KR20230081132A - 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 - Google Patents
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 Download PDFInfo
- Publication number
- KR20230081132A KR20230081132A KR1020210168921A KR20210168921A KR20230081132A KR 20230081132 A KR20230081132 A KR 20230081132A KR 1020210168921 A KR1020210168921 A KR 1020210168921A KR 20210168921 A KR20210168921 A KR 20210168921A KR 20230081132 A KR20230081132 A KR 20230081132A
- Authority
- KR
- South Korea
- Prior art keywords
- steel sheet
- composition
- weight
- galvanized steel
- dip galvanized
- Prior art date
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- 238000005260 corrosion Methods 0.000 title claims abstract description 169
- 230000007797 corrosion Effects 0.000 title claims abstract description 168
- 229910001335 Galvanized steel Inorganic materials 0.000 title claims abstract description 46
- 239000008397 galvanized steel Substances 0.000 title claims abstract description 46
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 239000008199 coating composition Substances 0.000 title 1
- 239000000203 mixture Substances 0.000 claims abstract description 163
- 238000004381 surface treatment Methods 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 22
- 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 66
- 229910000831 Steel Inorganic materials 0.000 claims description 57
- 239000010959 steel Substances 0.000 claims description 57
- 150000001845 chromium compounds Chemical class 0.000 claims description 51
- 239000007787 solid Substances 0.000 claims description 49
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 48
- 239000011248 coating agent Substances 0.000 claims description 47
- 238000012545 processing Methods 0.000 claims description 37
- 239000000654 additive Substances 0.000 claims description 35
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims description 35
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 35
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 32
- 230000000996 additive effect Effects 0.000 claims description 32
- 239000003795 chemical substances by application Substances 0.000 claims description 31
- 239000011247 coating layer Substances 0.000 claims description 28
- 239000002904 solvent Substances 0.000 claims description 28
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 26
- 238000007747 plating Methods 0.000 claims description 26
- 239000010410 layer Substances 0.000 claims description 25
- 235000019441 ethanol Nutrition 0.000 claims description 24
- 230000009467 reduction Effects 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 23
- 239000003054 catalyst Substances 0.000 claims description 21
- 239000003638 chemical reducing agent Substances 0.000 claims description 20
- 229910001430 chromium ion Inorganic materials 0.000 claims description 20
- 229910003023 Mg-Al Inorganic materials 0.000 claims description 17
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 16
- 238000000576 coating method Methods 0.000 claims description 16
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 16
- 239000011777 magnesium Substances 0.000 claims description 15
- 150000003682 vanadium compounds Chemical group 0.000 claims description 15
- 239000011230 binding agent Substances 0.000 claims description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 13
- 229910002651 NO3 Inorganic materials 0.000 claims description 13
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 13
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 13
- 229910052744 lithium Inorganic materials 0.000 claims description 13
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 13
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 13
- 229910000077 silane Inorganic materials 0.000 claims description 13
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 13
- BFDQRLXGNLZULX-UHFFFAOYSA-N titanium hydrofluoride Chemical compound F.[Ti] BFDQRLXGNLZULX-UHFFFAOYSA-N 0.000 claims description 13
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims description 10
- 229910017706 MgZn Inorganic materials 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000007602 hot air drying Methods 0.000 claims description 7
- 230000006698 induction Effects 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 238000010924 continuous production Methods 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 5
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004111 Potassium silicate Substances 0.000 claims description 4
- 239000004115 Sodium Silicate Substances 0.000 claims description 4
- 238000002441 X-ray diffraction Methods 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052913 potassium silicate Inorganic materials 0.000 claims description 4
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 4
- 238000005246 galvanizing Methods 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 3
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 claims description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 2
- JZDMNWBZPLJKBT-UHFFFAOYSA-N F.[Zr] Chemical compound F.[Zr] JZDMNWBZPLJKBT-UHFFFAOYSA-N 0.000 claims description 2
- 229910039444 MoC Inorganic materials 0.000 claims description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims description 2
- 229910021551 Vanadium(III) chloride Inorganic materials 0.000 claims description 2
- 229910021542 Vanadium(IV) oxide Inorganic materials 0.000 claims description 2
- QDAYJHVWIRGGJM-UHFFFAOYSA-B [Mo+4].[Mo+4].[Mo+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Mo+4].[Mo+4].[Mo+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QDAYJHVWIRGGJM-UHFFFAOYSA-B 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
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 2
- GPBUGPUPKAGMDK-UHFFFAOYSA-N azanylidynemolybdenum Chemical compound [Mo]#N GPBUGPUPKAGMDK-UHFFFAOYSA-N 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- XDBSEZHMWGHVIL-UHFFFAOYSA-M hydroxy(dioxo)vanadium Chemical compound O[V](=O)=O XDBSEZHMWGHVIL-UHFFFAOYSA-M 0.000 claims description 2
- OBTSLRFPKIKXSZ-UHFFFAOYSA-N lithium potassium Chemical compound [Li].[K] OBTSLRFPKIKXSZ-UHFFFAOYSA-N 0.000 claims description 2
- VVNXEADCOVSAER-UHFFFAOYSA-N lithium sodium Chemical compound [Li].[Na] VVNXEADCOVSAER-UHFFFAOYSA-N 0.000 claims description 2
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 2
- 150000002751 molybdenum Chemical class 0.000 claims description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 2
- LNDHQUDDOUZKQV-UHFFFAOYSA-J molybdenum tetrafluoride Chemical compound F[Mo](F)(F)F LNDHQUDDOUZKQV-UHFFFAOYSA-J 0.000 claims description 2
- TXCOQXKFOPSCPZ-UHFFFAOYSA-J molybdenum(4+);tetraacetate Chemical compound [Mo+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O TXCOQXKFOPSCPZ-UHFFFAOYSA-J 0.000 claims description 2
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 claims description 2
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 claims description 2
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 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
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 2
- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 claims description 2
- JBIQAPKSNFTACH-UHFFFAOYSA-K vanadium oxytrichloride Chemical compound Cl[V](Cl)(Cl)=O JBIQAPKSNFTACH-UHFFFAOYSA-K 0.000 claims description 2
- HQYCOEXWFMFWLR-UHFFFAOYSA-K vanadium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[V+3] HQYCOEXWFMFWLR-UHFFFAOYSA-K 0.000 claims description 2
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 claims description 2
- BKXZLZVGNZNKGG-UHFFFAOYSA-N P(=O)(=O)[V] Chemical compound P(=O)(=O)[V] BKXZLZVGNZNKGG-UHFFFAOYSA-N 0.000 claims 1
- 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 1
- 239000005078 molybdenum compound Substances 0.000 claims 1
- 150000002752 molybdenum compounds Chemical class 0.000 claims 1
- 239000004035 construction material Substances 0.000 abstract description 5
- 239000007769 metal material Substances 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 45
- 230000000052 comparative effect Effects 0.000 description 42
- 230000000704 physical effect Effects 0.000 description 25
- 238000006722 reduction reaction Methods 0.000 description 24
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 22
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 21
- 238000011156 evaluation Methods 0.000 description 18
- 230000008859 change Effects 0.000 description 16
- 238000002474 experimental method Methods 0.000 description 14
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 12
- HQHWIOUCOLWWOD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propyl 2-aminoacetate Chemical compound CCO[Si](C)(OCC)CCCOC(=O)CN HQHWIOUCOLWWOD-UHFFFAOYSA-N 0.000 description 12
- 229910052804 chromium Inorganic materials 0.000 description 12
- 239000011651 chromium Substances 0.000 description 12
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 11
- 206010016100 Faeces discoloured Diseases 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 10
- 238000003754 machining Methods 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 239000003513 alkali Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 229910001297 Zn alloy Inorganic materials 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000005530 etching Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000002845 discoloration Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000010186 staining Methods 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 230000002542 deteriorative effect Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000003517 fume Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical group [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- 229910000861 Mg alloy Inorganic materials 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000003666 anti-fingerprint Effects 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000013256 coordination polymer Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- PLIMYDKDFNSOAB-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-aminoacetate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)CN PLIMYDKDFNSOAB-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- ITMMSVVGGCCDLS-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-aminoacetate Chemical compound CO[Si](OC)(OC)CCCOC(=O)CN ITMMSVVGGCCDLS-UHFFFAOYSA-N 0.000 description 1
- LVACOMKKELLCHJ-UHFFFAOYSA-N 3-trimethoxysilylpropylurea Chemical compound CO[Si](OC)(OC)CCCNC(N)=O LVACOMKKELLCHJ-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- XNLPZZOCLLAQIM-UHFFFAOYSA-N acetyl acetate;vanadium Chemical compound [V].CC(=O)OC(C)=O XNLPZZOCLLAQIM-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- -1 alkoxy silanes Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- INJVFBCDVXYHGQ-UHFFFAOYSA-N n'-(3-triethoxysilylpropyl)ethane-1,2-diamine Chemical compound CCO[Si](OCC)(OCC)CCCNCCN INJVFBCDVXYHGQ-UHFFFAOYSA-N 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 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 description 1
- 229910052725 zinc Inorganic materials 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
- C23C22/24—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 hexavalent chromium compounds
- C23C22/33—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 hexavalent chromium compounds containing also phosphates
-
- 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
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- C—CHEMISTRY; METALLURGY
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Abstract
본 발명은 금속재료, 특히 건자재 용도로 사용되는 용융아연합금 도금강판의 내식성, 내흑변성 등을 향상시키기 위한 표면처리용 조성물, 상기 조성물을 이용하여 표면처리된 삼원계 용융아연도금강판 및 이의 제조방법에 관한 것이다.The present invention relates to a surface treatment composition for improving the corrosion resistance and blackening resistance of hot-dip galvanized steel sheets used for metal materials, particularly construction materials, a ternary hot-dip galvanized steel sheet surface-treated using the composition, and a method for manufacturing the same It is about.
Description
본 발명은 금속재료, 특히 건자재 용도로 사용되는 용융아연합금 도금강판의 내식성, 내흑변성 등을 향상시키기 위한 표면처리용 조성물, 상기 조성물을 이용하여 표면처리된 삼원계 용융아연도금강판 및 이의 제조방법에 관한 것이다.The present invention relates to a surface treatment composition for improving the corrosion resistance and blackening resistance of hot-dip galvanized steel sheets used for metal materials, particularly construction materials, a ternary hot-dip galvanized steel sheet surface-treated using the composition, and a method for manufacturing the same It is about.
일반적으로 순수 아연도금강판에 비하여, 적청 내식성이 우수한 강재로서 마그네슘(Mg), 알루미늄(Al) 등을 함유한 아연합금층을 가진 강판은 노출면의 대부분이 아연(Zn) 또는 아연합금(Zn alloy)으로 이루어져 있어, 일반 환경, 특히 습윤 분위기에 노출되었을 때 표면에 백청의 발청 현상이 발생한다. 또한, 도금층에 함유되어 있는 Mg 및 Al이 Zn보다 산소 친화력이 좋아, 아연에 결합하는 산소가 부족하게 되면서 흑변 현상도 일어나기 쉽다.In general, compared to pure galvanized steel sheets, most of the exposed surface of a steel sheet having a zinc alloy layer containing magnesium (Mg) or aluminum (Al) as a steel material having excellent red rust corrosion resistance is zinc (Zn) or zinc alloy (Zn alloy) ), and when exposed to a general environment, especially a humid atmosphere, a rusting phenomenon of white rust occurs on the surface. In addition, since Mg and Al contained in the plating layer have a better oxygen affinity than Zn, oxygen binding to zinc is insufficient, and blackening is likely to occur.
이러한 문제점을 해결하기 위하여 종래에는, 방청 처리의 일환으로 도금 처리된 강판에 6가 크롬을 함유한 크로메이트 처리를 행하거나, 금속표면을 5~100mg/m2의 크로메이트로 전처리 후 유기 피막을 형성하였다. 하지만, 이와 같이 표면처리를 삼원계 아연도금강판에 적용하는 경우 여전히 흑색으로 변하거나 흑점이 발생하는 결함 문제가 있어 왔다.In order to solve this problem, conventionally, as part of the anti-rust treatment, a chromate treatment containing hexavalent chromium was performed on the plated steel sheet, or the metal surface was pretreated with 5 to 100 mg/m 2 of chromate, and then an organic film was formed. . However, when the surface treatment is applied to the ternary galvanized steel sheet, there is still a problem of turning black or generating black spots.
이에, 최근에는 6가 크롬을 함유하지 않는 내식용 금속 코팅제를 개발하고, 이로부터 도금강판의 내식성 및 내흑변성을 확보하는 방법을 적용하였다.Accordingly, recently, a corrosion-resistant metal coating agent not containing hexavalent chromium was developed, and a method of securing corrosion resistance and blackening resistance of a plated steel sheet was applied therefrom.
예를 들어, 특허문헌 1 내지 3에서는 3가 크롬을 함유하는 조성물에 강판을 침적시켜 화성 처리하는 방식으로 내식성 및 흑변성을 확보하고자 하였으나, 이 공정을 철강사의 연속 공정에 적용하기에 침적시간이 길고, 화성 처리 방법은 내지문성 저하 등의 문제를 가지고 있다.For example, in Patent Documents 1 to 3, corrosion resistance and blackening were attempted by immersing the steel sheet in a composition containing trivalent chromium and chemically treating it, but the immersion time was too long to apply this process to the continuous process of steel yarn. Long, chemical conversion treatment methods have problems such as deterioration in anti-fingerprint properties.
또한, 특허문헌 4 및 5에서는 스프레이 또는 롤코터 방식으로 철강사의 연속라인에 적용이 가능하고, 내지문성을 확보하는 방법을 개시하고 있다. 하지만, 다공질의 실리카 성분을 사용함에 의해 습윤한 분위기에서 변색 발생이 심한 Mg, Al 합금 강판에는 적합하지 않다. 뿐만 아니라, 다공질의 실리카는 흡습 성질이 강해서 Mg, Al, Zn 합금 강판에는 급격한 변색 발생을 유발시키는 문제가 있다.In addition, Patent Literatures 4 and 5 can be applied to a continuous line of steel yarn by a spray or roll coater method, and discloses a method for securing anti-fingerprint property. However, due to the use of a porous silica component, it is not suitable for Mg and Al alloy steel sheets that cause severe discoloration in a humid atmosphere. In addition, porous silica has a strong hygroscopic property, causing rapid discoloration in Mg, Al, and Zn alloy steel sheets.
그리고, 건자재용 철강 소재로서 사용되어지기 위해서는 고객 사용시 가공 부위의 내식성뿐만 아니라, 옥외 고온고습 환경에서도 사용이 가능하도록 흑화 변색 안정성을 부여할 필요성이 높아지고 있다.And, in order to be used as a steel material for construction materials, there is a growing need to impart blackening and discoloration stability so that it can be used in an outdoor high temperature and high humidity environment as well as corrosion resistance of the processed part when used by customers.
본 발명의 일 측면은, 건자재용 용융아연합금 도금강판을 제공함에 있어서, 내식성, 내흑변성 등을 우수하게 부여할 수 있는 삼원계 용융아연도금강판 표면처리용 조성물과, 이를 이용하여 표면처리된 삼원계 용융아연도금강판 및 이의 제조방법을 제공하고자 하는 것이다.One aspect of the present invention, in providing a hot-dip galvanized steel sheet for construction materials, is a composition for surface treatment of a ternary hot-dip galvanized steel sheet capable of providing excellent corrosion resistance, blackening resistance, etc., and a ternary surface-treated composition using the same It is intended to provide a hot-dip galvanized steel sheet and a manufacturing method thereof.
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. The subject of the present invention will be understood from the entire contents of this specification, and those skilled in the art will have no difficulty in understanding the additional subject of the present invention.
