설명한다.First, a solution composition for surface treatment of plated steel sheets according to one aspect of the present invention will be described in detail.
본 발명에 따른 용액 조성물은 3가 크롬 화합물 1~10중량%, 산도 조절제 0.1~5중량%, 밀착성 향상제 1~20중량%, 내식성 개선제 1~20중량%, 점상 부식 개선제 0.1~5.0중량%, 장기 내식성 향상제 1~10중량%, 윤활제 0.1~3.0중량%, 조용제 1~20중량% 및 잔량 용제를 포함할 수 있다.The solution composition according to the present invention contains 1 to 10% by weight of a trivalent chromium compound, 0.1 to 5% by weight of an acidity regulator, 1 to 20% by weight of an adhesion improver, 1 to 20% by weight of a corrosion resistance improver, 0.1 to 5.0% by weight of a pitting corrosion improver, It may contain 1 to 10% by weight of a long-term corrosion resistance improver, 0.1 to 3.0% by weight of a lubricant, 1 to 20% by weight of a co-solvent, and the remaining amount of solvent.
본 발명의 용액 조성물의 함량은 전체 100중량%를 기준으로 한다.The content of the solution composition of the present invention is based on 100% by weight of the total.
후술하여 구체적으로 설명하겠지만, 상기 용액 조성물은 조성물을 도포할 수 있는 기재(substrate)의 적어도 일면에 코팅층을 형성할 수 있다. 본 발명에서 상기 기재는 앞서 언급한 도금강판, 예컨대 아연계 도금강판일 수 있으며, 비 제한적인 일예로서 Zn-Mg-Al계 삼원계 합금도금강판일 수 있다.As will be described in detail later, the solution composition can form a coating layer on at least one surface of a substrate on which the composition can be applied. In the present invention, the base material may be the above-mentioned plated steel sheet, for example, a zinc-based plated steel plate, and as a non-limiting example, it may be a Zn-Mg-Al-based ternary alloy plated steel plate.
하기에서는, 상기 용액 조성물을 구성하는 각 성분에 대하여 상세히 설명한다.In the following, each component constituting the solution composition will be described in detail.
3가 크롬 화합물 1~10 중량% (이하, %)Trivalent chromium compound 1-10% by weight (hereinafter, %)
상기 3가 크롬 화합물은 강판의 표면에서 주로 불용성 피막을 형성하여, 베리어 효과(Barrier effect)에 의한 내식성 향상을 도모한다.The trivalent chromium compound mainly forms an insoluble film on the surface of the steel sheet, thereby improving corrosion resistance through a barrier effect.
본 발명의 용액 조성물에서 상기 3가 크롬 화합물의 함량이 1% 미만이면 견고한 불용성 피막을 충분히 형성하지 못하여 강판의 표면으로 침투하는 수분을 효과적으로 차단하지 못하며, 그 결과 내식성을 확보할 수 없게 된다. 반면, 그 함량이 10%를 초과하게 되면 과도한 크롬 성분으로 인하여 이물 결함이 발생할 우려가 있다.If the content of the trivalent chromium compound in the solution composition of the present invention is less than 1%, a strong insoluble film cannot be sufficiently formed and moisture penetrating into the surface of the steel sheet cannot be effectively blocked, and as a result, corrosion resistance cannot be secured. On the other hand, if the content exceeds 10%, there is a risk of foreign matter defects occurring due to excessive chromium content.
본 발명에서 상기 3가 크롬 화합물의 종류에 대해 특별히 제한하지는 아니하나, 바람직하게는 황산크롬, 질산크롬, 인산크롬, 불화크롬 및 이들의 혼합물로 이루어진 군에서 선택된 하나 이상의 것일 수 있다.In the present invention, the type of the trivalent chromium compound is not particularly limited, but is preferably one or more selected from the group consisting of chromium sulfate, chromium nitrate, chromium phosphate, chromium fluoride, and mixtures thereof.
산도 조절제 0.1~5%Acidity regulator 0.1~5%
본 발명의 용액 조성물에서 산도 조절제는 용액의 pH를 조절하여 조성물 내 성분들이 용액 내에서 안정하게 존재하고, 코팅 조건하에서 적절하게 반응하여 피막을 안정적으로 형성할 수 있도록 하는 역할을 한다.In the solution composition of the present invention, the acidity regulator controls the pH of the solution to ensure that the components in the composition exist stably in the solution and react appropriately under coating conditions to stably form a film.
이러한 산도 조절제의 함량이 0.1% 미만이면 용액의 pH가 높아져 용액 안정성이 저하될 우려가 있고, 반면 그 함량이 5%를 초과하게 되면 건조 후 잔류산으로 인해 내식성 등을 확보하지 못하게 될 수 있다.If the content of the acidity regulator is less than 0.1%, the pH of the solution may increase and there is a risk that solution stability may deteriorate. On the other hand, if the content exceeds 5%, corrosion resistance, etc. may not be secured due to residual acid after drying.
본 발명에서 상기 산도 조절제의 종류에 대해 특별히 제한하지는 아니하나, 바람직하게는 인산, 질산, 황산, 불산, 염산, (NH4)H2PO4, (NH4)2HPO4, NaH2PO4, Na2HPO4, 피트산(Phytic acid), 글리콜릭산, 젖산, 초산, 옥살릭산 및 이들의 혼합물로 이루어진 군에서 선택된 하나 이상의 것일 수 있다.In the present invention, the type of the acidity regulator is not particularly limited, but preferably phosphoric acid, nitric acid, sulfuric acid, hydrofluoric acid, hydrochloric acid, (NH 4 )H 2 PO 4 , (NH 4 ) 2 HPO 4 , NaH 2 PO 4 , Na 2 HPO 4 , phytic acid, glycolic acid, lactic acid, acetic acid, oxalic acid, and mixtures thereof.
밀착성 향상제 1~20%Adhesion improver 1~20%
본 발명의 용액 조성물에서 밀착성 향상제는 상기 3가 크롬 화합물 등과 결합하고, 강판과도 결합하여 코팅층의 밀착성 및 내식성 등을 향상시키는 역할을 한다.In the solution composition of the present invention, the adhesion improver combines with the trivalent chromium compound and the like and also with the steel plate to improve the adhesion and corrosion resistance of the coating layer.
이러한 밀착성 향상제의 함량이 1% 미만이면 강판과의 밀착성을 충분히 확보하지 못하여 이물 결함이 발생할 수 있다. 반면, 그 함량이 20%를 초과하게 되면 도막 형성 후 잔존하는 양이 과도하여 내식성 등을 확보하지 못할 수 있다.If the content of the adhesion improver is less than 1%, adhesion to the steel plate may not be sufficiently secured and foreign matter defects may occur. On the other hand, if the content exceeds 20%, the amount remaining after forming the coating film is excessive, and corrosion resistance, etc. may not be secured.
본 발명에서 상기 밀착성 향상제의 종류에 대해 특별히 제한하지는 아니하나, 바람직하게는 비닐메톡시 실란, 비닐트리메톡시 실란(VTMS), 비닐에폭시 실란, 비닐트리에폭시 실란, 3-아미노프로필트리에폭시 실란, 3-글리시독시프로필트리메톡시 실란, 3-메타글리옥시프로필트리메톡시 실란, γ-글리시독시프로필트리에톡시실란, γ-글리시독시트리메틸디메톡시실란, N-(3-(trimethoxysilyl)propyl)ethylenediamine (AEAPTMS), 2-(3,4-Epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-Epoxycyclohexyl)ethyltriethoxysilane, 3-(2,3-Epoxypropoxy)propyltrimethoxysilane, 3-(2,3-Epoxypropoxy)propyltriethoxysilane, 3-(2,3-Epoxypropoxy)propylmethyldiethoxysilane, 3-(2,3-Epoxypropoxy)propylmethyldimethoxysilane, 3-Aminopropyltriethoxysilane, 3-Aminopropyltrimethoxysilane, 3-Aminopropylmethyldiethoxysilane, N-(2-Aminoethyl-3-aminopropyl)methyldimethoxysilane, N-(2-Aminoethyl-3-aminopropyl)trimethoxysilane, Diethylenetriaminopropyltrimethoxysilane, 3-Ureidopropyltrimethoxysilane, N-Phenylaminopropyltrimethoxysilane, (3-Glycidyloxypropyl)trimethoxysilane (GPTMS), Methyltrimethoxysilane (MTMS) 및 이들의 혼합물로 이루어진 군에서 선택된 하나 이상의 것일 수 있다.In the present invention, the type of the adhesion improver is not particularly limited, but preferably vinylmethoxy silane, vinyltrimethoxy silane (VTMS), vinylepoxy silane, vinyltriepoxy silane, 3-aminopropyltriepoxy silane, 3-glycidoxypropyltrimethoxy silane, 3-metaglyoxypropyltrimethoxy silane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxytrimethyldimethoxysilane, N-(3-(trimethoxysilyl )propyl)ethylenediamine (AEAPTMS), 2-(3,4-Epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-Epoxycyclohexyl)ethyltriethoxysilane, 3-(2,3-Epoxypropoxy)propyltrimethoxysilane, 3-(2,3-Epoxypropoxy) propyltriethoxysilane, 3-(2,3-Epoxypropoxy)propylmethyldiethoxysilane, 3-(2,3-Epoxypropoxy)propylmethyldimethoxysilane, 3-Aminopropyltriethoxysilane, 3-Aminopropyltrimethoxysilane, 3-Aminopropylmethyldiethoxysilane, N-(2-Aminoethyl-3-aminopropyl)methyldimethoxysilane, N -(2-Aminoethyl-3-aminopropyl)trimethoxysilane, Diethylenetriaminopropyltrimethoxysilane, 3-Ureidopropyltrimethoxysilane, N-Phenylaminopropyltrimethoxysilane, (3-Glycidyloxypropyl)trimethoxysilane (GPTMS), Methyltrimethoxysilane (MTMS), and mixtures thereof. .