본 발명의 일 측면은, 고형분 100중량%에 대하여, (a) 크롬 화합물 15~45중량%, (b) 방청 피막제 45~75중량%, (c) 방청 에칭제 0.1~3.0중량%, (d) 내식성 첨가제 0.1~5.0중량%, (e) 흑변 개선제(I) 0.5~3.0중량%, (f) 흑변 개선제(II) 0.1~2.0중량% 및 (g) 가공부 내식성 개선제 0.1~1.0중량%를 포함하고,One aspect of the present invention, based on 100% by weight of solid content, (a) 15 to 45% by weight of a chromium compound, (b) 45 to 75% by weight of an anticorrosive coating agent, (c) 0.1 to 3.0% by weight of an anticorrosive etchant, (d) ) 0.1 to 5.0% by weight of corrosion resistance additive, (e) 0.5 to 3.0% by weight of blackening improver (I), (f) 0.1 to 2.0% by weight of blackening improver (II) and (g) 0.1 to 1.0% by weight of processing part corrosion resistance improver include,
상기 크롬 화합물은 질산크롬(A) 및 크롬산염(B) 용액에 (h)환원제인 아인산을 0.5~5.0중량% 및 (i) 촉매제인 인산을 0.1~2.0중량%로 포함하여 얻는 것인 삼원계 용융아연도금강판 표면처리용 조성물을 제공한다.The chromium compound is a ternary system obtained by including (h) 0.5 to 5.0 wt% of phosphorous acid as a reducing agent and (i) 0.1 to 2.0 wt% of phosphoric acid as a catalyst in a solution of chromium nitrate (A) and chromate (B). A composition for surface treatment of hot-dip galvanized steel sheet is provided.
본 발명의 다른 일 측면은, 강판; 상기 강판의 적어도 일면에 형성된 Zn-Mg-Al계 도금층; 및 상기 도금층 상에 형성된 표면처리 코팅층을 포함하며,Another aspect of the present invention, a steel plate; a Zn-Mg-Al-based plating layer formed on at least one surface of the steel sheet; And a surface treatment coating layer formed on the plating layer,
상기 표면처리 코팅층은 상기의 표면처리용 조성물로 형성된 코팅층인 표면처리된 삼원계 용융아연도금강판을 제공한다.The surface treatment coating layer provides a surface-treated ternary hot-dip galvanized steel sheet that is a coating layer formed of the above surface treatment composition.
본 발명의 또 다른 일 측면은, 강판의 적어도 일면에 용융아연도금처리하여 Zn-Mg-Al계 도금층을 형성하는 단계; 상기 도금층 상에 상기의 표면처리용 조성물을 코팅처리하는 단계; 및 상기 코팅처리된 강판을 건조처리하는 단계를 포함하는 표면처리된 삼원계 용융아연도금강판의 제조방법을 제공한다.Another aspect of the present invention comprises the steps of forming a Zn-Mg-Al-based plating layer by hot-dip galvanizing treatment on at least one surface of a steel sheet; coating the surface treatment composition on the plating layer; and drying the coated steel sheet.
본 발명에 의하면, 장시간 보관 후 사용하더라도 침전 및 응집이 발생하지 않는 우수한 용액 안정성을 가질 뿐만 아니라, 이러한 조성물로 표면처리된 삼원계 용융아연도금강판은 가공부 내식성이 우수하고, 고온고습 환경 하에서 내흑변성이 우수한 효과가 있다.According to the present invention, not only does it have excellent solution stability in which precipitation and aggregation do not occur even after long-term storage and use, but the ternary hot-dip galvanized steel sheet surface-treated with this composition has excellent corrosion resistance at the processing part and black resistance under high temperature and high humidity environment. Denaturation has an excellent effect.
본 발명의 발명자들은 건자재용 용융아연합금 도금강판, 예컨대 삼원계(Zn-Mg-Al계) 용융아연도금강판의 내식성, 특히 가공부 내식성과 내흑변성 등의 특성을 부여할 수 있는 용액 조성물을 얻기 위하여 깊이 연구하였다.The inventors of the present invention obtain a solution composition capable of imparting properties such as corrosion resistance, particularly processing part corrosion resistance and blackening resistance, to hot-dip galvanized steel sheets for construction materials, such as ternary (Zn-Mg-Al-based) hot-dip galvanized steel sheets. studied in depth for
그 결과, 크롬 화합물에 더하여 방청 피막제, 방청 에칭제, 내식성 첨가제, 흑변 개선제(I 및 II), 가공부 내식성 개선제를 적정량으로 혼합한 조성물을 제공할 수 있으며, 이 조성물의 용액 안정성이 높고, 이를 용융아연합금 도금강판에 표면처리하는 경우 의도하는 효과를 얻을 수 있음을 확인하고, 본 발명을 완성하기에 이르렀다.As a result, it is possible to provide a composition in which, in addition to a chromium compound, an anti-rust coating agent, an anti-corrosive etchant, a corrosion resistance additive, a blackening improver (I and II), and a corrosion resistance improver for a processing part are mixed in an appropriate amount, and the solution stability of this composition is high. It was confirmed that the intended effect can be obtained when surface treatment is applied to the hot-dip zinc alloy plated steel sheet, and the present invention has been completed.
이하, 본 발명에 대하여 상세히 설명한다.Hereinafter, the present invention will be described in detail.
먼저, 본 발명의 일 측면에 따른 삼원계 용융아연도금강판 표면처리용 조성물에 대하여 구체적으로 설명한다.First, a composition for surface treatment of a ternary hot-dip galvanized steel sheet according to an aspect of the present invention will be described in detail.
본 발명에 따른 조성물은 고형분 100중량%에 대하여, (a) 크롬 화합물 15~45중량%, (b) 방청 피막제 45~75중량%, (c) 방청 에칭제 0.1~3.0중량%, (d) 내식성 첨가제 0.1~5.0중량%, (e) 흑변 개선제(I) 0.5~3.0중량%, (f) 흑변 개선제(II) 0.1~2.0중량% 및 (g) 가공부 내식성 개선제 0.1~1.0중량%를 포함할 수 있다.The composition according to the present invention, based on 100% by weight of solid content, (a) 15 to 45% by weight of a chromium compound, (b) 45 to 75% by weight of an anticorrosive coating agent, (c) 0.1 to 3.0% by weight of an anticorrosive etchant, (d) 0.1 to 5.0% by weight of corrosion resistance additive, (e) 0.5 to 3.0% by weight of blackening improver (I), (f) 0.1 to 2.0% by weight of blackening improver (II) and (g) 0.1 to 1.0% by weight of processing part corrosion resistance improver can do.
본 발명의 조성물은 상기 크롬 화합물을 얻기 위하여 (h) 환원제 및 (i) 촉매제를 더 포함하며, 상기 조성물 총 중량은 상기 환원제와 촉매제의 함량까지 포함한 것을 의미한다.The composition of the present invention further includes (h) a reducing agent and (i) a catalyst in order to obtain the chromium compound, and the total weight of the composition means including the contents of the reducing agent and the catalyst.
본 발명의 조성물은 상기 조성물 총 중량을 기준으로 고형분 함량은 5~20중량%이다.The composition of the present invention has a solid content of 5 to 20% by weight based on the total weight of the composition.
후술하여 구체적으로 설명하겠지만, 상기 조성물은 조성물을 도포할 수 있는 기재(substrate)의 적어도 일면에 코팅층을 형성할 수 있다. 본 발명에서 상기 기재는 앞서 언급한 강판, 예컨대 삼원계 용융아연도금강판일 수 있으며, 구체적으로 Zn-Mg-Al계 합금 도금강판일 수 있다.As will be described in detail later, the composition may form a coating layer on at least one surface of a substrate on which the composition can be applied. In the present invention, the substrate may be the above-mentioned steel sheet, for example, a ternary hot-dip galvanized steel sheet, and specifically, may be a Zn-Mg-Al-based alloy-coated steel sheet.
하기에서는, 상기 조성물을 구성하는 각 성분에 대하여 상세히 설명한다.In the following, each component constituting the composition will be described in detail.
(a) 크롬 화합물 15~45중량%(a) 15 to 45% by weight of a chromium compound
본 발명의 조성물에서 크롬 화합물은 필수적인 성분으로서, 내식성 및 내흑변성 등을 확보하는 작용을 한다.In the composition of the present invention, the chromium compound is an essential component, and serves to secure corrosion resistance and blackening resistance.
상기 크롬 화합물은 질산크롬(A)과 크롬산염(B)을 용매(물)에 용해하여 제조하므로, 질산크롬(A)과 크롬산염(B)을 포함한다. 이때, 상기 질산크롬과 크롬산염의 함량비(A/A+B)가 0.3~0.6인 것이 바람직하다. 상기 함량비가 0.3 미만이면 구현하고자 하는 내식성 및 내흑변성이 저하되며, 반면 0.6을 초과하게 되면 용액 안정성이 낮아지는 문제가 있다.Since the chromium compound is prepared by dissolving chromium nitrate (A) and chromate (B) in a solvent (water), it includes chromium nitrate (A) and chromate (B). At this time, it is preferable that the content ratio (A/A+B) of the chromium nitrate and chromate is 0.3 to 0.6. If the content ratio is less than 0.3, corrosion resistance and blackening resistance to be realized are deteriorated, whereas if the content ratio exceeds 0.6, solution stability is lowered.
보다 구체적으로, 상기 크롬 화합물은 상기 질산크롬(A)과 크롬산염(B)을 용해한 용액 상에 3가 크롬 이온과 6가 크롬 이온 형태로 존재하는데, 이 중 6가 크롬 이온을 3가 크롬으로 환원시키기 위하여 (h) 환원제인 아인산(Phosphorous acid)을 0.5~5.0중량%로 첨가한다. 이때, 환원 반응이 원활히 일어날 수 있도록 (i) 촉매제로서 인산을 0.1~2.0중량%로 첨가하는 것이 바람직하다. More specifically, the chromium compound exists in the form of trivalent chromium ion and hexavalent chromium ion in the solution in which the chromium nitrate (A) and chromate (B) are dissolved. In order to reduce (h) phosphorous acid, a reducing agent, is added in an amount of 0.5 to 5.0% by weight. At this time, it is preferable to add 0.1 to 2.0% by weight of phosphoric acid as (i) a catalyst so that the reduction reaction can occur smoothly.
이로부터, 환원비(3가 크롬 이온/(3가 크롬 이온+6가 크롬 이온))가 0.75~0.90인 크롬 화합물을 얻을 수 있다. 상기 환원비가 0.75 미만이면 3가 크롬 이온의 함량이 부족하여 차폐 효과에 의한 내식성을 확보할 수 없고, 내흑변성이 부족할 우려가 있으며, 반면 그 값이 0.90을 초과하게 되면 상대적으로 6가 크롬 이온이 부족하게 되어 자기수복 효과가 저하되어 가공부 내식성이 저하되는 문제가 있다.From this, a chromium compound having a reduction ratio (trivalent chromium ion/(trivalent chromium ion + hexavalent chromium ion)) of 0.75 to 0.90 can be obtained. If the reduction ratio is less than 0.75, the content of trivalent chromium ions is insufficient, making it impossible to secure corrosion resistance due to the shielding effect and there is a risk of insufficient blackening resistance. On the other hand, if the value exceeds 0.90, hexavalent chromium ions are There is a problem that the self-healing effect is lowered due to the lack of corrosion resistance of the processed part.
상기 아인산의 함량이 0.5중량% 미만이면 크롬 화합물의 환원비가 0.75 이하로 낮아지는 문제가 있고, 반면 그 함량이 5.0중량%를 초과하게 되면 상기 환원비가 0.9를 초과하게 되는 문제가 있다.If the content of phosphorous acid is less than 0.5% by weight, there is a problem that the reduction ratio of the chromium compound is lowered to 0.75 or less, whereas if the content exceeds 5.0% by weight, there is a problem that the reduction ratio exceeds 0.9.
상기 촉매제로 사용된 인산은 자유산을 공급해줌으로써 아인산에 의한 6가 크롬 이온이 3가 크롬 이온으로 원활하게 환원되어지는 것을 촉진시키는 역할을 한다. 이러한 인산의 함량이 0.1중량% 미만이면 촉매 작용이 불충분하게 되고, 반면 그 함량이 2.0중량%를 초과하게 되면 자유산이 과도하게 존재하여 내식성을 저해할 우려가 있다.Phosphoric acid used as the catalyst serves to promote the smooth reduction of hexavalent chromium ions to trivalent chromium ions by phosphorous acid by supplying free acid. If the content of phosphoric acid is less than 0.1% by weight, the catalytic action becomes insufficient, whereas if the content exceeds 2.0% by weight, free acid may be excessively present, which may impair corrosion resistance.
여기서, 상기 환원제 및 촉매제의 함량은 본 발명 조성물의 고형분 100중량%에 대한 것임을 밝혀둔다.Here, it should be noted that the content of the reducing agent and the catalyst is based on 100% by weight of the solid content of the composition of the present invention.
본 발명의 조성물의 고형분 100중량%에 대하여, 상기 크롬 화합물의 함량이 15중량% 미만이면 견조한 불용성 피막층(코팅층)이 얇아지게 되어 내식성이 요구되는 도금강판의 표면에서 수분 침투를 효과적으로 차단시키지 못하게 된다. 그 결과, 흑변을 유발시키고, 내식성 또한 저하되는 문제가 있다. 반면, 그 함량이 45중량%를 초과하게 되면 내식성 향상을 위해 첨가되는 그 외 성분들, 구체적으로 방청 피막제, 방청 에칭제, 내식성 첨가제, 흑변 개선제(I 및 II), 가공부 내식성 개선제 등의 함량이 상대적으로 감소되어 충분한 내식성, 내흑변성 등을 확보하기 곤란한 문제가 있다.With respect to 100% by weight of the solid content of the composition of the present invention, if the content of the chromium compound is less than 15% by weight, the solid insoluble film layer (coating layer) becomes thin, so that the surface of the coated steel sheet requiring corrosion resistance cannot effectively block moisture penetration. . As a result, there is a problem that blackening is caused and corrosion resistance is also lowered. On the other hand, when the content exceeds 45% by weight, the contents of other components added to improve corrosion resistance, specifically, rust-preventive coating agents, rust-preventive etchants, corrosion-resistant additives, blackening improvers (I and II), processing part corrosion resistance improvers, etc. This is relatively reduced, so there is a problem that it is difficult to secure sufficient corrosion resistance, blackening resistance, and the like.
(b) 방청 피막제 45~75중량%(b) 45 to 75% by weight of anti-rust coating agent
본 발명의 조성물에서 방청 피막제는 상기 크롬 화합물과 함께 주 성분으로서, 기본적인 내식성, 내흑변성 등을 확보하는 역할을 한다. 특히, 도금강판(삼원계 용융아연도금강판)을 표면처리하는 경우, 환경 안정성, 특히 고온고습 환경 하에서 크롬 화합물의 피막 흡습으로 인한 피막 박리를 방지하여 환경 안정성을 우수하게 유지하는 역할을 한다.In the composition of the present invention, the rust-preventive coating agent is a main component together with the chromium compound, and serves to secure basic corrosion resistance, blackening resistance, and the like. In particular, in the case of surface treatment of plated steel sheet (ternary hot-dip galvanized steel sheet), environmental stability, in particular, plays a role in maintaining excellent environmental stability by preventing film peeling due to film absorption of chromium compounds in a high temperature and high humidity environment.
상기 방청 피막제로서는 유기 실란 졸-겔 바인더를 사용할 수 있다.An organic silane sol-gel binder can be used as the anti-rust coating agent.