내식성 개선제 1~20% Corrosion resistance improver 1~20%
본 발명의 용액 조성물에서 내식성 개선제는 상기 3가 크롬 화합물과 밀착성 향상제 등과의 사이에 존재할 수 있는 간극을 채우면서 부동태 피막을 형성하여 부식 생성을 억제하는 역할을 한다.In the solution composition of the present invention, the corrosion resistance improver fills the gap that may exist between the trivalent chromium compound and the adhesion improver and forms a passive film to suppress corrosion.
이러한 내식성 개선제의 함량이 1% 미만이면 부동태 피막을 충분히 형성하지 못하여 내식성 확보에 어려움이 있으며, 반면 그 함량이 20%를 초과하게 되면 지나치게 높은 고형분으로 인해 용액 안정성이 저하될 수 있다.If the content of this corrosion resistance improver is less than 1%, it is difficult to secure corrosion resistance because a passive film cannot be sufficiently formed. On the other hand, if the content exceeds 20%, solution stability may be reduced due to excessively high solid content.
본 발명에서 상기 내식성 개선제의 종류에 대해 특별히 제한하지는 아니하나, 바람직하게는 바나딜 아세틸아세토네이트(Vanadyl acetylacetonate), 메타바나딘산암모늄(Ammonium metavanadate), 메타바나딘산칼륨(Potassium metavanadate), 메타바나딘산나트륨(Sodium metavanadate), 바나듐 삼산화물(Vanadium trioxide), 바나듐 아세틸아세테이트, 암모늄 메타바나데이트, 산화규소 및 이들의 혼합물로 이루어진 군에서 선택된 하나 이상의 것일 수 있다.In the present invention, the type of the corrosion resistance improver is not particularly limited, but preferably vanadyl acetylacetonate, ammonium metavanadate, potassium metavanadate, metavanadate, etc. It may be one or more selected from the group consisting of sodium metavanadate, vanadium trioxide, vanadium acetylacetate, ammonium metavanadate, silicon oxide, and mixtures thereof.
점상 부식 개선제 0.1~5.0%, Spot corrosion improver 0.1~5.0%,
본 발명의 용액 조성물에서 점상 부식 개선제는 상기 내식성 개선제와 함께 부식 인자의 국부적 침투를 방지하여 점상 형태로 발생하는 점상 부식을 최소화하는 역할을 한다.In the solution composition of the present invention, the punctate corrosion improver acts together with the corrosion resistance improver to prevent local penetration of corrosion factors and thereby minimize pitt corrosion that occurs in the form of spots.
본 발명의 용액 조성물에서 상기 점상 부식 개선제의 함량이 0.1% 미만이면 부식 인자의 국부적 침투를 차단하지 못하여 점상 부식이 발생하는 문제가 있다. 반면, 그 함량이 5.0%를 초과하게 되면 용액의 pH가 지나치게 상승하여 용액 안정성이 저하될 우려가 있다.If the content of the spotting corrosion improver in the solution composition of the present invention is less than 0.1%, there is a problem in that spotting corrosion occurs because local penetration of corrosion factors cannot be blocked. On the other hand, if the content exceeds 5.0%, the pH of the solution may increase excessively and there is a risk that solution stability may decrease.
본 발명에서 상기 점상 부식 개선제의 종류에 대하여 특별히 제한하지는 아니하나, 바람직하게는 에틸렌다이아민, 헥사메틸렌다이아민, 트리메틸아민, 메틸아민, 디페닐아민, 에틸렌아민, 아닐린, 톨루이딘, 피페리딘, 아지리딘, 피리딘, 알라닌, 프로필아민, 디이소프로필아민, 모노이소프로필아민, 디부틸아민, 디프로필아민 및 이들의 혼합물로 이루어진 군에서 선택된 하나 이상의 것일 수 있다.In the present invention, the type of the pitting corrosion improver is not particularly limited, but preferably ethylenediamine, hexamethylenediamine, trimethylamine, methylamine, diphenylamine, ethyleneamine, aniline, toluidine, piperidine, It may be one or more selected from the group consisting of aziridine, pyridine, alanine, propylamine, diisopropylamine, monoisopropylamine, dibutylamine, dipropylamine, and mixtures thereof.
장기 내식성 향상제 1~10%, Long-term corrosion resistance improver 1-10%,
본 발명의 용액 조성물에서 장기 내식성 향상제는 코팅 후 부식 과정에서 아연합금 도금층의 부식 생성물과 결합하여 내식성을 향상시키는 소위 시몬콜레이트 (simonkolleite)의 형성을 활성화하여 아연합금(일예로, 삼원계 용융아연합금) 도금가판의 장기 내식성을 향상시키는 역할을 한다. In the solution composition of the present invention, the long-term corrosion resistance improver combines with the corrosion products of the zinc alloy plating layer during the post-coating corrosion process to activate the formation of so-called simonkolleite, which improves corrosion resistance of the zinc alloy (e.g., ternary molten zinc alloy). ) It plays a role in improving the long-term corrosion resistance of plated plates.
상기 장기 내식성 향상제의 함량이 1% 미만인 경우에는 상기 시몬콜레이트 형성에 기여하는 역할이 부족하여 장기 내식성이 개선되지 못할 수 있다. 반면 10%를 초과하는 경우에는 지나치게 많은 크롬 성분으로 인해 이물결함이 발생할 수 있다. If the content of the long-term corrosion resistance improver is less than 1%, the long-term corrosion resistance may not be improved due to insufficient contribution to the formation of simoncholate. On the other hand, if it exceeds 10%, foreign matter defects may occur due to too much chromium content.
본 발명에서 상기 장기 내식성 향상제의 종류에 대해서는 특별히 제한하지는 아니하나, 바람직하게는 염화크롬 무수물, 염화크롬 5수화물, 염화크롬 6수화물, 염화크롬 9수화물 및 이들의 혼합물로 이루어진 군으로부터 선택되는 하나 이상의 것일 수 있다. In the present invention, the type of the long-term corrosion resistance improver is not particularly limited, but is preferably one or more selected from the group consisting of chromium chloride anhydrous, chromium chloride pentahydrate, chromium chloride hexahydrate, chromium chloride nonahydrate, and mixtures thereof. It could be.
윤활제 0.1~3.0%Lubricant 0.1~3.0%
본 발명의 용액 조성물에서 윤활제는 강판 표면의 슬립성을 향상시켜 가공성을 향상시키고 이물결함 발생을 억제하는 역할을 한다. In the solution composition of the present invention, the lubricant improves the slip properties of the surface of the steel sheet, thereby improving processability and suppressing the occurrence of foreign material defects.
상기 윤활제의 함량이 0.1% 미만이면 강판 표면이 슬립성이 충분하지 않아 이물결함이 발생할 수 있다. 반면, 그 함량이 3.0% 초과하게 되면 윤활제의 지나치게 높은 함량으로 인해 용액 안정성이 저하될 수 있다. If the content of the lubricant is less than 0.1%, the slipperiness of the surface of the steel sheet is not sufficient and foreign matter defects may occur. On the other hand, if the content exceeds 3.0%, solution stability may be reduced due to an excessively high content of lubricant.
본 발명에서 상기 윤활제의 종류에 대해서 특별히 제한하지는 아니하나, 바람직하게는 Polytetrafluoroethylene(PTFE), Polyethylene(PE), Carnauba계 왁스 및 이들의 혼합물로 이루어진 군으로부터 선택되는 하나 이상의 것일 수 있다.In the present invention, the type of lubricant is not particularly limited, but is preferably one or more selected from the group consisting of Polytetrafluoroethylene (PTFE), Polyethylene (PE), Carnauba-based wax, and mixtures thereof.