구체적으로, 상기 유기 실란 졸-겔 바인더로는 2-(3,4에폭시사이클로헥실)-에틸트리메톡시실란, 3-글리실옥시프로필 트리메톡시실란, 3-글리실옥시프로필 메틸디에톡시실란, 3-글리실옥시프로필 트리에톡시실란, N-2-(아미노에틸)-3-아미노프로필 메틸디메톡시실란, N-2-(아미노에틸)-3-아미노프로필 트리메톡시실란, N-2-(아미노에틸)-3-아미노프로필 트리에톡시실란, 3-아미노프로필 트리메톡시 실란, 3-아미노프로필 트리에톡시 실란, 3-우레이도 프로필트리메톡시 실란 및 3-우레이도 프로필트리알콕시 실란으로 이루어지는 그룹으로부터 선택된 2종 또는 3종 이상의 실리콘 화합물일 수 있다.Specifically, as the organosilane sol-gel binder, 2-(3,4epoxycyclohexyl)-ethyltrimethoxysilane, 3-glycyloxypropyl trimethoxysilane, 3-glycyloxypropyl methyldiethoxysilane , 3-glycyloxypropyl triethoxysilane, N-2-(aminoethyl)-3-aminopropyl methyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyl trimethoxysilane, N- 2-(Aminoethyl)-3-aminopropyl triethoxysilane, 3-aminopropyl trimethoxy silane, 3-aminopropyl triethoxy silane, 3-ureido propyltrimethoxy silane and 3-ureido propyltri It may be two or three or more silicone compounds selected from the group consisting of alkoxy silanes.
본 발명의 조성물의 고형분 100중량%에 대하여 상기 방청 피막제의 함량이 45중량% 미만이면 견고한 피막층을 형성할 수 없게 되어 내식성 및 환경 안정성의 확보가 어려운 문제가 있다. 반면, 그 함량이 75중량%를 초과하게 되면 크롬 화합물의 함량이 감소되어 내흑변성이 저하되는 문제가 있다.If the content of the rust-preventive coating agent is less than 45% by weight with respect to 100% by weight of the solid content of the composition of the present invention, it is difficult to form a solid coating layer, which makes it difficult to secure corrosion resistance and environmental stability. On the other hand, when the content exceeds 75% by weight, the content of the chromium compound is reduced and blackening resistance is deteriorated.
(c) 방청 에칭제 0.1~3.0중량%(c) 0.1 to 3.0% by weight of an anti-rust etchant
본 발명의 조성물에서 방청 에칭제는 도금강판에 표면처리하는 경우, 표면을 에칭시켜 표면처리된 조성물이 견조한 결합을 형성함에 의해 방청 효과를 증대시켜주는 역할을 한다.In the composition of the present invention, the rust-preventive etchant serves to increase the rust-preventive effect by etching the surface and forming a strong bond between the surface-treated composition when the coated steel sheet is surface-treated.
상기 방청 에칭제로는 티탄불화수소산, 규화불화수소산 및 지르코늄불화수소산 중 1종 이상일 수 있다.The anti-rust etchant may be at least one of titanium hydrofluoric acid, silicic hydrofluoric acid, and zirconium hydrofluoric acid.
본 발명의 조성물의 고형분 100중량%에 대하여, 상기 방청 에칭제의 함량이 0.1중량% 미만이면 에칭 작용이 충분하지 못하여 표면처리된 조성물과 도금강판의 결합이 부족해져 내식성이 저하할 우려가 있다. 반면, 그 함량이 3.0중량%를 초과하게 되면 과도한 에칭 작용으로 인해 내흑변성이 저하하는 문제가 있다.If the content of the rust-preventive etchant is less than 0.1% by weight with respect to 100% by weight of the solid content of the composition of the present invention, the etching action is not sufficient, and the bonding between the surface-treated composition and the plated steel sheet is insufficient, so there is a risk of deterioration in corrosion resistance. On the other hand, when the content exceeds 3.0% by weight, there is a problem in that blackening resistance is lowered due to excessive etching action.
(d) 내식성 첨가제 0.1~5.0중량%(d) 0.1 to 5.0% by weight of anticorrosive additives
본 발명의 조성물에서 내식성 첨가제는 표면처리된 도금강판의 가공 중에 발생되어지는 균열 부위를 메워주는 역할을 하며, 이로부터 내식성을 향상시키는 데에 유리하다.In the composition of the present invention, the anticorrosive additive serves to fill cracks generated during the processing of the surface-treated coated steel sheet, and is advantageous in improving corrosion resistance therefrom.
상기 내식성 첨가제로는 리튬 실리카졸, 규산나트륨, 규산칼륨, 리튬-칼륨 실리케이트 및 리튬-소디움 실리케이트 중 1종 이상일 수 있다.The corrosion resistance additive may be at least one of lithium silica sol, sodium silicate, potassium silicate, lithium-potassium silicate and lithium-sodium silicate.
본 발명의 조성물의 고형분 100중량%에 대하여, 상기 내식성 첨가제의 함량이 0.1중량% 미만이면 표면처리된 도금강판의 가공 중 균열의 발생이 증대하여 가공부 내식성이 저하되며, 반면 그 함량이 5.0중량%를 초과하게 되면 용액 안정성이 열위하게 되는 문제가 있다.With respect to 100% by weight of the solid content of the composition of the present invention, if the content of the anticorrosive additive is less than 0.1% by weight, the occurrence of cracks during processing of the surface-treated coated steel sheet increases and the corrosion resistance of the processed part deteriorates, while the content is 5.0% by weight When the % is exceeded, there is a problem that solution stability is inferior.
(e) 흑변 개선제(I) 0.5~3.0중량%,(e) 0.5 to 3.0% by weight of a blackening improver (I);
본 발명의 조성물에서 흑변 개선제(I)은 도금강판이 고온고습 환경 하에서 아연(Zn)의 불완전 산화로 인해 검게 변하는 흑변 현상을 개선하는 역할을 한다.In the composition of the present invention, the blackening improving agent (I) serves to improve the blackening phenomenon in which a plated steel sheet turns black due to incomplete oxidation of zinc (Zn) under a high-temperature, high-humidity environment.
상기 흑변 개선제(I)로는 질산염, 질산암모늄 및 아질산염으로 이루어진 군에서 선택된 하나 이상일 수 있다.The blackening improver (I) may be at least one selected from the group consisting of nitrate, ammonium nitrate and nitrite.
본 발명의 조성물의 고형분 100중량%에 대하여, 상기 흑변 개선제(I)의 함량이 0.5중량% 미만이면 고온고습 환경 하에서 내흑변 효과가 부족하게 되고, 반면 그 함량이 3.0중량%를 초과하게 되면 용액 안정성이 저하되는 문제가 있다.With respect to 100% by weight of the solid content of the composition of the present invention, if the content of the blackening improver (I) is less than 0.5% by weight, the blackening resistance effect is insufficient in a high temperature and high humidity environment, whereas if the content exceeds 3.0% by weight, the solution There is a problem of deteriorating stability.
(f) 흑변 개선제(II) 0.1~2.0중량%(f) 0.1 to 2.0% by weight of blackening improver (II)
본 발명의 조성물에서 흑변 개선제(II)는 상기 흑변 개선제(I)과 함께 도금강판이 고온고습 환경 하에서 흑화 변색하는 현상을 개선하는 역할을 한다. In the composition of the present invention, the blackening improver (II) serves to improve the phenomenon of blackening and discoloration of the plated steel sheet under a high temperature and high humidity environment together with the blackening improver (I).
상기 흑변 개선제(II)로는 몰리브덴산염을 사용할 수 있다. Molybdate may be used as the blackening improver (II).
구체적으로, 상기 몰리브덴산염은 몰리브덴 산화물, 몰리브덴 황화물, 몰리브덴 아세트산염, 몰리브덴 인산염, 몰리브덴 탄화물, 몰리브덴 염화물, 몰리브덴 불소화물 및 몰리브덴 질화물로 이루어진 군에서 선택된 하나 이상일 수 있다.Specifically, the molybdenum salt may be one or more selected from the group consisting of molybdenum oxide, molybdenum sulfide, molybdenum acetate, molybdenum phosphate, molybdenum carbide, molybdenum chloride, molybdenum fluoride, and molybdenum nitride.
본 발명의 조성물의 고형분 100중량%에 대하여, 상기 흑변 개선제(II)의 함량이 0.1중량% 미만이면 고온고습 환경 하에서 내흑변 효과가 부족하게 되고, 반면 그 함량이 2.0중량%를 초과하게 되면 용액 안정성이 저하되는 문제가 있다.With respect to 100% by weight of the solid content of the composition of the present invention, if the content of the blackening improver (II) is less than 0.1% by weight, the blackening resistance effect is insufficient in a high temperature and high humidity environment, whereas if the content exceeds 2.0% by weight, the solution There is a problem of deteriorating stability.
(g) 가공부 내식성 개선제 0.1~1.0중량%(g) 0.1 to 1.0% by weight of a corrosion resistance improver for the processing part
본 발명의 조성물에서 가공부 내식성 개선제는 표면처리된 도금강판을 가공 처리하는 경우에 발생하는 크랙(crack) 균열 부위에서 도금층의 부식이 전파되는 것을 억제하는 역할을 한다.In the composition of the present invention, the processing part corrosion resistance improving agent serves to suppress the propagation of corrosion of the plating layer at cracks generated when the surface-treated coated steel sheet is processed.
상기 가공부 내식성 개선제로는 바나듐 화합물을 사용할 수 있다.A vanadium compound may be used as the corrosion resistance improving agent for the processing part.
구체적으로, 상기 바나듐 화합물로는 오산화바나듐, 메타바나딘산, 메타바나딘산 암모늄, 메타바나딘산 나트륨, 옥시삼염화 바나듐, 삼산화바나듐, 이산화바나듐, 옥시황산 바나듐, 바나듐 옥시아세틸아세테이트, 바나듐 아세틸아세테이트, 삼염화바나듐 및 인바나듐몰리브덴산으로 이루어진 군에서 선택된 하나 이상일 수 있다.Specifically, the vanadium compound includes vanadium pentoxide, metavanadic acid, ammonium metavanadate, sodium metavanadate, vanadium oxytrichloride, vanadium trioxide, vanadium dioxide, vanadium oxysulfate, vanadium oxyacetyl acetate, vanadium acetyl acetate , It may be at least one selected from the group consisting of vanadium trichloride and invanadium molybdic acid.
본 발명의 조성물의 고형분 100중량%에 대하여, 상기 가공부 내식성 개선제의 함량이 0.1중량% 미만이면 가공부 내식성이 저하되는 문제가 있고, 반면 그 함량이 1.0중량%를 초과하게 되면 내흑변성 및 용액 안정성이 저하되는 문제가 있다. With respect to 100% by weight of the solid content of the composition of the present invention, if the content of the corrosion resistance improver in the processing part is less than 0.1% by weight, there is a problem that the corrosion resistance of the processing part is lowered, whereas if the content exceeds 1.0% by weight, blackening resistance and solution There is a problem of deteriorating stability.
(j) 용제(j) Solvent
전술한 성분을 모두 포함하는 본 발명의 조성물은 고형분 함량이 5~20중량%이고, 잔부 성분으로서 용제를 포함할 수 있다. 본 발명에서 상기 용제로서 물을 사용할 수 있으며, 상기 물을 이용하여 상기 조성물에 첨가되는 성분들을 희석시킬 수 있다. 여기서, 물은 탈이온수 또는 증류수를 의미한다.The composition of the present invention including all of the above components has a solid content of 5 to 20% by weight, and may include a solvent as a remaining component. In the present invention, water may be used as the solvent, and components added to the composition may be diluted using the water. Here, water means deionized water or distilled water.
상기 용제의 함량은 80~95중량%인 것이 바람직하다. 상기 용제의 함량이 80중량% 미만이면 도금강판에 본 발명의 조성물을 액상(용액)의 상태로 코팅처리함에 있어서 퍼짐성이 충분하지 않을 우려가 있다. 반면, 그 함량이 95%를 초과하게 되면 상기 조성물을 코팅처리한 후 건조된 조성물의 부착량이 확보되지 못할 우려가 있다.The content of the solvent is preferably 80 to 95% by weight. If the content of the solvent is less than 80% by weight, there is a concern that spreadability may not be sufficient in coating the coated steel sheet with the composition of the present invention in a liquid (solution) state. On the other hand, if the content exceeds 95%, there is a concern that the adhesion amount of the dried composition cannot be secured after coating the composition.
본 발명에서는 상기 용제로서 물 이외에 보조 용제를 더 포함하는 것이 바람직하며, 상기 보조 용제로는 에틸알코올, 메틸알코올(Methanol), 이소프로필 알코올(Isopropyl alcohol), 1-메톡시-2-프로판올 및 2-부톡시에탄올로 이루어진 군에서 선택된 하나 이상일 수 있다.In the present invention, it is preferable to further include an auxiliary solvent in addition to water as the solvent, and the auxiliary solvent includes ethyl alcohol, methyl alcohol (Methanol), isopropyl alcohol, 1-methoxy-2-propanol and 2 - It may be one or more selected from the group consisting of butoxyethanol.
상기 보조 용제는 상기 용제의 전체 함량 대비 20~40중량%로 함유할 수 있다. 상기 보조 용제의 함량이 전체 용제 함량 중 20% 미만이면 용액 조성물을 구성하는 성분들이 안정적으로 용제 중에 분산되지 못할 우려가 있으며, 반면 그 함량이 40%를 초과하게 되면 내식성이 저하되고 용액 냄새로 인하여 작업 환경이 나빠지는 문제가 있다.The auxiliary solvent may be contained in 20 to 40% by weight based on the total content of the solvent. If the content of the auxiliary solvent is less than 20% of the total solvent content, there is a concern that the components constituting the solution composition may not be stably dispersed in the solvent. On the other hand, if the content exceeds 40%, corrosion resistance is lowered and solution odor There is a problem that the work environment deteriorates.
이하, 본 발명의 다른 일 측면에 따른 상술한 조성물을 표면처리하여 일정의 코팅층을 가지는 표면처리된 강판, 구체적으로 표면처리된 삼원계 용융아연도금강판에 대하여 상세히 설명한다.Hereinafter, a surface-treated steel sheet having a predetermined coating layer by surface-treating the above-described composition according to another aspect of the present invention, specifically, a surface-treated ternary hot-dip galvanized steel sheet will be described in detail.
본 발명에서 상기 조성물은 도금강판에 표면처리할 수 있으며, 바람직하게는 삼원계(Zn-Mg-Al계) 용융아연도금강판에 표면처리할 수 있다.In the present invention, the composition may be surface-treated on a coated steel sheet, preferably a ternary (Zn-Mg-Al-based) hot-dip galvanized steel sheet.
즉, 본 발명의 표면처리된 강판은 강판; 상기 강판의 적어도 일면에 형성된 Zn-Mg-Al계 도금층; 및 상기 도금층 상에 형성된 표면처리 코팅층을 포함할 수 있다.That is, the surface-treated steel sheet of the present invention is a steel sheet; a Zn-Mg-Al-based plating layer formed on at least one surface of the steel sheet; and a surface treatment coating layer formed on the plating layer.
여기서, 상기 강판은 도금강판을 얻을 수 있는 소지강판(base steel sheet)인 것으로서, 특히 삼원계(Zn-Mg-Al계) 용융아연도금강판을 얻을 수 있는 강판이라면 어떠한 것도 무방하다.Here, the steel sheet is a base steel sheet from which a coated steel sheet can be obtained, and in particular, any steel sheet from which a ternary (Zn-Mg-Al-based) hot-dip galvanized steel sheet can be obtained.
상기 Zn-Mg-Al계 도금층은 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.The composition of the Zn-Mg-Al-based plating layer may include magnesium (Mg): 4.0 to 7.0%, aluminum (Al): 11.0 to 19.5%, the balance Zn and other unavoidable impurities, by weight%.
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 serves to improve the corrosion resistance of the plated steel sheet, and the content thereof is preferably 4.0% or more to ensure excellent corrosion resistance, which is the purpose of the present invention. However, if the Mg content is excessive, dross may be generated in the plating bath and an intermetallic compound having high hardness may be excessively formed in the plating layer to deteriorate the bendability of the steel sheet. It can be capped at 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 작업으로 인해 문제가 초래될 수 있다. 따라서, 상기 Al은 19.5% 이하로 그 함량을 제한하는 것이 바람직하다.On the other hand, since there is a risk of dross generation due to Mg oxidation in the plating bath by adding the Mg content to 4.0% or more, it is preferable to include the aluminum (Al) at 11.0% or more in consideration of this. However, if the Al content is excessive, problems may arise due to high-temperature work, such as an increase in the melting point of the plating bath and an excessively high operating temperature resulting in erosion of the plating bath structure and deterioration of the steel sheet. Therefore, it is preferable 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.Except for Mg and Al, the remaining composition is zinc (Zn), and unavoidable impurities may be unintentionally mixed in the process of manufacturing a coated steel sheet having a Zn-Mg-Al-based plating layer. At this time, it is revealed that the meaning of the unavoidable impurities will be easily understood by those skilled in the art.
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 Expression 1].
[관계식 1][Relationship 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 relational expression 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 X-ray diffraction of the (103) plane crystal for the MgZn 2 phase represents the integral strength.)
본 발명에서는 상기 Zn-Mg-Al계 도금층의 MgZn2상에 대해 상기 [관계식 1]로 제어함으로써 도금강판의 굽힘성, 백색도 등을 확보할 수 있다.In the present invention, by controlling the MgZn 2 phase of the Zn-Mg-Al-based plating layer according to [Relational Expression 1], it is possible to secure the bendability and whiteness of the plated steel sheet.
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 Expression 1] is less than 0.26, the existence ratio of (103) plane crystals for the MgZn 2 phase to (110) plane crystals for the MgZn 2 phase is excessive, resulting in insufficient bendability or whiteness. . On the other hand, when the value exceeds 0.65, the ratio of (110) plane crystals to the MgZn 2 phase compared to (103) plane crystals to the MgZn 2 phase is too excessive, so that the increase in diffuse reflection cannot be induced, resulting in insufficient whiteness. Problems can 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.In this case, 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 preferable to satisfy the value of [Relationship 1] within each range.
상술한 Zn-Mg-Al계 도금층의 상부에는 본 발명의 조성물을 용액 상태로 코팅처리함으로써 형성된 코팅층을 포함할 수 있으며, 이때 코팅층은 0.3~1.5㎛의 두께를 가지는 것이 바람직하다.A coating layer formed by coating the composition of the present invention in a solution state may be included on top of the above-described Zn-Mg-Al-based plating layer, and in this case, the coating layer preferably has a thickness of 0.3 to 1.5 μm.
상기 코팅층의 두께가 0.3㎛ 미만이면 도금강판 표면에 존재하는 조도의 산 부위에 표면처리 용액 조성물이 얇게 도포되어 내식성이 저하되는 문제가 있으며, 반면, 그 두께가 1.5㎛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 0.3 μm, the surface treatment solution composition is thinly applied to the roughness of the acid portion present on the surface of the coated steel sheet, resulting in a decrease in corrosion resistance. On the other hand, if the thickness exceeds 1.5 μm, the coating layer (coating layer) ) is formed thickly, which deteriorates workability and increases the cost of solution treatment, which is economically unfavorable.
여기서, 상기 두께는 건조 후의 두께를 의미한다.Here, the thickness means the thickness after drying.
나아가, 본 발명은 상기 조성물을 이용하여 표면처리된 강판, 구체적으로 표면처리된 삼원계 용융아연도금강판의 제조방법에 대하여 설명한다.Furthermore, the present invention describes a method for manufacturing a surface-treated steel sheet using the composition, specifically, a surface-treated ternary hot-dip galvanized steel sheet.
보다 상세하게는, 강판의 적어도 일면에 용융아연도금처리하여 Zn-Mg-Al계 도금층을 형성하는 단계; 상기 도금층 상에 본 발명의 조성물을 용액 상태로 도포하여 코팅처리하는 단계; 및 상기 코팅처리된 강판을 건조처리하는 단계를 포함할 수 있다.More specifically, forming a Zn-Mg-Al-based plating layer by hot-dip galvanizing treatment on at least one surface of the steel sheet; Coating the coating layer by applying the composition of the present invention in a solution state on the plating layer; and drying the coated steel sheet.
본 발명의 조성물을 용액 상태로 상기 강판에 도포함에 있어서, 일반적으로 사용되는 코팅법을 적용할 수 있으므로, 특별히 한정하지는 아니한다.In applying the composition of the present invention to the steel sheet in a solution state, a generally used coating method may be applied, and thus, it is not particularly limited.
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 may be performed by selecting one method from among methods such as bar coating, roll coating, spraying, dipping, spray squeezing, and dip squeezing.
상술한 코팅법에 의해 조성물을 도포하는 경우, 2.5~12.5㎛의 두께로 도포하는 것이 바람직하다. 상술한 범위 내로 조성물을 도포함으로써, 건조 후 의도하는 도막 두께, 바람직하게는 0.3~1.5㎛의 두께를 갖는 코팅층을 확보할 수 있다.When applying the composition by the above coating method, it is preferable to apply to a thickness of 2.5 ~ 12.5㎛. By applying the composition within the above-mentioned range, it is possible to secure a coating layer having an intended coating thickness after drying, preferably a thickness of 0.3 to 1.5 μm.
상기 조성물로 코팅처리된 강판을 건조처리하는 공정은 소재강판(강판)의 최종도달온도(PMT) 기준으로 40~200℃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 200° C. based on the final temperature (PMT) of the material steel sheet (steel sheet).
상기 소재강판의 최종도달온도 기준으로 40℃ 미만이면 견고한 피막구조 형성이 미흡하여 내식성 및 내흑변성이 열위해질 우려가 있다. 반면, 그 온도가 200℃를 초과하게 되면 피막의 경도가 과도하게 증가하여 가공부 내식성이 열위해지고, 후속 냉각 과정에서 증발한 수증기가 건조설비 상부에 응축되는 결로 현상을 일으켜 제품의 표면품질이 열위해 질 수 있다.If the temperature is lower than 40° C. based on the final temperature of the material steel sheet, the formation of a sturdy film structure may be insufficient, resulting in inferior corrosion resistance and blackening resistance. On the other hand, when the temperature exceeds 200℃, the hardness of the film excessively increases, resulting in inferior corrosion resistance at the processing part, and condensation occurs in which water vapor evaporated during the subsequent cooling process condenses on the upper part of the drying equipment, which deteriorates the surface quality of the product. can be for
한편, 상기 건조는 열풍건조로 또는 유도가열로에서 행해질 수 있다.Meanwhile, the drying may be performed in a hot air drying furnace or an induction heating furnace.
상기 열풍건조로를 이용하여 건조처리를 행하는 경우, 상기 열풍건조로의 내부 온도가 100~300℃로 유지되는 것이 바람직하다. 또한, 상기 유도가열로를 이용하여 건조처리를 행하는 경우에는 유도가열로에 인가되는 전류가 1000~5000A, 보다 유리하게는 1500~3500A인 것이 바람직하다.When the drying treatment is performed using the hot air drying furnace, it is preferable that the internal temperature of the hot air drying furnace is maintained at 100 to 300°C. In addition, when the drying treatment is performed using the induction heating furnace, it is preferable that the current applied to the induction heating furnace is 1000 to 5000 A, more advantageously 1500 to 3500 A.
상기 열풍건조로의 내부 온도가 100℃ 미만이거나, 유도가열로에 인가되는 전류가 1000A 미만이면 코팅처리된 조성물의 피막 결합이 완벽하게 이루어지지 못하여 내식성 및 내흑변성이 열위해질 수 있다. 반면, 상기 열풍건조로의 내부 온도가 300℃를 초과하거나, 유도가열로에 인가되는 전류가 5000A를 초과하게 되면 피막의 경도가 과도하게 증가하여 가공부 내식성이 저하하며, 후속 냉각 과정에서 수증기 및 흄(fume)의 발생으로 작업 생산성이 나빠지고, 증발한 수증기가 건조설비 상부에 응축되는 결로 현상을 일으켜 제품의 표면품질이 열위해질 수 있다.If the internal temperature of the hot air drying furnace is less than 100 ° C or the current applied to the induction heating furnace is less than 1000 A, the coating of the coated composition may not be perfectly bonded, resulting in poor corrosion resistance and blackening resistance. On the other hand, when the internal temperature of the hot air drying furnace exceeds 300 ° C or the current applied to the induction heating furnace exceeds 5000 A, the hardness of the film excessively increases and the corrosion resistance of the processing part decreases, and steam and fumes in the subsequent cooling process Productivity deteriorates due to the generation of fume, and the evaporated water vapor condenses on the top of the drying equipment to cause dew condensation, which can deteriorate the surface quality of the product.
상기에 따라 건조처리 공정을 완료함으로써 건조 상태의 피막층(코팅층)이 형성되면, 추가적으로 공냉 또는 수냉의 냉각 공정을 거쳐 최종 코팅처리된 강판을 얻을 수 있다.When a film layer (coating layer) in a dry state is formed by completing the drying treatment process according to the above, a final coated steel sheet may be obtained through an additional air cooling or water cooling process.
이때, 냉각 공정의 조건에 대해서는 특별히 한정하지 아니하며, 통상적으로 적용되는 수준임을 밝혀둔다.At this time, the conditions of the cooling process are not particularly limited, and it is revealed that they are generally applied levels.
본 발명에서 표면처리된 삼원계 용융아연도금강판을 제조하는 방법은 연속 공정으로 이루어질 수 있으며, 이때 연속 공정의 속도는 50~120mpm로 제한할 수 있다.In the present invention, the method for manufacturing the surface-treated ternary hot-dip galvanized steel sheet may be performed as a continuous process, and the speed of the continuous process may be limited to 50 to 120 mpm.
상기 연속 공정의 속도가 50mpm 미만이면 생산성이 저하되는 문제가 있으며, 반면 120mpm을 초과하게 되면 강판 표면에 도포된 용액 상태의 조성물이 건조되는 과정에서 용액이 비산하여 표면 결함을 유발시킬 우려가 있다.If the speed of the continuous process is less than 50 mpm, there is a problem in that productivity is lowered, whereas if it exceeds 120 mpm, the solution in the process of drying the composition applied to the surface of the steel sheet may scatter and cause surface defects.
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 exemplifying the practice of the present invention, and the present invention is not limited by the description of these examples. This is because the scope of the present invention is determined by the matters described in the claims and the matters reasonably inferred therefrom.
(실시예)(Example)
[시험용 시편의 제작][Production of test specimen]
삼원계(Zn-Mg-Al계) 용융아연합금 도금층이 중량%로, Mn: 5.0%, Al: 12.0%, 잔부 Zn 및 불가피한 불순물로 이루어지고, [관계식 1]의 값이 0.45인 삼원계 용융아연도금강판을 7cm(가로)×15cm(세로)의 크기로 절단하여 유분을 제거하였다.The ternary (Zn-Mg-Al) hot-dip zinc alloy coating layer is composed of Mn: 5.0%, Al: 12.0%, the balance Zn and unavoidable impurities in weight%, and the value of [Relationship 1] is 0.45. The galvanized steel sheet was cut into a size of 7 cm (width) × 15 cm (length) to remove oil.
이후, 하기에 따라 제조된 조성물을 상기 용융아연도금강판의 표면에 바 코터(bar coater)로 도포한 후 PMT 기준 60±20℃의 조건으로 경화시켜 시험용 시편을 제작하였다.Thereafter, the composition prepared according to the following was applied to the surface of the hot-dip galvanized steel sheet with a bar coater, and then cured under conditions of 60±20° C. based on PMT to prepare test specimens.
[시험 및 평가 방법][Test and evaluation method]
상기에 따라 제작된 시험용 시편에 대하여, 다음과 같은 방법들을 통해 평판 내식성, 가공부 내식성, 내흑변성, 내알칼리성, 이물 묻음성, 용액 안정성을 평가하고, 각 결과를 아래 표에 나타내었다.With respect to the test specimen prepared according to the above, plate corrosion resistance, processed part corrosion resistance, blackening resistance, alkali resistance, staining property, and solution stability were evaluated through the following methods, and each result is shown in the table below.
<평판 내식성><Platform corrosion resistance>
ASTM B117에 규정한 방법에 의거하여, 시편을 처리한 후 시간 경과에 따른 강판의 백청 발생율을 측정하였다. 이때, 평가기준은 다음과 같다.According to the method specified in ASTM B117, the white rust generation rate of the steel sheet over time was measured after the specimen was treated. At this time, the evaluation criteria are as follows.
◎: 백청 발생시까지 걸린 시간이 144시간 이상◎: Time taken until white rust occurs is 144 hours or more
○: 백청 발생시까지 걸린 시간이 96시간 이상 144시간 미만○: Time taken until white rust occurs is 96 hours or more and less than 144 hours
△: 백청 발생시까지 걸린 시간이 55시간 이상 96시간 미만△: Time taken until white rust occurs is 55 hours or more and less than 96 hours
×: 백청 발생시까지 걸린 시간이 55시간 미만×: Time taken until white rust occurs is less than 55 hours
<가공부 내식성><Corrosion resistance of processing part>
시편을 에릭슨 시험기(Erichsen tester)를 이용하여 6mm의 높이로 밀어 올린 후, 24시간 경과하였을 때 백청 발생 정도를 측정하였다. 이때, 평가기준은 다음과 같다.After the specimen was pushed up to a height of 6 mm using an Erichsen tester, the degree of white rust generation was measured after 24 hours. At this time, the evaluation criteria are as follows.
◎: 48시간 경과 후 백청 발생 면적 5% 미만◎: Less than 5% of white rust generation area after 48 hours
○: 48시간 경과 후 백청 발생 면적 5% 이상 7% 미만○: 5% or more and less than 7% of the area where white rust occurs after 48 hours
△: 48시간 경과 후 백청 발생 면적 7% 이상 10% 미만△: 7% or more and less than 10% of the area where white rust occurs after 48 hours
×: 48시간 경과 후 백청 발생 면적 10% 이상×: 10% or more of white rust generation area after 48 hours
<내흑변성><Blackening resistance>
시편을 50℃의 온도, 상대습도 95%로 유지되는 항온 항습기에 120시간 동안 방치함으로써, 시험 전/후의 시편 색상 변화(색차: ΔE)를 관찰하였다. 이때, 평가기준은 다음과 같다.The color change (color difference: ΔE) of the specimen before and after the test was observed by leaving the specimen in a constant temperature and humidity chamber maintained at a temperature of 50 ° C and a relative humidity of 95% for 120 hours. At this time, the evaluation criteria are as follows.
◎: ΔE ≤ 2◎: ΔE ≤ 2
○: 2 < ΔE ≤ 3○: 2 < ΔE ≤ 3
△: 3 < ΔE ≤ 4Δ: 3 < ΔE ≤ 4
×: ΔE > 4×: ΔE > 4
<내알칼리성><Alkali resistance>
시편을 60℃의 알칼리 탈지용액에 2분간 침적 후 수세, Air blowing 한 다음, 침적 전/후의 색차(ΔE)를 측정하였다. 알칼리 탈지 용액은 대한 파카라이징사의 Finecleaner L 4460 A: 20g/2.4L + L 4460 B: 12g/2.4L (pH=12)를 사용하였다. 이때, 평가기준은 다음과 같다.The specimen was immersed in an alkaline degreasing solution at 60 ° C. for 2 minutes, washed with water and air blown, and then the color difference (ΔE) before and after immersion was measured. As an alkaline degreasing solution, Daehan Parkarizing's Finecleaner L 4460 A: 20g/2.4L + L 4460 B: 12g/2.4L (pH=12) was used. At this time, the evaluation criteria are as follows.