조용제 1~20%Cho Yong-je 1~20%
본 발명의 용액 조성물에서 조용제는 코팅 작업 중 건조 과정에서 용제의 휘발 속도를 조절하여 건조 후 피막 표면의 결함을 억제하는 역할을 한다.In the solution composition of the present invention, the co-solvent controls the volatilization rate of the solvent during the drying process during the coating operation and serves to suppress defects on the film surface after drying.
이러한 조용제의 함량이 1% 미만이면 건조 중 휘발 속도를 조절하는 효과가 미비하여, 주 용제의 증발속도가 비점에서 급격히 끓어올라 소위 포핑(popping) 이라고 하는 표면 결함이 발생하고, 이로 인해 내식성 저하 등의 문제가 있다. 반면, 그 함량이 20%를 초과하게 되면 용액의 점도 및 밀도 등의 급격한 변화로 용액 안정성이 저하될 수 있다.If the content of this co-solvent is less than 1%, the effect of controlling the volatilization rate during drying is insufficient, and the evaporation rate of the main solvent rapidly boils at the boiling point, causing surface defects called popping, which leads to a decrease in corrosion resistance, etc. There is a problem. On the other hand, if the content exceeds 20%, solution stability may decrease due to rapid changes in solution viscosity and density.
본 발명에서 상기 조용제의 종류에 대해 특별히 제한하지는 아니하나, 바람직하게는 에탈올, 이소프로필알코올, 메탄올, 탈로우 알코올(Tallow alcohol), 2-부톡시에탄올(2-butoxyethanol), 디에틸렌 글리콜 모노부틸 에테르(Diethylene glycol monobutyl ether) 및 이들의 혼합물로 이루어진 군에서 선택된 하나 이상의 것일 수 있다.In the present invention, the type of co-solvent is not particularly limited, but preferably ethanol, isopropyl alcohol, methanol, tallow alcohol, 2-butoxyethanol, diethylene glycol mono. It may be one or more selected from the group consisting of butyl ether (diethylene glycol monobutyl ether) and mixtures thereof.
용제solvent
본 발명의 용액 조성물은 잔부 성분으로서 용제를 포함할 수 있으며, 본 발명에서 상기 용제로서 물(증류수, 탈이온수)를 사용할 수 있다.The solution composition of the present invention may include a solvent as a remaining component, and water (distilled water, deionized water) may be used as the solvent in the present invention.
다음으로, 본 발명의 다른 일 측면에 따른 상술한 용액 조성물로 표면처리하여 일정의 코팅층을 포함하는 표면처리된 강판에 대하여 구체적으로 설명한다.Next, a detailed description will be given of a surface-treated steel sheet including a certain coating layer by surface treatment with the above-described solution composition according to another aspect of the present invention.
본 발명에서 상기 조성물은 도금강판, 예컨대 아연계 도금강판일 수 있으며, 바람직하게는 Zn-Mg-Al계 삼원계 합금도금강판에 표면처리할 수 있다. In the present invention, the composition can be a plated steel sheet, for example, a zinc-based plated steel plate, and preferably can be surface-treated on a Zn-Mg-Al-based ternary alloy plated steel plate.
즉, 본 발명의 표면처리된 도금강판은 강판; 상기 강판의 적어도 일면에 형성된 도금층; 및 상기 도금층 상에 형성된 표면처리 코팅층을 포함할 수 있다. 여기서 상기 강판은 도금강판을 얻을 수 있는 소지강판(base steel sheet)인 것으로서, 특히 삼원계(Zn-Mg-Al계) 용융아연도금강판을 얻을 수 강판이라면 어떠한 것도 무방하다.That is, the surface-treated plated steel sheet of the present invention is a steel sheet; A plating layer formed on at least one surface of the steel sheet; And it may include a surface treatment coating layer formed on the plating layer. Here, the steel sheet is a base steel sheet from which a galvanized steel sheet can be obtained, and in particular, any steel sheet from which a ternary system (Zn-Mg-Al system) hot-dip galvanized steel sheet can be obtained.
일예로, 상기 Zn-Mg-Al계 도금층 그 조성이 중량%로, 마그네슘(Mg): 4.0~7.0%, 알루미늄(Al): 11.0~19.5%, 잔부 Zn 및 기타 불가피한 불순물을 포함할 수 있다.For example, the composition of the Zn-Mg-Al-based plating layer may include, in weight percent, magnesium (Mg): 4.0 to 7.0%, aluminum (Al): 11.0 to 19.5%, the balance Zn, and other unavoidable impurities.
상기 도금층 내의 마그네슘(Mg)은 도금강판의 내식성을 향상시키는 역할을 하는 원소로서, 본 발명에서 목적하는 우수한 내식성의 확보를 위해 그 함량이 4.0% 이상인 것이 바람직하다. 다만, 상기 Mg의 함량이 과도한 경우 도금욕 내에서 드로스를 발생시킬 우려가 있고, 도금층 내에서 경도가 높은 금속간 화합물을 과다하게 형성하여 강판의 굽힘성을 악화시킬 우려가 있으므로, 그 함량을 7.0%로 제한할 수 있다.Magnesium (Mg) in the plating layer is an element that plays a role in improving the corrosion resistance of the plated steel sheet, and its content is preferably 4.0% or more to ensure the excellent corrosion resistance desired in the present invention. However, if the content of Mg is excessive, there is a risk of generating dross in the plating bath, and there is a risk of deteriorating the bendability of the steel sheet by excessively forming high hardness intermetallic compounds in the plating layer. It can be limited to 7.0%.
한편, 상기 Mg의 함량을 4.0% 이상으로 첨가함에 의해 도금욕 내에서 Mg 산화에 의한 드로스 발생 위험성이 존재하므로, 이를 고려하여 상기 알루미늄(Al)을 11.0% 이상으로 포함하는 것이 바람직하다. 다만, 상기 Al의 함량이 과도할 경우 도금욕의 융점이 높아지고 그에 따른 조업 온도가 과도하게 높아져 도금욕 구조물의 침식 및 강판의 변성이 초래되는 등의 고온 작업에 따른 문제가 초래될 수 있다. 따라서, 상기 Al은 19.5% 이하로 그 함량을 제한하는 것이 바람직하다.Meanwhile, when the Mg content is added to 4.0% or more, there is a risk of dross generation due to Mg oxidation in the plating bath, so taking this into consideration, it is preferable to include aluminum (Al) at 11.0% or more. However, if the Al content is excessive, the melting point of the plating bath increases and the operating temperature accordingly becomes excessively high, which may cause problems due to high-temperature work, such as erosion of the plating bath structure and deterioration of the steel sheet. Therefore, it is desirable to limit the Al content to 19.5% or less.
상기 Mg과 Al을 제외한 잔부 조성은 아연(Zn)이며, Zn-Mg-Al계 도금층을 갖는 도금강판을 제조하는 과정에서 불가피한 불순물이 의도하지 않게 혼입될 수 있다. 이때 불가피한 불순물은 당해 기술분야의 기술자라면 그 의미를 쉽게 이해할 수 있을 것임을 밝혀둔다.The remaining composition excluding Mg and Al is zinc (Zn), and unavoidable impurities may be unintentionally mixed in the process of manufacturing a plated steel sheet with a Zn-Mg-Al-based plating layer. At this time, it should be noted that those skilled in the art can easily understand the meaning of inevitable impurities.
상술한 Zn-Mg-Al계 도금층의 조직이 하기 [관계식 1]을 만족하는 것이 바람직하다.It is preferable that the structure of the above-described Zn-Mg-Al-based plating layer satisfies the following [Relational Equation 1].
[관계식 1][Relational Expression 1]
0.26 ≤ I(110)/I(103) ≤ 0.650.26 ≤ I(110)/I(103) ≤ 0.65
(관계식 1에서, I(110)은 MgZn2상에 대한 (110)면 결정 피크의 X선 회절 적분 강도를 나타내고, 상기 I(103)은 MgZn2상에 대한 (103)면 결정의 X선 회절 적분 강도를 나타낸다.)(In equation 1, I (110) represents the X-ray diffraction integrated intensity of the (110) plane crystal peak for the MgZn 2 phase , and I (103) represents the Indicates the integrated intensity.)
상기 Zn-Mg-Al계 도금층의 MgZn2상에 대해 상기 [관계식 1]로 제어함으로써 도금강판의 굽힘성, 백색도 등을 확보할 수 있다.By controlling the MgZn 2 phase of the Zn-Mg-Al-based plating layer using the above [Relational Equation 1], the bendability, whiteness, etc. of the plated steel sheet can be secured.