◎: ΔE ≤ 2◎: ΔE ≤ 2
○: 2 < ΔE ≤ 3○: 2 < ΔE ≤ 3
△: 3 < ΔE ≤ 4Δ: 3 < ΔE ≤ 4
×: ΔE > 4×: ΔE > 4
<이물 묻음성><Foreign Substance Contamination>
시편을 백색 거즈를 부착한 금속 팁에 하중 2.5kg을 부가한 상태로 마찰시킨 후, 시험 전/후의 백색 거즈의 백색도 변화(백색도 색차: ΔL)를 관찰하였다 이때, 평가기준은 다음과 같다. After rubbing the specimen with a load of 2.5 kg applied to a metal tip to which a white gauze was attached, the change in whiteness (whiteness color difference: ΔL) of the white gauze before and after the test was observed. At this time, the evaluation criteria are as follows.
◎: ΔE ≤ 1.0◎: ΔE ≤ 1.0
○: 1.0 < ΔE ≤ 2.0○: 1.0 < ΔE ≤ 2.0
△: 2.0 < ΔL ≤ 2.5Δ: 2.0 < ΔL ≤ 2.5
×: ΔL > 2.5×: ΔL > 2.5
<용액 안정성><Solution stability>
각각의 표면처리용 조성물을 용기에 담아 50℃의 항온 오븐 속에 넣고, 7일 간 보관 한 후, 침전물 발생 여부를 육안으로 관찰하고, 점도 변화를 측정하였다. 이때, 평가기준은 다음과 같다.Each composition for surface treatment was placed in a container and placed in a constant temperature oven at 50° C., stored for 7 days, and then observed with the naked eye to determine whether a precipitate was generated, and the change in viscosity was measured. At this time, the evaluation criteria are as follows.
○: 침전 발생 없음, 점도 변화 1CP 미만○: No precipitation, viscosity change less than 1CP
△: 침전 발생 없음, 점도 변화 1~5CP△: No precipitation, change in viscosity 1 to 5 CP
×: 침전 발생 또는 점도 변화 5CP 초과×: occurrence of precipitation or change in viscosity exceeding 5 CP
실험 1. 크롬 화합물의 함량에 따른 물성 변화Experiment 1. Physical property change according to the content of chromium compound
우선, 표면처리용 조성물을 다음에 따라 제조하였다.First, a composition for surface treatment was prepared as follows.
질산크롬(A)와 크롬산염(B)을 물에 용해한 크롬 용액에 환원제로서 아인산, 촉매로서 인산을 첨가하여 크롬 화합물을 제조하였다. 이때, 상기 질산크롬(A)과 크롬산염(B)의 함량비(A/(A+B))를 0.5, 환원비는 0.85로 제어하였다.A chromium compound was prepared by adding phosphorous acid as a reducing agent and phosphoric acid as a catalyst to a chromium solution in which chromium nitrate (A) and chromate (B) were dissolved in water. At this time, the content ratio (A/(A+B)) of the chromium nitrate (A) and chromate (B) was controlled to 0.5 and the reduction ratio to 0.85.
이 크롬 화합물에 방청 피막제로서 유기 실란 졸-겔 바인더(3-글리실옥시프로필 메틸디에톡시실란 및 3-아미노프로필 트리에톡시 실란), 방청 에칭제로서 티탄불화수소산, 내식성 첨가제로서 리튬 실리카졸, 흑변 개선제(I)로서 질산염, 흑변 개선제(II)로서 몰리브덴 산화물인 몰리브덴 트리옥사이드, 가공부 내식성 개선제로서 바나듐 화합물인 오산화바나듐을 첨가하여 조성물을 제조하였다. 각 성분의 함량을 하기 표 1에 나타내었으며, 이때 건조 피막 상태에서는 용매(물, 에틸 알코올)가 제거됨을 감안하여, 고형분 100%를 기준으로 각 성분의 함량을 기재하였다.To this chromium compound, an organic silane sol-gel binder (3-glycyloxypropyl methyldiethoxysilane and 3-aminopropyl triethoxysilane) as a rust-preventive coating agent, titanium hydrofluoric acid as a rust-preventive etchant, lithium silica sol as a corrosion-resistant additive, A composition was prepared by adding nitrate as a blackening improving agent (I), molybdenum trioxide as a molybdenum oxide as a blackening improving agent (II), and vanadium pentoxide as a vanadium compound as a corrosion resistance improving agent in a processed part. The content of each component is shown in Table 1 below. At this time, considering that the solvent (water, ethyl alcohol) is removed in the dry film state, the content of each component is described based on 100% solid content.
그리고, 상기 조성물을 용액 상태로 제조함에 있어서, 제조된 조성물의 고형분 13% 기준으로 물을 61중량%, 에틸 알코올을 26중량%로 첨가하였다.And, in preparing the composition in a solution state, 61% by weight of water and 26% by weight of ethyl alcohol were added based on the solid content of 13% of the prepared composition.
하기 표 1의 함량에 따라 제조된 용액 조성물을 도포하여 건조 처리한 각 시편의 평판 내식성, 가공부 내식성, 내흑변성, 내알칼리성, 용액 안정성을 평가하였으며, 그 결과를 하기 표 1에 함께 나타내었다.Plate corrosion resistance, processing part corrosion resistance, blackening resistance, alkali resistance, and solution stability of each specimen coated with the solution composition prepared according to the contents of Table 1 and dried were evaluated, and the results are shown in Table 1 below.
화합물compound
원
제ring
one
my
매point
hawk
피막제rust
coating agent
에칭제rust
etchant
첨가제corrosion resistance
additive
개선제black stool
improver
개선제Machining corrosion resistance
improver
내식
성reputation
corrosion resistance
castle
내식
성processing department
corrosion resistance
castle
흑변
성my
black stool
castle
알칼리
성my
alkali
castle
안정성solution
stability
예1comparison
Example 1
상기 표 1에 나타낸 바와 같이, 크롬 화합물과 더불어 그 외 성분들이 본 발명에서 제안하는 함량에 따라 함유된 조성물을 표면처리하는 경우 모든 물성에서 양호 이상의 결과를 보였다.As shown in Table 1, in the case of surface treatment of the composition containing the chromium compound and other components according to the content proposed in the present invention, all physical properties showed better or better results.
반면, 크롬 화합물의 함량이 불충분한 비교예 1은 평판 내식성 및 가공부 내식성이 열위한 결과를 보였으며, 크롬 화합물의 함량이 과도한 비교예 2 역시 평판 내식성 및 가공부 내식성과 함께 내흑변성이 불량한 결과를 보였다.On the other hand, Comparative Example 1, in which the content of the chromium compound was insufficient, showed poor plate corrosion resistance and corrosion resistance in the processed part, and Comparative Example 2, in which the content of the chromium compound was excessive, also showed poor blackening resistance along with plate corrosion resistance and corrosion resistance in the processed part. showed
실험 2. 크롬 화합물의 함량비(A/(A+B))에 따른 물성 변화Experiment 2. Physical property change according to the chromium compound content ratio (A/(A+B))
고형분 100중량%를 기준으로 크롬 화합물 28중량%에 방청 피막제로 유기 실란 졸-겔 바인더(3-글리실옥시프로필 메틸디에톡시실란 및 3-아미노프로필 트리에톡시 실란)를 64중량%, 방청 에칭제로 티탄불화수소산을 2.5중량%, 내식성 첨가제로 리튬 실리카졸을 1중량%, 흑변 개선제(I)로 질산염 1중량%, 흑변 개선제(II)로 몰리브덴 산화물인 몰리브덴 트리옥사이드를 0.5중량% 및 가공부 내식성 개선제로 바나듐 화합물인 오산화바나듐을 0.5중량% 첨가하여 조성물을 제조하였다. 이때 건조 피막 상태에서는 용매(물, 에틸 알코올)가 제거됨을 감안하여, 고형분 100%를 기준으로 각 성분의 함량을 나타낸 것이다.Based on 100% by weight of solid content, 64% by weight of an organic silane sol-gel binder (3-glycyloxypropyl methyldiethoxysilane and 3-aminopropyl triethoxy silane) as an anti-rust coating agent in 28% by weight of a chromium compound, anti-rust etching 2.5% by weight of zero titanium hydrofluoric acid, 1% by weight of lithium silica sol as a corrosion resistance additive, 1% by weight of nitrate as a blackening improver (I), 0.5% by weight of molybdenum trioxide, a molybdenum oxide, as a blackening improver (II), and processing A composition was prepared by adding 0.5% by weight of vanadium pentoxide, a vanadium compound, as a corrosion resistance improver. At this time, considering that the solvent (water, ethyl alcohol) is removed in the dry film state, the content of each component is shown based on 100% solid content.
상기 크롬 화합물은 질산크롬(A)와 크롬산염(B)을 물에 용해한 크롬 용액에 환원제로서 아인산 2중량%, 촉매로서 인산 0.5중량%를 첨가하여 크롬 화합물을 제조하였다. 이때, 상기 질산크롬(A)과 크롬산염(B)의 함량비(A/(A+B))를 아래 표 2와 같이 다르게 제어하였으며, 환원비는 0.85로 제어하였다.The chromium compound was prepared by adding 2% by weight of phosphorous acid as a reducing agent and 0.5% by weight of phosphoric acid as a catalyst to a chromium solution in which chromium nitrate (A) and chromate (B) were dissolved in water. At this time, the content ratio (A/(A+B)) of the chromium nitrate (A) and chromate (B) was controlled differently as shown in Table 2 below, and the reduction ratio was controlled to 0.85.
그리고, 상기 조성물을 용액 상태로 제조함에 있어서, 제조된 조성물의 고형분 13% 기준으로 물을 61중량%, 에틸 알코올을 26중량%로 첨가하였다.And, in preparing the composition in a solution state, 61% by weight of water and 26% by weight of ethyl alcohol were added based on the solid content of 13% of the prepared composition.
하기 표 2와 같이 질산크롬(A)과 크롬산염(B)의 함량비를 다르게 적용하여 제조된 용액 조성물을 도포하여 건조 처리한 각 시편의 평판 내식성, 가공부 내식성, 내흑변성, 용액 안정성을 평가하였으며, 그 결과를 하기 표 2에 함께 나타내었다.As shown in Table 2 below, the solution composition prepared by applying different content ratios of chromium nitrate (A) and chromate (B) was applied and dried to evaluate plate corrosion resistance, processing part corrosion resistance, blackening resistance, and solution stability. And the results are shown together in Table 2 below.
(A)chromium nitrate
(A)
(B)chromate
(B)
(A/(A+B))content ratio
(A/(A+B))
내식성reputation
corrosion resistance
내식성processing department
corrosion resistance
안정성solution
stability
7 example of invention
7
상기 표 2에 나타낸 바와 같이, 질산크롬과 크롬산염의 함량비가 본 발명에서 제안하는 범위를 만족하는 경우(발명예 4 내지 7)에는 모든 물성에서 양호 이상의 결과를 보였다.As shown in Table 2, when the content ratio of chromium nitrate and chromate satisfies the range proposed in the present invention (Inventive Examples 4 to 7), all physical properties showed better or better results.
반면, 상기 함량비가 너무 작은 비교예 3은 평판 내식성, 가공부 내식성 및 내흑변성이 열위한 결과를 보였으며, 그 함량비가 과도한 비교예 4의 경우에는 용액 안정성이 열위하였다.On the other hand, Comparative Example 3, in which the content ratio was too small, showed poor plate corrosion resistance, processed part corrosion resistance, and blackening resistance, and in the case of Comparative Example 4, in which the content ratio was excessive, solution stability was inferior.
실험 3. 크롬 화합물의 환원비에 따른 물성 변화Experiment 3. Physical property change according to reduction ratio of chromium compound
상기 실험 2에서 사용된 조성물의 크롬 화합물의 환원비, 즉 3가 크롬 이온과 6가 크롬 이온의 환원비(3가 크롬 이온/(3가 크롬 이온+6가 크롬 이온))만을 다르게 제어한 조성물을 제조하였다. 이때, 질산크롬(A)과 크롬산염(B)의 함량비(A/(A+B))를 0.5로 제어하였다.The reduction ratio of the chromium compound of the composition used in Experiment 2, that is, the composition in which only the reduction ratio of trivalent chromium ion and hexavalent chromium ion (trivalent chromium ion/(trivalent chromium ion + hexavalent chromium ion)) is controlled differently was manufactured. At this time, the content ratio (A/(A+B)) of chromium nitrate (A) and chromate (B) was controlled to 0.5.
이후, 상기 실험 2와 동일하게 제조된 조성물의 고형분 13% 기준으로 물 61중량%, 에틸 알코올 26중량%를 첨가하여 용액 조성물을 얻었다.Thereafter, 61% by weight of water and 26% by weight of ethyl alcohol were added based on the solid content of 13% of the composition prepared in the same manner as in Experiment 2 to obtain a solution composition.
하기 표 3의 환원비를 다르게 적용하여 제조된 용액 조성물을 도포하여 건조 처리한 각 시편의 평판 내식성, 가공부 내식성, 내흑변성, 용액 안정성을 평가하였으며, 그 결과를 하기 표 3에 함께 나타내었다.Plate corrosion resistance, processing part corrosion resistance, blackening resistance, and solution stability of each specimen coated with a solution composition prepared by applying different reduction ratios in Table 3 below and dried were evaluated, and the results are shown in Table 3 below.
(3가 크롬 이온+6가 크롬 이온)Trivalent chromium ion/
(trivalent chromium ion + hexavalent chromium ion)
내식성reputation
corrosion resistance
내식성processing department
corrosion resistance
안정성solution
stability
11 example of invention
11
상기 표 3에 나타낸 바와 같이, 크롬 화합물의 환원비가 본 발명에서 제안하는 범위를 만족하는 경우(발명예 8 내지 11)에는 모든 물성에서 양호 이상의 결과를 보였다.As shown in Table 3, when the reduction ratio of the chromium compound satisfies the range proposed in the present invention (Inventive Examples 8 to 11), all physical properties showed better or better results.
반면, 크롬 화합물의 환원비가 너무 작은 비교예 5는 평판 내식성, 가공부 내식성 및 내흑변성이 열위한 결과를 보였으며, 크롬 화합물의 환원비가 과도한 비교예 6의 경우에는 가공부 내식성과 용액 안정성이 열위하였다.On the other hand, Comparative Example 5, in which the reduction ratio of the chromium compound was too small, showed poor plate corrosion resistance, machined part corrosion resistance, and blackening resistance. did
실험 4. 환원제의 함량에 따른 물성 변화Experiment 4. Physical property change according to reducing agent content
표면처리용 조성물을 다음에 따라 제조하였다.A composition for surface treatment was prepared as follows.
질산크롬(A)와 크롬산염(B)을 물에 용해한 크롬 용액에 환원제로서 아인산, 촉매로서 인산을 첨가하여 크롬 화합물을 제조하였다. 이때, 상기 질산크롬(A)과 크롬산염(B)의 함량비(A/(A+B))를 0.5, 환원비는 0.85로 제어하였다.A chromium compound was prepared by adding phosphorous acid as a reducing agent and phosphoric acid as a catalyst to a chromium solution in which chromium nitrate (A) and chromate (B) were dissolved in water. At this time, the content ratio (A/(A+B)) of the chromium nitrate (A) and chromate (B) was controlled to 0.5 and the reduction ratio to 0.85.
이 크롬 화합물에 방청 피막제로서 유기 실란 졸-겔 바인더(3-글리실옥시프로필 메틸디에톡시실란 및 3-아미노프로필 트리에톡시 실란), 방청 에칭제로서 티탄불화수소산, 내식성 첨가제로서 리튬 실리카졸, 흑변 개선제(I)로서 질산염, 흑변 개선제(II)로서 몰리브덴 산화물인 몰리브덴 트리옥사이드, 가공부 내식성 개선제로서 바나듐 화합물인 오산화바나듐을 첨가하여 조성물을 제조하였다. 각 성분의 함량을 하기 표 4에 나타내었으며, 이때 건조 피막 상태에서는 용매(물, 에틸 알코올)가 제거됨을 감안하여, 고형분 100%를 기준으로 각 성분의 함량을 기재하였다.To this chromium compound, an organic silane sol-gel binder (3-glycyloxypropyl methyldiethoxysilane and 3-aminopropyl triethoxysilane) as a rust-preventive coating agent, titanium hydrofluoric acid as a rust-preventive etchant, lithium silica sol as a corrosion-resistant additive, A composition was prepared by adding nitrate as a blackening improving agent (I), molybdenum trioxide as a molybdenum oxide as a blackening improving agent (II), and vanadium pentoxide as a vanadium compound as a corrosion resistance improving agent in a processed part. The content of each component is shown in Table 4 below, and considering that solvents (water, ethyl alcohol) are removed in the dry film state, the content of each component is described based on 100% solid content.
그리고, 상기 조성물을 용액 상태로 제조함에 있어서, 제조된 조성물의 고형분 13% 기준으로 물을 61중량%, 에틸 알코올을 26중량%로 첨가하였다.And, in preparing the composition in a solution state, 61% by weight of water and 26% by weight of ethyl alcohol were added based on the solid content of 13% of the prepared composition.
하기 표 4의 함량에 따라 제조된 용액 조성물을 도포하여 건조 처리한 각 시편의 평판 내식성, 가공부 내식성, 내흑변성, 용액 안정성을 평가하였으며, 그 결과를 하기 표 4에 함께 나타내었다.Plate corrosion resistance, processing part corrosion resistance, blackening resistance, and solution stability of each specimen coated with the solution composition prepared according to the contents of Table 4 and dried were evaluated, and the results are shown in Table 4 below.
화합물chrome
compound
원one
제my
매point
hawk
피막제rust
coating agent
에칭제rust
etchant
첨가제corrosion resistance
additive
개선제black stool
improver
개선제Machining corrosion resistance
improver
내식성reputation
corrosion resistance
내식성processing department
corrosion resistance
흑변성my
blackening
안정성solution
stability
예7comparison
yes 7
예15invent
yes15
상기 표 4에 나타낸 바와 같이, 발명예 12 내지 15는 본 발명에서 제안하는 함량을 모두 만족하는 조성물로 표면처리된 경우로, 모든 물성에서 양호 이상의 결과를 보였다.As shown in Table 4, Inventive Examples 12 to 15 were surface-treated with compositions satisfying all the contents proposed in the present invention, and showed better or better results in all physical properties.
반면, 환원제의 함량이 불충분한 비교예 7은 평판 내식성, 가공부 내식성 및 내흑변성이 열위한 결과를 보였으며, 환원제의 함량이 과도한 비교예 8은 가공부 내식성과 용액 안정성이 불량한 결과를 보였다.On the other hand, Comparative Example 7, in which the content of the reducing agent was insufficient, showed poor plate corrosion resistance, corrosion resistance and blackening resistance in the processed part, and Comparative Example 8, in which the content of the reducing agent was excessive, showed poor corrosion resistance and solution stability in the processed part.
실험 5. 촉매의 함량에 따른 물성 변화Experiment 5. Physical property change according to catalyst content
표면처리용 조성물을 다음에 따라 제조하였다.A composition for surface treatment was prepared as follows.
질산크롬(A)와 크롬산염(B)을 물에 용해한 크롬 용액에 환원제로서 아인산, 촉매로서 인산을 첨가하여 크롬 화합물을 제조하였다. 이때, 상기 질산크롬(A)과 크롬산염(B)의 함량비(A/(A+B))를 0.5, 환원비는 0.85로 제어하였다.A chromium compound was prepared by adding phosphorous acid as a reducing agent and phosphoric acid as a catalyst to a chromium solution in which chromium nitrate (A) and chromate (B) were dissolved in water. At this time, the content ratio (A/(A+B)) of the chromium nitrate (A) and chromate (B) was controlled to 0.5 and the reduction ratio to 0.85.
이 크롬 화합물에 방청 피막제로서 유기 실란 졸-겔 바인더(3-글리실옥시프로필 메틸디에톡시실란 및 3-아미노프로필 트리에톡시 실란), 방청 에칭제로서 티탄불화수소산, 내식성 첨가제로서 리튬 실리카졸, 흑변 개선제(I)로서 질산염, 흑변 개선제(II)로서 몰리브덴 산화물인 몰리브덴 트리옥사이드, 가공부 내식성 개선제로서 바나듐 화합물인 오산화바나듐을 첨가하여 조성물을 제조하였다. 각 성분의 함량을 하기 표 5에 나타내었으며, 이때 건조 피막 상태에서는 용매(물, 에틸 알코올)가 제거됨을 감안하여, 고형분 100%를 기준으로 각 성분의 함량을 기재하였다.To this chromium compound, an organic silane sol-gel binder (3-glycyloxypropyl methyldiethoxysilane and 3-aminopropyl triethoxysilane) as a rust-preventive coating agent, titanium hydrofluoric acid as a rust-preventive etchant, lithium silica sol as a corrosion-resistant additive, A composition was prepared by adding nitrate as a blackening improving agent (I), molybdenum trioxide as a molybdenum oxide as a blackening improving agent (II), and vanadium pentoxide as a vanadium compound as a corrosion resistance improving agent in a processed part. The content of each component is shown in Table 5 below. At this time, considering that the solvent (water, ethyl alcohol) is removed in the dry film state, the content of each component is described based on 100% solid content.
그리고, 상기 조성물을 용액 상태로 제조함에 있어서, 제조된 조성물의 고형분 13% 기준으로 물을 61중량%, 에틸 알코올을 26중량%로 첨가하였다.And, in preparing the composition in a solution state, 61% by weight of water and 26% by weight of ethyl alcohol were added based on the solid content of 13% of the prepared composition.
하기 표 5의 함량에 따라 제조된 용액 조성물을 도포하여 건조 처리한 각 시편의 평판 내식성, 가공부 내식성, 내흑변성, 용액 안정성을 평가하였으며, 그 결과를 하기 표 5에 함께 나타내었다.Plate corrosion resistance, processed part corrosion resistance, blackening resistance, and solution stability of each specimen coated with the solution composition prepared according to the contents of Table 5 and dried were evaluated, and the results are shown in Table 5 below.
화합물chrome
compound
원
제ring
one
my
매hawk
피막제rust
coating agent
에칭제rust
etchant
첨가제corrosion resistance
additive
개선제black stool
improver
개선제Machining corrosion resistance
improver
내식성reputation
corrosion resistance
내식성processing department
corrosion resistance
흑변성my
blackening
안정성solution
stability
예9comparison
yes 9
예19invent
yes19
상기 표 5에 나타낸 바와 같이, 발명예 16 내지 19는 본 발명에서 제안하는 함량을 모두 만족하는 조성물로 표면처리된 경우로, 모든 물성에서 양호 이상의 결과를 보였다.As shown in Table 5, Inventive Examples 16 to 19 were surface-treated with compositions satisfying all the contents proposed in the present invention, and showed better or better results in all physical properties.
반면, 촉매를 첨가하지 아니한 비교예 9는 평판 내식성, 가공부 내식성 및 내흑변성이 열위한 결과를 보였으며, 촉매의 함량이 과도한 비교예 10은 평판 내식성 및 가공부 내식성이 불량한 결과를 보였다.On the other hand, Comparative Example 9 in which no catalyst was added showed poor plate corrosion resistance, processed part corrosion resistance, and blackening resistance, and Comparative Example 10, in which the catalyst content was excessive, showed poor plate corrosion resistance and processed part corrosion resistance.
실험 6. 방청 피막제의 함량에 따른 물성 변화Experiment 6. Physical property change according to the content of anti-rust coating agent
표면처리용 조성물을 다음에 따라 제조하였다.A composition for surface treatment was prepared as follows.
질산크롬(A)와 크롬산염(B)을 물에 용해한 크롬 용액에 환원제로서 아인산, 촉매로서 인산을 첨가하여 크롬 화합물을 제조하였다. 이때, 상기 질산크롬(A)과 크롬산염(B)의 함량비(A/(A+B))를 0.5, 환원비는 0.85로 제어하였다.A chromium compound was prepared by adding phosphorous acid as a reducing agent and phosphoric acid as a catalyst to a chromium solution in which chromium nitrate (A) and chromate (B) were dissolved in water. At this time, the content ratio (A/(A+B)) of the chromium nitrate (A) and chromate (B) was controlled to 0.5 and the reduction ratio to 0.85.
이 크롬 화합물에 방청 피막제로서 유기 실란 졸-겔 바인더(3-글리실옥시프로필 메틸디에톡시실란 및 3-아미노프로필 트리에톡시 실란), 방청 에칭제로서 티탄불화수소산, 내식성 첨가제로서 리튬 실리카졸, 흑변 개선제(I)로서 질산염, 흑변 개선제(II)로서 몰리브덴 산화물인 몰리브덴 트리옥사이드, 가공부 내식성 개선제로서 바나듐 화합물인 오산화바나듐을 첨가하여 조성물을 제조하였다. 각 성분의 함량을 하기 표 6에 나타내었으며, 이때 건조 피막 상태에서는 용매(물, 에틸 알코올)가 제거됨을 감안하여, 고형분 100%를 기준으로 각 성분의 함량을 기재하였다.To this chromium compound, an organic silane sol-gel binder (3-glycyloxypropyl methyldiethoxysilane and 3-aminopropyl triethoxysilane) as a rust-preventive coating agent, titanium hydrofluoric acid as a rust-preventive etchant, lithium silica sol as a corrosion-resistant additive, A composition was prepared by adding nitrate as a blackening improving agent (I), molybdenum trioxide as a molybdenum oxide as a blackening improving agent (II), and vanadium pentoxide as a vanadium compound as a corrosion resistance improving agent in a processed part. The content of each component is shown in Table 6 below. At this time, considering that the solvent (water, ethyl alcohol) is removed in the dry film state, the content of each component is described based on 100% solid content.
그리고, 상기 조성물을 용액 상태로 제조함에 있어서, 제조된 조성물의 고형분 13% 기준으로 물을 61중량%, 에틸 알코올을 26중량%로 첨가하였다.And, in preparing the composition in a solution state, 61% by weight of water and 26% by weight of ethyl alcohol were added based on the solid content of 13% of the prepared composition.
하기 표 6의 함량에 따라 제조된 용액 조성물을 도포하여 건조 처리한 각 시편의 평판 내식성, 가공부 내식성, 내흑변성, 이물 묻음성을 평가하였으며, 그 결과를 하기 표 6에 함께 나타내었다.Plate corrosion resistance, processed part corrosion resistance, blackening resistance, and staining of foreign substances were evaluated for each specimen dried by applying the solution composition prepared according to the contents of Table 6 below, and the results are shown in Table 6 below.
화합물chrome
compound
원
제ring
one
my
매point
hawk
피막제coating agent
에칭제rust
etchant
첨가제corrosion resistance
additive
개선제black stool
improver
개선제Machining corrosion resistance
improver
내식성reputation
corrosion resistance
내식성processing department
corrosion resistance
흑변성my
blackening
묻음성alien substance
soiling
예11comparison
Example 11
예23invent
yes23
상기 표 6에 나타낸 바와 같이, 발명예 20 내지 23은 본 발명에서 제안하는 함량을 모두 만족하는 조성물로 표면처리된 경우로, 모든 물성에서 양호 이상의 결과를 보였다.As shown in Table 6, Inventive Examples 20 to 23 were surface-treated with compositions satisfying all the contents proposed in the present invention, and showed better or better results in all physical properties.
반면, 방청 피막제의 함량이 불충분한 비교예 11은 평판 내식성, 가공부 내식성 및 이물 묻음성이 열위한 결과를 보였으며, 방청 피막제의 함량이 과도한 비교예 12는 내흑변성이 불량한 결과를 보였다.On the other hand, Comparative Example 11, in which the content of the rust-preventive coating agent was insufficient, showed poor plate corrosion resistance, processed part corrosion resistance, and staining of foreign matter, and Comparative Example 12, in which the content of the rust-preventive coating agent was excessive, showed poor blackening resistance.
실험 7. 방청 에칭제의 함량에 따른 물성 변화Experiment 7. Physical property change according to the content of anti-rust etchant
표면처리용 조성물을 다음에 따라 제조하였다.A composition for surface treatment was prepared as follows.
질산크롬(A)와 크롬산염(B)을 물에 용해한 크롬 용액에 환원제로서 아인산, 촉매로서 인산을 첨가하여 크롬 화합물을 제조하였다. 이때, 상기 질산크롬(A)과 크롬산염(B)의 함량비(A/(A+B))를 0.5, 환원비는 0.85로 제어하였다.A chromium compound was prepared by adding phosphorous acid as a reducing agent and phosphoric acid as a catalyst to a chromium solution in which chromium nitrate (A) and chromate (B) were dissolved in water. At this time, the content ratio (A/(A+B)) of the chromium nitrate (A) and chromate (B) was controlled to 0.5 and the reduction ratio to 0.85.
이 크롬 화합물에 방청 피막제로서 유기 실란 졸-겔 바인더(3-글리실옥시프로필 메틸디에톡시실란 및 3-아미노프로필 트리에톡시 실란), 방청 에칭제로서 티탄불화수소산, 내식성 첨가제로서 리튬 실리카졸, 흑변 개선제(I)로서 질산염, 흑변 개선제(II)로서 몰리브덴 산화물인 몰리브덴 트리옥사이드, 가공부 내식성 개선제로서 바나듐 화합물인 오산화바나듐을 첨가하여 조성물을 제조하였다. 각 성분의 함량을 하기 표 7에 나타내었으며, 이때 건조 피막 상태에서는 용매(물, 에틸 알코올)가 제거됨을 감안하여, 고형분 100%를 기준으로 각 성분의 함량을 기재하였다.To this chromium compound, an organic silane sol-gel binder (3-glycyloxypropyl methyldiethoxysilane and 3-aminopropyl triethoxysilane) as a rust-preventive coating agent, titanium hydrofluoric acid as a rust-preventive etchant, lithium silica sol as a corrosion-resistant additive, A composition was prepared by adding nitrate as a blackening improving agent (I), molybdenum trioxide as a molybdenum oxide as a blackening improving agent (II), and vanadium pentoxide as a vanadium compound as a corrosion resistance improving agent in a processed part. The content of each component is shown in Table 7 below. At this time, considering that the solvent (water, ethyl alcohol) is removed in the dry film state, the content of each component is described based on 100% solid content.
그리고, 상기 조성물을 용액 상태로 제조함에 있어서, 제조된 조성물의 고형분 13% 기준으로 물을 61중량%, 에틸 알코올을 26중량%로 첨가하였다.And, in preparing the composition in a solution state, 61% by weight of water and 26% by weight of ethyl alcohol were added based on the solid content of 13% of the prepared composition.
하기 표 7의 함량에 따라 제조된 용액 조성물을 도포하여 건조 처리한 각 시편의 평판 내식성, 가공부 내식성, 내흑변성, 이물 묻음성을 평가하였으며, 그 결과를 하기 표 7에 함께 나타내었다.Plate corrosion resistance, processed part corrosion resistance, blackening resistance, and staining of foreign substances were evaluated for each specimen coated with the solution composition prepared according to the contents of Table 7 and dried, and the results are shown in Table 7 below.