상기 [관계식 1]로 정의되는 값이 0.26 미만이면 MgZn2상에 대한 (110)면 결정 대비 MgZn2상에 대한 (103)면 결정의 존재 비율이 과다하여, 굽힘성이나 백색도가 불충분해질 수 있다. 반면, 상기 값이 0.65를 초과하게 되면 MgZn2상에 대한 (103)면 결정 대비 MgZn2상에 대한 (110)면 결정의 존재 비율이 너무 과다하여, 난반사의 증대를 유도하지 못해 백색도가 불충분해지는 문제가 생길 수 있다.If the value defined by [Relational Equation 1] is less than 0.26, the presence ratio of (103) face crystals for the MgZn 2 phase compared to (110) face crystals for the MgZn 2 phase is excessive, and bendability or whiteness may become insufficient. . On the other hand, if the above value exceeds 0.65, the ratio of the presence of (110) face crystals for the MgZn 2 phase compared to the (103) face crystals for the MgZn 2 phase is too excessive, and the increase in diffuse reflection cannot be induced, resulting in insufficient whiteness. Problems may arise.
이때, 상기 I(110)은 적분 강도의 값이 120~200의 범위를 가질 수 있으며, 상기 I(103)은 적분 강도의 값이 240~300의 범위일 수 있다. 이와 같이, 각 범위 내에서 상기 [관계식 1]의 값을 만족하는 것이 바람직하다. At this time, the I (110) may have an integrated intensity value in the range of 120 to 200, and the I (103) may have an integrated intensity value in the range of 240 to 300. In this way, it is desirable to satisfy the value of [Relational Equation 1] within each range.
상술한 Zn-Mg-Al계 도금층의 상부에는 본 발명의 조성물을 용액 상태로 코팅처리함으로써 형성된 코팅층을 포함할 수 있으며, 이때 코팅층은 0.1~2.0㎛의 두께를 가지는 것이 바람직하다.The upper part of the above-described Zn-Mg-Al-based plating layer may include a coating layer formed by coating the composition of the present invention in a solution state, and in this case, the coating layer preferably has a thickness of 0.1 to 2.0 μm.
상기 코팅층의 두께가 0.1㎛ 미만이면 도금강판 표면에 존재하는 조도의 산 부위에 표면처리 용액 조성물이 얇게 도포되어 내식성이 저하되는 문제가 있으며, 반면, 그 두께가 2.0㎛를 초과하게 되면 피막층(코팅층)이 두껍게 형성됨으로 인해 가공성이 열화되고 용액처리 비용이 상승하여 경제적으로 불리하게 된다.If the thickness of the coating layer is less than 0.1㎛, there is a problem that the surface treatment solution composition is applied thinly to the acidic roughness existing on the surface of the plated steel sheet, resulting in a decrease in corrosion resistance. On the other hand, if the thickness exceeds 2.0㎛, the coating layer (coating layer) ) is formed thickly, which deteriorates processability and increases the cost of solution treatment, making it economically disadvantageous.
여기서, 상기 두께는 건조 후의 두께를 의미한다Here, the thickness refers to the thickness after drying.
나아가, 본 발명은 상기 조성물을 이용하여 표면처리된 강판을 제조하는 방법에 대하여 설명한다.Furthermore, the present invention describes a method of manufacturing a surface-treated steel sheet using the composition.
보다 상세하게는 적어도 일면에 도금층이 형성된 도금강판을 제공하는 단계; 상기 도금층 상에 상술한 용액 조성물을 코팅처리하는 단계; 및 상기 코팅처리된 강판을 건조처리하는 단계를 포함할 수 있다. More specifically, providing a plated steel sheet with a plating layer formed on at least one surface; Coating the above-described solution composition on the plating layer; And it may include drying the coated steel sheet.
본 발명의 조성물을 용액 상태로 상기 강판에 도포함에 있어서, 일반적으로 사용되는 코팅법을 적용할 수 있으므로, 특별히 한정하지는 아니한다.When applying the composition of the present invention to the steel sheet in a solution state, a generally used coating method can be applied, so there is no particular limitation.
예를 들면, 바코팅, 롤코팅, 스프레이, 침적, 스프레이 스퀴징, 침적 스퀴징 등의 방법 중에서 하나의 방법을 선택하여 코팅 공정을 수행할 수 있다.For example, the coating process can be performed by selecting one method among methods such as bar coating, roll coating, spraying, dipping, spray squeezing, and dipping squeezing.
상기 조성물로 코팅처리된 강판을 건조처리하는 공정은 소재(강판)의 최종도달온도(PMT) 기준으로 40~280℃의 온도 범위에서 행해지는 것이 바람직하다.The process of drying the steel sheet coated with the composition is preferably performed in a temperature range of 40 to 280°C based on the final temperature (PMT) of the material (steel sheet).
상기 소재의 최종도달온도 기준으로 40℃ 미만이면 견고한 피막구조 형성이 미흡하여 내식성 및 내흑변성이 열위해질 우려가 있다. 반면, 그 온도가 280℃를 초과하게 되면 피막의 경도가 과도하게 증가하여 가공부 내식성이 열위해지고, 과도한 열로 인한 황변 현상 등 표면 품질이 열위해질 수 있다.If the final temperature of the material is less than 40°C, there is a risk that corrosion resistance and blackening resistance may be deteriorated due to insufficient formation of a sturdy film structure. On the other hand, if the temperature exceeds 280°C, the hardness of the film may increase excessively, resulting in poor corrosion resistance of the processed part, and poor surface quality such as yellowing due to excessive heat.
상기 건조처리가 완료된 강판은 건조 후 두께로 0.1~2.0㎛의 코팅층을 가질 수 있다.The steel sheet on which the drying treatment has been completed may have a coating layer with a thickness of 0.1 to 2.0 μm after drying.
본 발명에서 상기 건조처리를 행하기 위한 수단으로는 특별히 한정하지는 아니하나, 인덕션 오븐 또는 열풍건조로 등의 설비를 이용할 수 있음을 밝혀두며, 이들 설비의 조건은 통상의 조건에 의할 수 있다.In the present invention, the means for performing the drying treatment are not particularly limited, but it is noted that equipment such as an induction oven or hot air drying furnace can be used, and the conditions of these equipment can be conventional conditions.
(실시예) (Example)
이하, 본 발명을 실시예를 통하여 보다 상세하게 설명한다. 그러나, 이러한 실시예의 기재는 본 발명의 실시를 예시하기 위한 것일 뿐 이러한 실시예의 기재에 의하여 본 발명이 제한되는 것은 아니다. 본 발명의 권리범위는 특허청구범위에 기재된 사항과 이로부터 합리적으로 유추되는 사항에 의하여 결정되는 것이기 때문이다.Hereinafter, the present invention will be described in more detail through examples. However, the description of these examples is only for illustrating the implementation of the present invention, and the present invention is not limited by the description of these examples. This is because the scope of rights of the present invention is determined by matters stated in the patent claims and matters reasonably inferred therefrom.
먼저, 표면처리용 용액 조성물의 물성을 측정하기 위해 다음과 같은 물질을 사용하여 용액 조성물을 제조하였다. 증류수에 산도 조절제로 인산을 넣고 약 40℃에서 3가 크롬 화합물인 질산크롬과 장기 내식성 향상제인 염화크롬 9수화물을 첨가한 후 약 30분간 교반하였다. 같은 방식으로 밀착성 향상제인 GPTMS를 첨가하고, 내식성 개선제인 산화규소, 점상 부식 개선제인 에틸렌다이아민, 조용제인 에탄올, 윤활제인 Polyethylene(PE)을 30분 간격으로 첨가하면서 교반하였다. First, to measure the physical properties of the solution composition for surface treatment, the solution composition was prepared using the following materials. Phosphoric acid as an acidity regulator was added to distilled water, and chromium nitrate, a trivalent chromium compound, and chromium chloride nonahydrate, a long-term corrosion resistance improver, were added at about 40°C and stirred for about 30 minutes. In the same manner, GPTMS, an adhesion improver, was added, and silicon oxide, a corrosion resistance improver, ethylenediamine, a spotting corrosion improver, ethanol, a co-solvent, and Polyethylene (PE), a lubricant, were added at 30-minute intervals and stirred.
이때 각 성분의 함량(중량%, 나머지는 용제임)은 하기 표 1 및 2에 나타내었다. At this time, the content (% by weight, the rest is solvent) of each component is shown in Tables 1 and 2 below.