화합물chrome
compound
원
제ring
one
my
매point
hawk
피막제rust
coating agent
에칭제etchant
첨가제corrosion resistance
additive
개선제black stool
improver
개선제Machining corrosion resistance
improver
내식성reputation
corrosion resistance
내식성processing department
corrosion resistance
흑변성my
blackening
묻음성alien substance
soiling
예13comparison
Example 13
예27invent
yes27
상기 표 7에 나타낸 바와 같이, 발명예 24 내지 27은 본 발명에서 제안하는 함량을 모두 만족하는 조성물로 표면처리된 경우로, 모든 물성에서 양호 이상의 결과를 보였다.As shown in Table 7, Inventive Examples 24 to 27 were surface-treated with compositions satisfying all the contents proposed in the present invention, and showed better or better results in all physical properties.
반면, 방청 에칭제를 함유하지 않는 비교예 13은 평판 내식성과 가공부 내식성이 열위한 결과를 보였으며, 방청 에칭제의 함량이 과도한 비교예 14는 내흑변성이 불량한 결과를 보였다.On the other hand, Comparative Example 13, which did not contain the rust-preventive etchant, showed poor plate corrosion resistance and processed part corrosion resistance, and Comparative Example 14, which had an excessive amount of the rust-preventive etchant, showed poor blackening resistance.
실험 8. 내식성 첨가제의 함량에 따른 물성 변화Experiment 8. Changes in physical properties according to the content of anticorrosive additives
표면처리용 조성물을 다음에 따라 제조하였다.A composition for surface treatment was prepared as follows.
질산크롬(A)와 크롬산염(B)을 물에 용해한 크롬 용액에 환원제로서 아인산, 촉매로서 인산을 첨가하여 크롬 화합물을 제조하였다. 이때, 상기 질산크롬(A)과 크롬산염(B)의 함량비(A/(A+B))를 0.5, 환원비는 0.85로 제어하였다.A chromium compound was prepared by adding phosphorous acid as a reducing agent and phosphoric acid as a catalyst to a chromium solution in which chromium nitrate (A) and chromate (B) were dissolved in water. At this time, the content ratio (A/(A+B)) of the chromium nitrate (A) and chromate (B) was controlled to 0.5 and the reduction ratio to 0.85.
이 크롬 화합물에 방청 피막제로서 유기 실란 졸-겔 바인더(3-글리실옥시프로필 메틸디에톡시실란 및 3-아미노프로필 트리에톡시 실란), 방청 에칭제로서 티탄불화수소산, 내식성 첨가제로서 리튬 실리카졸, 흑변 개선제(I)로서 질산염, 흑변 개선제(II)로서 몰리브덴 산화물인 몰리브덴 트리옥사이드, 가공부 내식성 개선제로서 바나듐 화합물인 오산화바나듐을 첨가하여 조성물을 제조하였다. 각 성분의 함량을 하기 표 8에 나타내었으며, 이때 건조 피막 상태에서는 용매(물, 에틸 알코올)가 제거됨을 감안하여, 고형분 100%를 기준으로 각 성분의 함량을 기재하였다.To this chromium compound, an organic silane sol-gel binder (3-glycyloxypropyl methyldiethoxysilane and 3-aminopropyl triethoxysilane) as a rust-preventive coating agent, titanium hydrofluoric acid as a rust-preventive etchant, lithium silica sol as a corrosion-resistant additive, A composition was prepared by adding nitrate as a blackening improving agent (I), molybdenum trioxide as a molybdenum oxide as a blackening improving agent (II), and vanadium pentoxide as a vanadium compound as a corrosion resistance improving agent in a processed part. The contents of each component are shown in Table 8 below, and considering that solvents (water, ethyl alcohol) are removed in the dry film state, the contents of each component are described based on 100% solid content.
그리고, 상기 조성물을 용액 상태로 제조함에 있어서, 제조된 조성물의 고형분 13% 기준으로 물을 61중량%, 에틸 알코올을 26중량%로 첨가하였다.And, in preparing the composition in a solution state, 61% by weight of water and 26% by weight of ethyl alcohol were added based on the solid content of 13% of the prepared composition.
하기 표 8의 함량에 따라 제조된 용액 조성물을 도포하여 건조 처리한 각 시편의 평판 내식성, 가공부 내식성, 내흑변성, 용액 안정성을 평가하였으며, 그 결과를 하기 표 8에 함께 나타내었다.Plate corrosion resistance, processed part corrosion resistance, blackening resistance, and solution stability of each specimen coated with the solution composition prepared according to the contents of Table 8 and dried were evaluated, and the results are shown in Table 8 below.
화합물chrome
compound
원
제ring
one
my
매point
hawk
피막제rust
coating agent
에칭제rust
etchant
첨가제additive
개선제black stool
improver
개선제Machining corrosion resistance
improver
내식성reputation
corrosion resistance
내식성processing department
corrosion resistance
흑변성my
blackening
안정성solution
stability
예15comparison
yes15
예31invent
yes31
상기 표 8에 나타낸 바와 같이, 발명예 28 내지 31은 본 발명에서 제안하는 함량을 모두 만족하는 조성물로 표면처리된 경우로, 모든 물성에서 양호 이상의 결과를 보였다.As shown in Table 8, Inventive Examples 28 to 31 were surface-treated with compositions satisfying all the contents proposed in the present invention, and showed better or better results in all physical properties.
반면, 내식성 첨가제를 첨가하지 않는 비교예 15는 가공부 내식성이 불량한 결과를 보였으며, 내식성 첨가제의 함량이 과도한 비교예 16은 용액 안정성이 열위한 결과를 보였다.On the other hand, Comparative Example 15, in which no anticorrosive additive was added, showed poor corrosion resistance at the processed part, and Comparative Example 16, in which the anticorrosive additive content was excessive, showed poor solution stability.
실험 9. 흑변 개선제(I)의 함량에 따른 물성 변화Experiment 9. Physical property change according to the content of the blackening improver (I)
표면처리용 조성물을 다음에 따라 제조하였다.A composition for surface treatment was prepared as follows.
질산크롬(A)와 크롬산염(B)을 물에 용해한 크롬 용액에 환원제로서 아인산, 촉매로서 인산을 첨가하여 크롬 화합물을 제조하였다. 이때, 상기 질산크롬(A)과 크롬산염(B)의 함량비(A/(A+B))를 0.5, 환원비는 0.85로 제어하였다.A chromium compound was prepared by adding phosphorous acid as a reducing agent and phosphoric acid as a catalyst to a chromium solution in which chromium nitrate (A) and chromate (B) were dissolved in water. At this time, the content ratio (A/(A+B)) of the chromium nitrate (A) and chromate (B) was controlled to 0.5 and the reduction ratio to 0.85.
이 크롬 화합물에 방청 피막제로서 유기 실란 졸-겔 바인더(3-글리실옥시프로필 메틸디에톡시실란 및 3-아미노프로필 트리에톡시 실란), 방청 에칭제로서 티탄불화수소산, 내식성 첨가제로서 리튬 실리카졸, 흑변 개선제(I)로서 질산염, 흑변 개선제(II)로서 몰리브덴 산화물인 몰리브덴 트리옥사이드, 가공부 내식성 개선제로서 바나듐 화합물인 오산화바나듐을 첨가하여 조성물을 제조하였다. 각 성분의 함량을 하기 표 9에 나타내었으며, 이때 건조 피막 상태에서는 용매(물, 에틸 알코올)가 제거됨을 감안하여, 고형분 100%를 기준으로 각 성분의 함량을 기재하였다.To this chromium compound, an organic silane sol-gel binder (3-glycyloxypropyl methyldiethoxysilane and 3-aminopropyl triethoxysilane) as a rust-preventive coating agent, titanium hydrofluoric acid as a rust-preventive etchant, lithium silica sol as a corrosion-resistant additive, A composition was prepared by adding nitrate as a blackening improving agent (I), molybdenum trioxide as a molybdenum oxide as a blackening improving agent (II), and vanadium pentoxide as a vanadium compound as a corrosion resistance improving agent in a processed part. The content of each component is shown in Table 9 below. At this time, considering that the solvent (water, ethyl alcohol) is removed in the dry film state, the content of each component is described based on 100% solid content.
그리고, 상기 조성물을 용액 상태로 제조함에 있어서, 제조된 조성물의 고형분 13% 기준으로 물을 61중량%, 에틸 알코올을 26중량%로 첨가하였다.And, in preparing the composition in a solution state, 61% by weight of water and 26% by weight of ethyl alcohol were added based on the solid content of 13% of the prepared composition.
하기 표 9의 함량에 따라 제조된 용액 조성물을 도포하여 건조 처리한 각 시편의 평판 내식성, 가공부 내식성, 내흑변성, 용액 안정성을 평가하였으며, 그 결과를 하기 표 9에 함께 나타내었다.Plate corrosion resistance, processed part corrosion resistance, blackening resistance, and solution stability of each specimen coated with the solution composition prepared according to the contents of Table 9 and dried were evaluated, and the results are shown in Table 9 below.
화합물chrome
compound
원
제ring
one
my
매point
hawk
피막제rust
coating agent
에칭제rust
etchant
첨가제corrosion resistance
additive
개선제improver
개선제Machining corrosion resistance
improver
내식성reputation
corrosion resistance
내식성processing department
corrosion resistance
흑변성my
blackening
안정성solution
stability
예17comparison
yes17
예35invent
yes35
상기 표 9에 나타낸 바와 같이, 발명예 32 내지 35는 본 발명에서 제안하는 함량을 모두 만족하는 조성물로 표면처리된 경우로, 모든 물성에서 양호 이상의 결과를 보였다.As shown in Table 9, Inventive Examples 32 to 35 were surface-treated with compositions satisfying all the contents proposed in the present invention, and showed better or better results in all physical properties.
반면, 흑변 개선제(I)을 첨가하지 않는 비교예 17은 내흑변성이 불량한 결과를 보였으며, 흑변 개선제(I)의 함량이 과도한 비교예 18은 용액 안정성이 열위한 결과를 보였다.On the other hand, Comparative Example 17, in which the blackening improver (I) was not added, showed poor blackening resistance, and Comparative Example 18, in which the amount of the blackening improver (I) was excessive, showed poor solution stability.
실험 10. 흑변 개선제(II)의 함량에 따른 물성 변화Experiment 10. Physical property change according to the content of the blackening improver (II)
표면처리용 조성물을 다음에 따라 제조하였다.A composition for surface treatment was prepared as follows.
질산크롬(A)와 크롬산염(B)을 물에 용해한 크롬 용액에 환원제로서 아인산, 촉매로서 인산을 첨가하여 크롬 화합물을 제조하였다. 이때, 상기 질산크롬(A)과 크롬산염(B)의 함량비(A/(A+B))를 0.5, 환원비는 0.85로 제어하였다.A chromium compound was prepared by adding phosphorous acid as a reducing agent and phosphoric acid as a catalyst to a chromium solution in which chromium nitrate (A) and chromate (B) were dissolved in water. At this time, the content ratio (A/(A+B)) of the chromium nitrate (A) and chromate (B) was controlled to 0.5 and the reduction ratio to 0.85.
이 크롬 화합물에 방청 피막제로서 유기 실란 졸-겔 바인더(3-글리실옥시프로필 메틸디에톡시실란 및 3-아미노프로필 트리에톡시 실란), 방청 에칭제로서 티탄불화수소산, 내식성 첨가제로서 리튬 실리카졸, 흑변 개선제(I)로서 질산염, 흑변 개선제(II)로서 몰리브덴 산화물인 몰리브덴 트리옥사이드, 가공부 내식성 개선제로서 바나듐 화합물인 오산화바나듐을 첨가하여 조성물을 제조하였다. 각 성분의 함량을 하기 표 10에 나타내었으며, 이때 건조 피막 상태에서는 용매(물, 에틸 알코올)가 제거됨을 감안하여, 고형분 100%를 기준으로 각 성분의 함량을 기재하였다.To this chromium compound, an organic silane sol-gel binder (3-glycyloxypropyl methyldiethoxysilane and 3-aminopropyl triethoxysilane) as a rust-preventive coating agent, titanium hydrofluoric acid as a rust-preventive etchant, lithium silica sol as a corrosion-resistant additive, A composition was prepared by adding nitrate as a blackening improving agent (I), molybdenum trioxide as a molybdenum oxide as a blackening improving agent (II), and vanadium pentoxide as a vanadium compound as a corrosion resistance improving agent in a processed part. The content of each component is shown in Table 10 below, and considering that solvents (water, ethyl alcohol) are removed in the dry film state, the content of each component is described based on 100% solid content.
그리고, 상기 조성물을 용액 상태로 제조함에 있어서, 제조된 조성물의 고형분 13% 기준으로 물을 61중량%, 에틸 알코올을 26중량%로 첨가하였다.And, in preparing the composition in a solution state, 61% by weight of water and 26% by weight of ethyl alcohol were added based on the solid content of 13% of the prepared composition.
하기 표 10의 함량에 따라 제조된 용액 조성물을 도포하여 건조 처리한 각 시편의 평판 내식성, 가공부 내식성, 내흑변성, 용액 안정성을 평가하였으며, 그 결과를 하기 표 10에 함께 나타내었다.Plate corrosion resistance, processed part corrosion resistance, blackening resistance, and solution stability of each specimen coated with the solution composition prepared according to the contents of Table 10 and dried were evaluated, and the results are shown together in Table 10 below.
화합물chrome
compound
원
제ring
one
my
매point
hawk
피막제rust
coating agent
에칭제rust
etchant
첨가제corrosion resistance
additive
개선제improver
개선제Machining corrosion resistance
improver
내식성reputation
corrosion resistance
내식성processing department
corrosion resistance
흑변성my
blackening
안정성solution
stability
예19comparison
yes19
상기 표 10에 나타낸 바와 같이, 발명예 36 내지 38은 본 발명에서 제안하는 함량을 모두 만족하는 조성물로 표면처리된 경우로, 모든 물성에서 양호 이상의 결과를 보였다.As shown in Table 10, Inventive Examples 36 to 38 were surface-treated with compositions satisfying all the contents proposed in the present invention, and showed better or better results in all physical properties.
반면, 흑변 개선제(II)를 첨가하지 않는 비교예 19는 내흑변성이 불량한 결과를 보였으며, 흑변 개선제(II)의 함량이 과도한 비교예 20은 용액 안정성이 열위한 결과를 보였다.On the other hand, Comparative Example 19, in which the blackening improver (II) was not added, showed poor blackening resistance, and Comparative Example 20, in which the blackening improver (II) content was excessive, showed poor solution stability.
실험 11. 가공부 내식성 개선제의 함량에 따른 물성 변화Experiment 11. Changes in physical properties according to the content of the corrosion resistance improver in the processing part
표면처리용 조성물을 다음에 따라 제조하였다.A composition for surface treatment was prepared as follows.
질산크롬(A)와 크롬산염(B)을 물에 용해한 크롬 용액에 환원제로서 아인산, 촉매로서 인산을 첨가하여 크롬 화합물을 제조하였다. 이때, 상기 질산크롬(A)과 크롬산염(B)의 함량비(A/(A+B))를 0.5, 환원비는 0.85로 제어하였다.A chromium compound was prepared by adding phosphorous acid as a reducing agent and phosphoric acid as a catalyst to a chromium solution in which chromium nitrate (A) and chromate (B) were dissolved in water. At this time, the content ratio (A/(A+B)) of the chromium nitrate (A) and chromate (B) was controlled to 0.5 and the reduction ratio to 0.85.