화합물trivalent chromium
compound
조절제acidity
conditioner
향상제Adhesion
enhancer
개선제corrosion resistance
improver
개선제Pitting corrosion
improver
상기와 같이 제조된 표면처리용 용액 조성물을 이용하여 중량%로, Mg: 4.0~7.0%, Al: 11.0~19.5%, 잔부 Zn 및 기타 불가피한 불순물을 포함하는 삼원계 용융아연합금도금강판 시편을 7cm×15cm (가로 × 세로)로 절단하여 탈지한 후 피막부착량이 Cr을 기준으로 약 35mg/m2 (약 0.4㎛ 두께 수준) 되도록 바코팅을 하여 시편을 제작하였다. 이때 건조는 50℃에서 수행하였다.Using the solution composition for surface treatment prepared as above, a ternary hot-dip zinc alloy plated steel sheet specimen containing Mg: 4.0~7.0%, Al: 11.0~19.5%, balance Zn, and other inevitable impurities in weight percent was 7 cm long. A specimen was produced by cutting it into × 15 cm (width × height), degreasing it, and then bar coating it so that the film adhesion amount was about 35 mg/m 2 (about 0.4 μm thick) based on Cr. At this time, drying was performed at 50°C.
상기에 따라 제조된 용액 조성물 및 이를 이용하여 표면처리된 도금강판 시편의 물성을 측정하기 위하여, 다음과 같은 방법 및 기준으로 용액 안정성, 평판 내식성, 가공부 내식성, 조관유 침해성, 내알칼리성, 점상 부식 내식성, 내흑변성, 이물 결함, 장기 내식성을 측정하였다. In order to measure the physical properties of the solution composition prepared above and the coated steel specimen surface treated using it, solution stability, flat plate corrosion resistance, processing part corrosion resistance, crude oil penetration, alkali resistance, and spotting were measured using the following methods and standards. Corrosion resistance, blackening resistance, foreign matter defects, and long-term corrosion resistance were measured.
용액 안정성solution stability
상기에 방법에 의해 제조된 코팅 조성물을 제조한 직후, 각각 초기 점도(Vi)를 측정하고, 50℃의 오븐에 120시간 보관 후 다시 25℃로 냉각시킨 후, 25℃에서의 나중 점도(Vl)를 측정한 후, 하기의 수학식 1에 대입하였으며, 그 결과를 하기의 평가 기준에 따라 평가하였다. Immediately after preparing the coating composition prepared by the above method, the initial viscosity (Vi) was measured, stored in an oven at 50 ° C for 120 hours, cooled again to 25 ° C, and the final viscosity at 25 ° C (Vl) After measuring, it was substituted into Equation 1 below, and the results were evaluated according to the evaluation criteria below.
[수학식 1][Equation 1]
△V = (Vl - Vi)/ Vi × 100 (%)△V = (Vl - Vi)/ Vi × 100 (%)
<용액 안정성의 평가 기준><Evaluation criteria for solution stability>
○: △V가 20(%) 미만이거나 육안 관찰시 겔화 현상이 보이지 않음○: △V is less than 20 (%) or no gelation phenomenon is visible when observed with the naked eye.
×: △V가 20(%) 이상이거나 육안 관찰시 겔화 현상이 보임×: △V is 20 (%) or more or gelation phenomenon is visible when observed with the naked eye
평판 내식성flat plate corrosion resistance
ASTM B117에서 규정한 방법에 의거하여, 각 강판(시편)에 대해 용액 조성물을 처리한 후 시간 경과에 따라 강판의 백청 발생율을 측정하였다.According to the method specified in ASTM B117, each steel sheet (specimen) was treated with a solution composition and the white rust generation rate of the steel sheet was measured over time.
<평판 내식성 평가 기준><Plate corrosion resistance evaluation criteria>
○: 백청 발생 시간이 144시간 이상○: White rust generation time is 144 hours or more.
△: 백청 발생 시간이 96시간 이상 144시간 미만△: White rust occurrence time is more than 96 hours and less than 144 hours.
×: 백청 발생 시간이 96시간 미만×: White rust generation time is less than 96 hours
가공부 내식성Machining part corrosion resistance
상기에 따라 표면처리된 강판(시편)을 에릭슨 테스터(Erichsen tester)를 이용하여 6mm의 높이로 밀어 올린 후, 24시간 경과하였을 때 백청 발생 정도를 측정하였다.The steel plate (specimen) surface-treated as above was pushed up to a height of 6 mm using an Erichsen tester, and the degree of white rust was measured after 24 hours.
<가공부 내식성 평가 기준><Corrosion resistance evaluation criteria for machining parts>
○: 백청 발생 없거나, 발생하더라도 상당히 미세한 경우○: If white rust does not occur, or if it does occur, it is very subtle.
△: 원에 백청이 발생하여 일부 흘렀으나, 밖으로 흘러나가지 않은 경우△: When white rust occurs in the circle and some flows out, but does not flow out.
×: 백청이 발생하여 원 밖으로 흘러나간 경우×: When white rust occurs and flows out of the circle
조관유 침해성Crude oil invasiveness
상기에 따라 표면처리된 강판(시편)을 상온에서 조관유에 침적하여 24시간 유지 후, 침적 전/후의 색차를 측정하였다. 이때, 조관유는 국내 범우 BW WELL MP-411을 10% 물에 희석하여 사용하였다.The steel sheet (specimen) surface-treated as above was immersed in crude oil at room temperature, maintained for 24 hours, and the color difference before and after immersion was measured. At this time, the crude oil used was domestic BW WELL MP-411 diluted in 10% water.
<조관유 침해성 평가 기준><Criteria for assessing crude oil invasiveness>
○: ΔE ≤ 2○: ΔE ≤ 2
△: 2 < ΔE ≤ 3△: 2 < ΔE ≤ 3
×: 3 < ΔE×: 3 < ΔE
내알칼리성Alkali resistance
상기에 따라 표면처리된 강판(시편)을 60℃의 탈지용액에 2분간 침적한 후 수세, 에어 블로잉(air blowing)한 후, 전/후의 색차를 측정하였다. 이때, 알칼리 탈지 용액은 파카라이징사의 Finecleaner L 4460 A: 20g/2.4L + L 4460 B: 12g/2.4L (pH=12)를 사용하였다.The steel sheet (specimen) surface-treated as above was immersed in a degreasing solution at 60°C for 2 minutes, then washed with water and air blown, and the color difference before and after was measured. At this time, the alkaline degreasing solution used was Parkerizing's Finecleaner L 4460 A: 20g/2.4L + L 4460 B: 12g/2.4L (pH=12).
<내알칼리성 평가 기준><Alkali resistance evaluation criteria>
○: ΔE ≤ 2○: ΔE ≤ 2
△: 2 < ΔE ≤ 4△: 2 < ΔE ≤ 4
×: 4 < ΔE×: 4 < ΔE
점상 부식 내식성Pitting corrosion resistance
상기에 따라 표면처리된 강판(시편)의 표면에 분무기를 이용하여 이슬이 맺히도록 한 다음, 상기 분무 처리된 강판 두 장을 서로 맞대어 포장한 후 항온항습기에 넣어 고온 습도(42℃, 95%)에서 6시간, 저온 습도(15℃, 60%)에서 6시간을 1사이클로 하여 총 8사이클(cycle) 동안 행한 후, 표면의 점상 결함 개수를 측정하였다. 이때, 강판의 스캔 면적을 150×50mm2로 설정하고, 이를 100배로 확대하여 부식성 점상 결함 면적이 29500㎛2 이상인 것의 개수만을 세었다.Dew is formed on the surface of the steel sheet (specimen) treated as above using a sprayer, then the two sprayed steel sheets are packed side by side and placed in a constant temperature and humidity chamber at high temperature and humidity (42°C, 95%). After performing a total of 8 cycles, with 6 hours at low temperature and humidity (15°C, 60%) as one cycle, the number of point defects on the surface was measured. At this time, the scan area of the steel plate was set to 150 × 50 mm 2 and magnified 100 times, and only the number of corrosive point defects with an area of 29500 ㎛ 2 or more was counted.
<점상 부식 내식성 평가 기준><Standards for evaluation of spot corrosion resistance>
○: 점상 개수 ≤ 20○: Number of dots ≤ 20
△: 20 < 점상 개수 ≤ 40△: 20 < Number of dots ≤ 40
×: 40 < 점상 개수×: 40 < Number of dots
내흑변성Blackening resistance
강판의 내흑변성을 평가하기 위하여 3가크롬 표면처리 조성물로 처리된 강판의 색차를 측정한 후 항온항습기에 넣고 온도 50℃ 및 상대습도 95%의 조건에서 120시간 동안 유지 후 강판을 꺼내어 색차를 측정하였다.In order to evaluate the blackening resistance of the steel sheet, the color difference of the steel sheet treated with the trivalent chromium surface treatment composition was measured, placed in a constant temperature and humidity chamber, maintained for 120 hours at a temperature of 50℃ and relative humidity of 95%, then the steel sheet was taken out and the color difference was measured. did.
<내흑변성 평가 기준><Evaluation criteria for blackening resistance>
○: ΔE ≤ 3○: ΔE ≤ 3
△: 3< ΔE ≤ 5△: 3< ΔE ≤ 5
×: 5 < ΔE×: 5 < ΔE
이물결함Foreign body defect
상기 표면처리 조성물로 처리된 강판의 이물결함을 평가하기 위하여 표면적이 약 4cm2인 탐침에 흰색 거즈를 씌운 뒤 탐침의 위에 무게 10kg의 무게추를 올려놓고 100회를 왕복 마찰시킨 뒤 마찰 전후 거즈의 백색도(ΔL=Lbefore-Lafter) 값을 측정하였다. 이 때 고습조건을 모사하기 위하여 강판과 탐침 등은 모두 습도 챔버를 만들어 가습기 등으로 습도를 95% 이상 유지하며 마찰 평가를 진행하였다. In order to evaluate foreign matter defects in the steel sheet treated with the surface treatment composition, a probe with a surface area of about 4 cm 2 was covered with white gauze, a weight of 10 kg was placed on top of the probe, and the gauze was rubbed back and forth 100 times before and after friction. Whiteness (ΔL=L before -L after ) values were measured. At this time, in order to simulate high humidity conditions, a humidity chamber was created for both the steel plate and probe, and the friction evaluation was conducted while maintaining the humidity above 95% using a humidifier.
<이물결함 평가 기준><Foreign matter defect evaluation criteria>
○: ΔL ≤ 2.5○: ΔL ≤ 2.5
△: 2.5 < ΔL ≤ 5△: 2.5 < ΔL ≤ 5
×: 5 < ΔL×: 5 < ΔL
장기 내식성long-term corrosion resistance
장기 내식성을 평가하기 위하여 상기 표면처리 조성물로 처리된 강판을 [ISO 14993]에 의거하여 Cyclic corrosion test를 [Salt spray 2hr (5%NaCl, 35℃) → Drying 4hr (25%RH, 60℃) → Humid 2hr (95%RH, 50℃)] 진행하며 적청이 발생하는 시간을 측정하였다. 이 때 도금강판의 도금부착량은 단면 기준 150g/m2이다. In order to evaluate long-term corrosion resistance, the steel sheet treated with the above surface treatment composition was subjected to a cyclic corrosion test in accordance with [ISO 14993] [Salt spray 2hr (5%NaCl, 35℃) → Drying 4hr (25%RH, 60℃) → Humid 2hr (95%RH, 50℃)] and measured the time for red rust to occur. At this time, the plating adhesion amount of the plated steel sheet is 150g/m 2 based on the cross section.
<장기 내식성 평가 기준><Long-term corrosion resistance evaluation criteria>
○: 200일 ≤ 적청발생시기○: 200 days ≤ Red rust occurrence period
△: 150일 < 적청발생시기 ≤ 200일△: 150 days < red rust occurrence period ≤ 200 days
×: 적청발생시기 < 150일×: Red rust occurrence period < 150 days
상기 물성 측정 결과는 하기 표 3 및 4에 나타내었다.The physical property measurement results are shown in Tables 3 and 4 below.
본 발명에 따른 발명예 1 내지 16의 경우 용액안정성, 평판 내식성,가공부 내식성, 조관유 침해성, 내알칼리성, 점상 부식 내식성, 내흑변성, 장기 내식성 및 이물결함 등이 매우 우수함을 알 수 있다. 도 2에 도시된 바와 같이, 발명예 3은 표면에 적청이 발생하지 않음을 알 수 있다. In the case of Inventive Examples 1 to 16 according to the present invention, it can be seen that solution stability, plate corrosion resistance, processing part corrosion resistance, crude oil penetration, alkali resistance, spotting corrosion resistance, blackening resistance, long-term corrosion resistance, and foreign matter defects are very excellent. As shown in Figure 2, it can be seen that red rust does not occur on the surface of Inventive Example 3.
비교예 1의 경우, 3가크롬 화합물의 함량이 부족하여 베리어 효과(Barrier effect)에 의한 내식성이 열위하여 평판내식성, 가공부 내식성, 점상 부식 내식성 및 장기내식성이 부족함을 알 수 있다. 도 1에 나타난 바와 같이, 비교예 1은 적청이 발생한 것을 알 수 있다. In the case of Comparative Example 1, it can be seen that the content of the trivalent chromium compound is insufficient and the corrosion resistance due to the barrier effect is poor, resulting in insufficient flat plate corrosion resistance, machining part corrosion resistance, spot corrosion resistance, and long-term corrosion resistance. As shown in Figure 1, it can be seen that red rust occurred in Comparative Example 1.
비교예 2의 경우, 3가 크롬 화합물의 함량이 지나치게 많아 이물결함이 발생함을 알 수 있다.In the case of Comparative Example 2, it can be seen that the content of the trivalent chromium compound was too high, causing foreign matter defects.
비교예 3의 경우, 산도 조절제의 함량이 부족하여 용액안정성이 부족하고 이로 인해 평판 내식성, 가공부 내식성, 점상 부식 내식성, 내흑변성 및 장기 내식성이 열위함을 알 수 있다. In the case of Comparative Example 3, the content of the acidity regulator was insufficient, resulting in insufficient solution stability, which resulted in poor plate corrosion resistance, processing part corrosion resistance, spotting corrosion resistance, blackening resistance, and long-term corrosion resistance.
비교예 4의 경우, 산도조절제의 함량이 지나치게 많아 잔류산으로 인해 평판내식성, 가공 부내식성, 점상 부식 내식성 및 장기내식성이 부족함을 알 수 있다. In the case of Comparative Example 4, it can be seen that the content of the acidity regulator was too high and the plate corrosion resistance, processing corrosion resistance, pitting corrosion resistance, and long-term corrosion resistance were insufficient due to residual acid.
비교예 5의 경우, 밀착성 향상제의 함량이 부족하여 이물결함이 발생함을 알 수 있다. In the case of Comparative Example 5, it can be seen that foreign matter defects occurred due to insufficient content of the adhesion improver.
비교예 6의 경우, 밀착성 향상제의 함량이 지나치게 많아 잔존하는 미반응 실란으로 인해 평판 내식성, 가공부 내식성, 점상 부식 내식성 및 장기 내식성이 부족함을 알 수 있다. In the case of Comparative Example 6, it can be seen that the flat plate corrosion resistance, machining area corrosion resistance, pitting corrosion resistance, and long-term corrosion resistance are insufficient due to the unreacted silane remaining due to the excessively high content of the adhesion improver.
비교예 7의 경우, 내식성 개선제의 함량이 부족하여 평판 내식성, 가공부 내식성, 점상 부식 내식성 및 장기 내식성이 부족함을 알 수 있다. In the case of Comparative Example 7, it can be seen that the content of the corrosion resistance improver is insufficient, resulting in insufficient plate corrosion resistance, machined part corrosion resistance, pitting corrosion resistance, and long-term corrosion resistance.
비교예 8의 경우, 내식성 개선제의 함량이 지나치게 많아 높은 고형분으로 인해 용액 안정성이 부족하고 이로 인해 평판 내식성, 가공부 내식성, 점상 부식 내식성, 내흑변성 및 장기 내식성이 열위함을 알 수 있다. In the case of Comparative Example 8, the content of the corrosion resistance improver was too high, resulting in insufficient solution stability due to the high solid content, which resulted in poor plate corrosion resistance, machined part corrosion resistance, pitting corrosion resistance, blackening resistance, and long-term corrosion resistance.
비교예 9의 경우, 점상 부식 개선제의 함량이 부족하여 점상 부식 내식성이 열위함을 알 수 있다. In the case of Comparative Example 9, it can be seen that the pitting corrosion resistance is inferior due to the insufficient content of the pitting corrosion improver.
비교예 10의 경우, 점상 부식 개선제의 함량이 지나치게 많아 용액 안정성이 부족하고 이로 인해 가공부 내식성, 조관유 침해성, 내흑변성 및 장기 내식성이 열위함을 알 수 있다. In the case of Comparative Example 10, it can be seen that the content of the pitting corrosion improver was too high, resulting in insufficient solution stability, which resulted in poor corrosion resistance of processed parts, penetration of crude oil, blackening resistance, and long-term corrosion resistance.
비교예 11의 경우, 장기 내식성 향상제의 함량이 부족하여 장기 내식성이 열위함을 알 수 있다. In the case of Comparative Example 11, it can be seen that the long-term corrosion resistance is inferior due to the insufficient content of the long-term corrosion resistance improver.
비교예 12의 경우, 장기 내식성 향상제의 함량이 지나치게 많아 이물결함이 발생함을 알 수 있다.In the case of Comparative Example 12, it can be seen that the content of the long-term corrosion resistance improver was too high, causing foreign body defects.
비교예 13의 경우, 윤활제의 함량이 부족하여 이물결함이 발생함을 알 수 있다.In the case of Comparative Example 13, it can be seen that foreign matter defects occurred due to insufficient lubricant content.
비교예 14의 경우, 윤활제의 함량이 지나치게 많아 용액 안정성이 부족하고 이로 인해 가공부 내식성과 장기 내식성이 열위함을 알 수 있다. In the case of Comparative Example 14, the lubricant content was too high, resulting in insufficient solution stability, which resulted in poor corrosion resistance of the machined part and long-term corrosion resistance.
비교예 15의 경우, 조용제의 함량이 부족하여 표면결함이 발생하고 이로 인해 평판 내식성, 가공부 내식성 및 장기 내식성이 열위함을 알 수 있다. In the case of Comparative Example 15, surface defects occurred due to insufficient content of the co-lubricant, which resulted in poor plate corrosion resistance, processing part corrosion resistance, and long-term corrosion resistance.
비교예 16의 경우, 조용제의 함량이 지나치게 많아 용액 안정성이 부족하고 이로 인해 가공부 내식성, 내흑변성 및 장기 내식성이 열위함을 알 수 있다.In the case of Comparative Example 16, it can be seen that the solution stability is insufficient because the content of the co-solvent is too high, and as a result, the corrosion resistance of the processed part, blackening resistance, and long-term corrosion resistance are inferior.
Claims (17)
산도 조절제 0.1~5중량%,
밀착성 향상제 1~20중량%,
내식성 개선제 1~20중량%,
점상 부식 개선제 0.1~5.0중량%,
장기 내식성 향상제 1~10중량%,
윤활제 0.1~3.0중량%,
조용제 1~20중량% 및
잔량 용제를 포함하는 표면처리용 용액 조성물.
1 to 10% by weight of trivalent chromium compound,
Acidity regulator 0.1~5% by weight,
Adhesion improver 1-20% by weight,
Corrosion resistance improver 1~20% by weight,
Spot corrosion improver 0.1 to 5.0% by weight,
1 to 10% by weight of long-term corrosion resistance improver,
Lubricant 0.1~3.0% by weight,
1 to 20% by weight of solvent and
A solution composition for surface treatment containing a residual amount of solvent.
상기 3가 크롬 화합물은 황산크롬, 질산크롬, 인산크롬, 불화크롬 및 이들의 혼합물로 이루어진 군에서 선택된 하나 이상의 것인 표면처리용 용액 조성물.
In claim 1,
A solution composition for surface treatment, wherein the trivalent chromium compound is one or more selected from the group consisting of chromium sulfate, chromium nitrate, chromium phosphate, chromium fluoride, and mixtures thereof.
상기 산도 조절제는 인산, 질산, 황산, 불산, 염산, (NH4)H2PO4, (NH4)2HPO4, NaH2PO4, Na2HPO4, 피트산(Phytic acid), 글리콜릭산, 젖산, 초산, 옥살릭산 및 이들의 혼합물로 이루어진 군에서 선택된 하나 이상의 것인 표면처리용 용액 조성물.
In claim 1,
The acidity regulator is phosphoric acid, nitric acid, sulfuric acid, hydrofluoric acid, hydrochloric acid, (NH 4 )H 2 PO 4 , (NH 4 ) 2 HPO 4 , NaH 2 PO 4 , Na 2 HPO 4 , phytic acid, glycolic acid. , a solution composition for surface treatment that is at least one selected from the group consisting of lactic acid, acetic acid, oxalic acid, and mixtures thereof.
상기 밀착성 향상제는 비닐메톡시 실란, 비닐트리메톡시 실란(VTMS), 비닐에폭시 실란, 비닐트리에폭시 실란, 3-아미노프로필트리에폭시 실란, 3-글리시독시프로필트리메톡시 실란, 3-메타글리옥시프로필트리메톡시 실란, γ-글리시독시프로필트리에톡시실란, γ-글리시독시트리메틸디메톡시실란, N-(3-(trimethoxysilyl)propyl)ethylenediamine (AEAPTMS), 2-(3,4-Epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-Epoxycyclohexyl)ethyltriethoxysilane, 3-(2,3-Epoxypropoxy)propyltrimethoxysilane, 3-(2,3-Epoxypropoxy)propyltriethoxysilane, 3-(2,3-Epoxypropoxy)propylmethyldiethoxysilane, 3-(2,3-Epoxypropoxy)propylmethyldimethoxysilane , 3-Aminopropyltriethoxysilane, 3-Aminopropyltrimethoxysilane, 3-Amonopropylmethydiethoxysilane, N-(2-Aminoethyl-3-aminopropyl)methyldimethoxysilane, N-(2-Aminoethyl-3-aminopropyl)trimethoxysilane, Diethylenetriaminopropyltrimethoxysilane, 3-Ureidopropyltrimethoxysilane, N-Phenylaminopropyltrimethoxysilane, (3-Glycidyloxypropyl)trimethoxysilane(GPTMS), Methyltrimethoxysilane(MTMS) 및 이들의 혼합물로 이루어진 군으로부터 선택되는 하나 이상의 것인 표면처리용 용액 조성물.
In claim 1,
The adhesion improvers include vinyl methoxy silane, vinyl trimethoxy silane (VTMS), vinyl epoxy silane, vinyl triepoxy silane, 3-aminopropyltriepoxy silane, 3-glycidoxypropyltrimethoxy silane, and 3-metagly. Oxypropyltrimethoxy silane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxytrimethyldimethoxysilane, N-(3-(trimethoxysilyl)propyl)ethylenediamine (AEAPTMS), 2-(3,4- Epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-Epoxycyclohexyl)ethyltriethoxysilane, 3-(2,3-Epoxypropoxy)propyltrimethoxysilane, 3-(2,3-Epoxypropoxy)propyltriethoxysilane, 3-(2,3-Epoxypropoxy)propylmethyldiethoxysilane, 3- (2,3-Epoxypropoxy)propylmethyldimethoxysilane, 3-Aminopropyltriethoxysilane, 3-Aminopropyltrimethoxysilane, 3-Amonopropylmethydiethoxysilane, N-(2-Aminoethyl-3-aminopropyl)methyldimethoxysilane, N-(2-Aminoethyl-3-aminopropyl)trimethoxysilane, Diethylenetriaminopropyltrimethoxysilane , 3 -A solution composition for surface treatment that is one or more selected from the group consisting of Ureidopropyltrimethoxysilane, N-Phenylaminopropyltrimethoxysilane, (3-Glycidyloxypropyl)trimethoxysilane (GPTMS), Methyltrimethoxysilane (MTMS), and mixtures thereof.
상기 내식성 개선재는 바나딜 아세틸아세토네이트(Vanadyl acetylacetonate), 메타바나딘산암모늄(Ammonium metavanadate), 메타바나딘산칼륨(Potassium metavanadate), 메타바나딘산나트륨(Sodium metavanadate), 바나듐 삼산화물(Vanadium trioxide), 바나듐 아세틸아세테이트, 암모늄 메타바나데이트, 산화규소 및 이들의 혼합물로 이루어진 군에서 선택된 하나 이상의 것인 표면처리용 용액 조성물.
In claim 1,
The corrosion resistance improving material includes vanadyl acetylacetonate, ammonium metavanadate, potassium metavanadate, sodium metavanadate, and vanadium trioxide. ), a solution composition for surface treatment that is at least one selected from the group consisting of vanadium acetylacetate, ammonium metavanadate, silicon oxide, and mixtures thereof.
상기 점상 부식 개선재는 에틸렌다이아민, 헥사메틸렌다이아민, 트리메틸아민, 메틸아민, 디페닐아민, 에틸렌아민, 아닐린, 톨루이딘, 피페리딘, 아지리딘, 피리딘, 알라닌, 프로필아민, 디이소프로필아민, 모노이소프로필아민, 디부틸아민, 디프로필아민 및 이들의 혼합물로 이루어진 군에서 선택된 하나 이상의 것인 표면처리용 용액 조성물.
In claim 1,
The spot corrosion improving agent includes ethylenediamine, hexamethylenediamine, trimethylamine, methylamine, diphenylamine, ethyleneamine, aniline, toluidine, piperidine, aziridine, pyridine, alanine, propylamine, diisopropylamine, A solution composition for surface treatment, which is at least one selected from the group consisting of monoisopropylamine, dibutylamine, dipropylamine, and mixtures thereof.
상기 장기 내식성 향상제는 염화크롬 무수물, 염화크롬 5수화물, 염화크롬 6수화물, 염화크롬 9수화물 및 이들의 혼합물로 이루어진 군으로부터 선택되는 하나 이상의 것인 표면처리용 용액 조성물.
In claim 1,
The long-term corrosion resistance improver is a solution composition for surface treatment, wherein the long-term corrosion resistance improver is at least one selected from the group consisting of chromium chloride anhydride, chromium chloride pentahydrate, chromium chloride hexahydrate, chromium chloride nonahydrate, and mixtures thereof.
상기 윤활제는 Polytetrafluoroethylene(PTFE), Polyethylene(PE), Carnauba계 왁스 및 이들의 혼합물로 이루어진 군으로부터 선택되는 하나 이상의 것인 표면처리용 용액 조성물.
In claim 1,
The lubricant is a solution composition for surface treatment, wherein the lubricant is one or more selected from the group consisting of Polytetrafluoroethylene (PTFE), Polyethylene (PE), Carnauba-based wax, and mixtures thereof.
상기 조용제는 에탈올, 이소프로필알코올, 메탄올, 탈로우 알코올(Tallow alcohol), 2-부톡시에탄올(2-butoxyethanol), 디에틸렌 글리콜 모노부틸 에테르(Diethylene glycol monobutyl ether) 및 이들의 혼합물로 이루어진 군에서 선택된 하나 이상의 것인 표면처리용 용액 조성물.
In claim 1,
The co-solvent is a group consisting of ethanol, isopropyl alcohol, methanol, tallow alcohol, 2-butoxyethanol, Diethylene glycol monobutyl ether, and mixtures thereof. A solution composition for surface treatment that is one or more selected from .
상기 용제는 물인 표면처리용 용액 조성물.
In claim 1,
A solution composition for surface treatment wherein the solvent is water.
상기 강판의 적어도 일면에 형성된 도금층; 및
상기 도금층 상에 형성된 표면처리 코팅층을 포함하며,
상기 표면처리 코팅층은 청구항 1 내지 10 중 어느 한 항의 용액 조성물로 형성된 것인 표면처리된 도금강판.
steel plate;
A plating layer formed on at least one surface of the steel sheet; and
It includes a surface treatment coating layer formed on the plating layer,
The surface-treated coating layer is a surface-treated plated steel sheet formed from the solution composition of any one of claims 1 to 10.
상기 도금층은 중량%로 마그네슘(Mg): 4.0~7.0%, 알루미늄(Al): 11.0~19.5%, 잔부 Zn 및 기타 불가피한 불순물을 포함하는 표면처리된 도금강판.
In claim 11,
The plating layer is a surface-treated plated steel sheet containing magnesium (Mg): 4.0-7.0%, aluminum (Al): 11.0-19.5%, and the balance Zn and other inevitable impurities in weight percent.
상기 도금층은 하기 관계식 1을 만족하는 표면처리된 도금강판.
[관계식 1]
0.26 ≤ I(110)/I(103) ≤ 0.65
(관계식 1에서, I(110)은 MgZn2상에 대한 (110)면 결정 피크의 X선 회절 적분 강도를 나타내고, 상기 I(103)은 MgZn2상에 대한 (103)면 결정의 X선 회절 적분 강도를 나타낸다.)
In claim 12,
The plating layer is a surface-treated plated steel sheet that satisfies the following equation 1.
[Relational Expression 1]
0.26 ≤ I(110)/I(103) ≤ 0.65
(In equation 1, I (110) represents the X-ray diffraction integrated intensity of the (110) plane crystal peak for the MgZn 2 phase , and I (103) represents the Indicates the integrated intensity.)
상기 표면처리 코팅층은 0.1~2.0㎛의 두께를 가지는 것인 표면처리된 도금강판.
In claim 11,
A surface-treated plated steel sheet wherein the surface treatment coating layer has a thickness of 0.1 to 2.0 μm.
상기 도금층 상에 청구항 1 내지 10 중 어느 한 항의 용액 조성물을 코팅처리하는 단계; 및
상기 코팅처리된 강판을 건조처리하는 단계
를 포함하는 표면처리된 도금강판의 제조방법.
Providing a zinc alloy plated steel sheet having a plating layer formed on at least one surface;
Coating the solution composition of any one of claims 1 to 10 on the plating layer; and
Drying the coated steel sheet
Method for manufacturing a surface-treated plated steel sheet comprising.
상기 코팅처리는 바코팅, 롤코팅, 스프레이, 침적, 스프레이 스퀴징 및 침적 스퀴징으로 이루어진 군에서 선택된 어느 하나의 방법으로 행해지는 것인 표면처리된 도금강판의 제조방법.
In claim 15,
The coating treatment is a method of manufacturing a surface-treated plated steel sheet, wherein the coating treatment is performed by any one method selected from the group consisting of bar coating, roll coating, spraying, dipping, spray squeezing, and dipping squeezing.
상기 건조는 강판의 최종도달온도(PMT) 기준으로 40~280℃의 온도 범위에서 행해지는 것인 표면처리된 도금강판의 제조방법.
In claim 15,
A method of manufacturing a surface-treated plated steel sheet, wherein the drying is carried out in a temperature range of 40 to 280° C. based on the final temperature (PMT) of the steel sheet.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/KR2023/019354 WO2024128623A1 (en) | 2022-12-12 | 2023-11-28 | Surface treatment solution composition for plated steel sheet, plated steel sheet surface-treated using same and method for manufacturing thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| KR20240087343A true KR20240087343A (en) | 2024-06-19 |
Family
ID=
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109804102B (en) | Surface treatment solution composition, galvanized steel sheet surface-treated with the composition, and method for producing the same | |
| US11634819B2 (en) | Solution composition for steel sheet surface treatment, zinc-based plated steel sheet surface-treated with same, and manufacturing method therefor | |
| JP5075321B2 (en) | Aqueous treatment agent for metal surface | |
| RU2418098C2 (en) | Material of zinc containing clad steel with composite coating distinguished with excellent corrosion and blackening resistance, adhesion of coating and alkali resistance | |
| JP2007327142A (en) | Corrosion-resistant surface-treated metal material and surface treatment agent therefor | |
| JP6796101B2 (en) | Manufacturing method of coated plated steel sheet and coated plated steel sheet | |
| KR101306405B1 (en) | Cr-FREE COATING SOLUTION WITH EXCELLENT CORROSION RESISTANCE AND METHOD FOR MANUFACTURING GALVANIZED STEEL SHEET USING THE COATING SOLUTION | |
| KR102142771B1 (en) | Solution composition for surface treating of steel sheet, galvanized steel sheet using the same, and manufacturing method of the same | |
| JP2002332574A (en) | Plated steel with chromate-free treated film having excellent corrosion resistance | |
| JP2003055777A (en) | Chromate-free treated hot dip zinc - aluminum alloy plated steel sheet having excellent weldability and corrosion resistance | |
| JP6667638B2 (en) | Composition for washing pickled steel sheet, method for washing pickled steel sheet using the same, and steel sheet obtained by this | |
| EP4071219A1 (en) | Surface treatment composition for ternary hot-dip galvannealed steel sheet, providing excellent corrosion resistance and surface color, ternary hot-dip galvannealed steel sheet surface-treated using same, and manufacturing method therefor | |
| KR20240087343A (en) | Surface treatment composition for plated steel sheet, plated steel sheet using same and method for manufacturing thereof | |
| EP4265820A1 (en) | Composition for surface treatment of steel sheet and steel sheet using same | |
| JP2001115273A (en) | HOT DIP Zn-Al SERIES PLATED STEEL SHEET EXCELLENT IN SECULAR BLACKENING RESISTANCE | |
| KR20230094547A (en) | Composition for surface treating of steel sheet, steel sheet using thereof, and manufacturing method of the same | |
| KR101500081B1 (en) | Coationg solution and coated steel sheet having high alkali resistance | |
| KR20230093920A (en) | Composition for surface treating of steel sheet, steel sheet using thereof, and manufacturing method of the same | |
| JP7060178B1 (en) | Surface-treated steel sheet for organic resin coating and its manufacturing method, and organic resin coated steel sheet and its manufacturing method | |
| KR102677276B1 (en) | Composition for surface treatment of steel sheet and steel sheet using the same | |
| KR20230081132A (en) | Coating composition for hot dip galvanized steel sheet having excellent corrosion resistant and anti-blackening, hot dip galvanized steel sheet prepared by using thereof, and manufacturing method the same | |
| JP5585484B2 (en) | Zinc-based plated steel with excellent blackening resistance | |
| JP3329241B2 (en) | Method for producing chromate-treated galvanized steel sheet with excellent black spot resistance, blackening resistance and corrosion resistance | |
| KR20230081109A (en) | Coating composition for hot dip galvanized steel sheet having excellent corrosion resistant and environmental stability, hot dip galvanized steel sheet prepared by using thereof, and manufacturing method the same | |
| KR960004781B1 (en) | Method for making a chromate solution of galvanized steel plates with an excellent sulfurizing resistance |