이 크롬 화합물에 방청 피막제로서 유기 실란 졸-겔 바인더(3-글리실옥시프로필 메틸디에톡시실란 및 3-아미노프로필 트리에톡시 실란), 방청 에칭제로서 티탄불화수소산, 내식성 첨가제로서 리튬 실리카졸, 흑변 개선제(I)로서 질산염, 흑변 개선제(II)로서 몰리브덴 산화물인 몰리브덴 트리옥사이드, 가공부 내식성 개선제로서 바나듐 화합물인 오산화바나듐을 첨가하여 조성물을 제조하였다. 각 성분의 함량을 하기 표 11에 나타내었으며, 이때 건조 피막 상태에서는 용매(물, 에틸 알코올)가 제거됨을 감안하여, 고형분 100%를 기준으로 각 성분의 함량을 기재하였다.To this chromium compound, an organic silane sol-gel binder (3-glycyloxypropyl methyldiethoxysilane and 3-aminopropyl triethoxysilane) as a rust-preventive coating agent, titanium hydrofluoric acid as a rust-preventive etchant, lithium silica sol as a corrosion-resistant additive, A composition was prepared by adding nitrate as a blackening improving agent (I), molybdenum trioxide as a molybdenum oxide as a blackening improving agent (II), and vanadium pentoxide as a vanadium compound as a corrosion resistance improving agent in a processed part. The content of each component is shown in Table 11 below. At this time, considering that the solvent (water, ethyl alcohol) is removed in the dry film state, the content of each component is described based on 100% solid content.
그리고, 상기 조성물을 용액 상태로 제조함에 있어서, 제조된 조성물의 고형분 13% 기준으로 물을 61중량%, 에틸 알코올을 26중량%로 첨가하였다.And, in preparing the composition in a solution state, 61% by weight of water and 26% by weight of ethyl alcohol were added based on the solid content of 13% of the prepared composition.
하기 표 11의 함량에 따라 제조된 용액 조성물을 도포하여 건조 처리한 각 시편의 평판 내식성, 가공부 내식성, 내흑변성, 용액 안정성을 평가하였으며, 그 결과를 하기 표 11에 함께 나타내었다.Plate corrosion resistance, processed part corrosion resistance, blackening resistance, and solution stability of each specimen coated with the solution composition prepared according to the contents of Table 11 and dried were evaluated, and the results are shown together in Table 11 below.
화합물chrome
compound
원
제ring
one
my
매point
hawk
피막제rust
coating agent
에칭제rust
etchant
첨가제corrosion resistance
additive
개선제black stool
improver
개선제improver
내식성reputation
corrosion resistance
내식성processing department
corrosion resistance
흑변성my
blackening
안정성solution
stability
예21comparison
yes21
상기 표 11에 나타낸 바와 같이, 발명예 39 내지 41은 본 발명에서 제안하는 함량을 모두 만족하는 조성물로 표면처리된 경우로, 모든 물성에서 양호 이상의 결과를 보였다.As shown in Table 11, Inventive Examples 39 to 41 were surface-treated with compositions satisfying all the contents proposed in the present invention, and showed better or better results in all physical properties.
반면, 가공부 내식성 첨가제를 첨가하지 않는 비교예 21은 가공부 내식성이 불량한 결과를 보였으며, 가공부 내식성 첨가제의 함량이 과도한 비교예 22는 내흑변성 및 용액 안정성이 열위한 결과를 보였다.On the other hand, Comparative Example 21, in which the anticorrosion additive was not added, showed poor corrosion resistance in the processed part, and Comparative Example 22, in which the content of the anticorrosive additive in the processed part was excessive, showed poor blackening resistance and solution stability.
실험 12. 코팅층 두께 및 건조 온도에 따른 물성 변화Experiment 12. Physical property change according to coating layer thickness and drying temperature
표면처리용 조성물을 다음에 따라 제조하였다.A composition for surface treatment was prepared as follows.
고형분 100중량%를 기준으로 크롬 화합물 28중량%, 방청 피막제로서 유기 실란 졸-겔 바인더(3-글리실옥시프로필 메틸디에톡시실란 및 3-아미노프로필 트리에톡시 실란)를 64중량%, 방청 에칭제로서 티탄불화수소산을 2.5중량%, 내식성 첨가제로서 리튬 실리카졸을 1중량%, 흑변 개선제(I)로서 질산염을 1중량%, 흑변 개선제(II)로서 몰리브덴 산화물인 몰리브덴 트리옥사이드를 0.5중량%, 가공부 내식성 개선제로 바나듐 화합물인 오산화바나듐을 0.5중량%로 첨가하여 조성물을 제조하였다.28% by weight of chromium compound based on 100% by weight of solid content, 64% by weight of organic silane sol-gel binder (3-glycyloxypropyl methyldiethoxysilane and 3-aminopropyl triethoxy silane) as an anti-rust coating agent, anti-rust etching 2.5% by weight of titanium hydrofluoric acid as a zero, 1% by weight of lithium silica sol as a corrosion resistance additive, 1% by weight of nitrate as a blackening improver (I), 0.5% by weight of molybdenum trioxide as a molybdenum oxide as a blackening improver (II), A composition was prepared by adding 0.5% by weight of vanadium pentoxide, which is a vanadium compound, as a corrosion resistance improver for the processing part.
상기 조성물 중 크롬 화합물은 질산크롬(A)와 크롬산염(B)을 물에 용해한 크롬 용액에 환원제로서 아인산을 2중량%, 촉매로서 인산을 0.5중량%로 첨가하여 제조하였으며, 상기 질산크롬(A)과 크롬산염(B)의 함량비(A/(A+B))는 0.5로 제어하고, 환원비는 0.85로 제어하였다.The chromium compound in the composition was prepared by adding 2% by weight of phosphorous acid as a reducing agent and 0.5% by weight of phosphoric acid as a catalyst to a chromium solution in which chromium nitrate (A) and chromate (B) were dissolved in water, and the chromium nitrate (A ) and chromate (B), the content ratio (A/(A+B)) was controlled to 0.5, and the reduction ratio was controlled to 0.85.
상기 조성물을 용액 상태로 제조함에 있어서, 제조된 조성물의 고형분 13% 기준으로 물을 61중량%, 에틸 알코올을 26중량%로 첨가하였다.In preparing the composition in a solution state, 61% by weight of water and 26% by weight of ethyl alcohol were added based on the solid content of 13% of the prepared composition.
상기에 따라 제조된 조성물을 용액 상태로 유분이 제거된 시편(7cm(가로)×15cm(세로) 크기의 삼원계 용융아연도금강판)에 바(bar) 코팅한 후 열풍건조로(내부 온도 250℃)에서 건조시켰다. 이때, 코팅층의 두께(건조 두께)와 PMT 기준 건조 온도를 다르게 제어하였으며, 각 시편의 평판 내식성, 가공부 내식성, 내흑변성 및 내알칼리성을 평가하고, 그 결과를 하기 표 12에 나타내었다.The composition prepared as described above is bar-coated on a specimen (a ternary hot-dip galvanized steel sheet with a size of 7 cm (width) × 15 cm (length)) from which oil is removed in a solution state, and then dried with hot air (internal temperature 250 ° C) ) and dried in At this time, the thickness (dry thickness) of the coating layer and the drying temperature based on PMT were controlled differently, and the plate corrosion resistance, processed part corrosion resistance, blackening resistance and alkali resistance of each specimen were evaluated, and the results are shown in Table 12 below.
(㎛)coating layer thickness
(μm)
(℃)drying temperature
(℃)
내식성reputation
corrosion resistance
내식성processing department
corrosion resistance
상기 표 12에 나타낸 바와 같이, 코팅층을 0.3~1.5㎛의 두께로 형성하고, PMT 기준 60℃로 건조를 실시한 발명예 42 내지 45는 모든 물성에서 양호 이상의 결과를 보였다. 뿐만 아니라, 코팅층을 0.8㎛의 두께로 형성하고, PMT 기준 40~200℃에서 건조를 실시한 발명예 46 내지 48에서도 양호 이상의 결과를 보였다.As shown in Table 12, inventive examples 42 to 45 in which a coating layer was formed to a thickness of 0.3 to 1.5 μm and dried at 60 ° C. based on PMT showed better or better results in all physical properties. In addition, inventive examples 46 to 48 in which a coating layer was formed to a thickness of 0.8 μm and dried at 40 to 200 ° C. based on PMT also showed better or better results.
반면, 코팅층의 두께가 0.2㎛로 얇은 비교예 23의 경우에는 내흑변성 및 내알칼리성이 우수하지 못하고, 평판 내식성 및 가공부 내식성이 매우 열위하였다. 코팅층이 과도하게 두껍게 형성된 비교예 24는 가공부 내식성이 불량한 결과를 보였다.On the other hand, in the case of Comparative Example 23, in which the thickness of the coating layer was as thin as 0.2 μm, the blackening resistance and alkali resistance were not excellent, and the corrosion resistance of the plate and the corrosion resistance of the processed part were very poor. Comparative Example 24, in which the coating layer was excessively thick, showed poor corrosion resistance of the processed part.
한편, 건조시 온도가 PMT 기준 40℃ 미만인 비교예 25는 조성물이 충분히 건조되지 못함에 따라 모든 물성에서 불량한 결과를 보였다. 건조시 온도가 PMT 기준 200℃를 초과한 비교예 26은 내흑변성이 불량한 결과를 보였다. 이는, 건조 공정을 완료한 후 최종적으로 냉각하는 동안 시편에서 발생된 수증기로 인해 건조설비 상부에 결로 현상이 발생하고, 시편 표면으로 흄(fume)이 떨어짐에 기인한 것이다.On the other hand, Comparative Example 25, in which the temperature during drying was less than 40 ° C. based on PMT, showed poor results in all physical properties as the composition was not sufficiently dried. Comparative Example 26, in which the drying temperature exceeded 200° C. based on PMT, showed poor blackening resistance. This is due to condensation occurring on the top of the drying equipment due to water vapor generated from the specimen during final cooling after completing the drying process, and fume falling to the surface of the specimen.
Claims (23)
(a) 크롬 화합물 15~45중량%,
(b) 방청 피막제 45~75중량%,
(c) 방청 에칭제 0.1~3.0중량%,
(d) 내식성 첨가제 0.1~5.0중량%,
(e) 흑변 개선제(I) 0.5~3.0중량%,
(f) 흑변 개선제(II) 0.1~2.0중량% 및
(g) 가공부 내식성 개선제 0.1~1.0중량%를 포함하고,
상기 크롬 화합물은 질산크롬(A) 및 크롬산염(B) 용액에 (h)환원제인 아인산을 0.5~5.0중량% 및 (i) 촉매제인 인산을 0.1~2.0중량%로 포함하여 얻는 것인 삼원계 용융아연도금강판 표면처리용 조성물.
With respect to 100% by weight of solid content,
(a) 15 to 45% by weight of a chromium compound;
(b) 45 to 75% by weight of an anti-rust coating agent;
(c) 0.1 to 3.0% by weight of an anti-rust etchant;
(d) 0.1 to 5.0% by weight of anticorrosive additive;
(e) 0.5 to 3.0% by weight of a blackening improver (I);
(f) 0.1 to 2.0% by weight of a blackening improver (II) and
(g) 0.1 to 1.0% by weight of a corrosion resistance improver for the processing part,
The chromium compound is obtained by including (h) 0.5 to 5.0% by weight of phosphorous acid as a reducing agent and (i) 0.1 to 2.0% by weight of phosphoric acid as a catalyst in a solution of chromium nitrate (A) and chromate (B). A composition for surface treatment of hot-dip galvanized steel sheet.
상기 질산크롬과 크롬산염의 함량비(A/A+B)가 0.3~0.6인 삼원계 용융아연도금강판 표면처리용 조성물.
According to claim 1,
A composition for surface treatment of a ternary hot-dip galvanized steel sheet wherein the content ratio (A/A+B) of the chromium nitrate and chromate is 0.3 to 0.6.
상기 크롬 화합물의 환원비(3가 크롬 이온/(3가 크롬 이온+6가 크롬 이온))가 0.75~0.90인 것을 특징으로 하는 삼원계 용융아연도금강판 표면처리용 조성물.
According to claim 1,
The ternary hot-dip galvanized steel sheet surface treatment composition, characterized in that the reduction ratio (trivalent chromium ion/(trivalent chromium ion + hexavalent chromium ion)) of the chromium compound is 0.75 to 0.90.
상기 방청 피막제는 유기 실란 졸-겔 바인더인 삼원계 용융아연도금강판 표면처리용 조성물.
According to claim 1,
The anti-rust coating agent is an organic silane sol-gel binder, a composition for surface treatment of a ternary hot-dip galvanized steel sheet.
상기 방청 에칭제는 티탄불화수소산, 규화불화수소산 및 지르코늄불화수소산으로 이루어진 군에서 선택된 하나 이상인 삼원계 용융아연도금강판 표면처리용 조성물.
According to claim 1,
The anti-rust etchant is at least one selected from the group consisting of titanium hydrofluoric acid, silicic hydrofluoric acid and zirconium hydrofluoric acid.
상기 내식성 첨가제는 리튬 실리카졸, 규산나트륨, 규산칼륨, 리튬-칼륨 실리케이트 및 리튬-소디움 실리케이트로 이루어진 군에서 선택된 하나 인상인 삼원계 용융아연도금강판 표면처리용 조성물.
According to claim 1,
The anti-corrosion additive is one selected from the group consisting of lithium silica sol, sodium silicate, potassium silicate, lithium-potassium silicate and lithium-sodium silicate.
상기 흑변 개선제(I)은 질산염, 질산암모늄 및 아질산염으로 이루어진 군에서 선택된 하나 이상인 삼원계 용융아연도금강판 표면처리용 조성물.
According to claim 1,
The blackening improver (I) is at least one selected from the group consisting of nitrate, ammonium nitrate, and nitrite.
상기 흑변 개선제(II)는 몰리브덴산염이며,
상기 몰리브덴산염은 몰리브덴 산화물, 몰리브덴 황화물, 몰리브덴 아세트산염, 몰리브덴 인산염, 몰리브덴 탄화물, 몰리브덴 염화물, 몰리브덴 불소화물 및 몰리브덴 질화물로 이루어진 군에서 선택된 하나 이상의 몰리브덴계 화합물인 삼원계 용융아연도금강판 표면처리용 조성물.
According to claim 1,
The blackening improver (II) is a molybdate,
The molybdenum salt is at least one molybdenum compound selected from the group consisting of molybdenum oxide, molybdenum sulfide, molybdenum acetate, molybdenum phosphate, molybdenum carbide, molybdenum chloride, molybdenum fluoride and molybdenum nitride Surface treatment composition for ternary hot-dip galvanized steel sheet .
상기 가공부 내식성 개선제는 바나듐 화합물이며,
상기 바나듐 화합물은 오산화바나듐, 메타바나딘산, 메타바나딘산 암모늄, 메타바나딘산 나트륨, 옥시삼염화 바나듐, 삼산화바나듐, 이산화바나듐, 옥시황산 바나듐, 바나듐 옥시아세틸아세테이트, 바나듐 아세틸아세테이트, 삼염화바나듐 및 인바나듐몰리브덴산으로 이루어진 군에서 선택된 하나 이상인 삼원계 용융아연도금강판 표면처리용 조성물.
According to claim 1,
The processing part corrosion resistance improving agent is a vanadium compound,
The vanadium compound is vanadium pentoxide, metavanadic acid, ammonium metavanadate, sodium metavanadate, vanadium oxytrichloride, vanadium trioxide, vanadium dioxide, vanadium oxysulfate, vanadium oxyacetylacetate, vanadium acetylacetate, vanadium trichloride and A composition for surface treatment of a ternary hot-dip galvanized steel sheet comprising at least one selected from the group consisting of phosphovanadium molybdic acid.
상기 조성물은 (j) 용제를 더 포함하며,
고형분 함량이 5~20중량%이고, 잔부 용제인 삼원계 용융아연도금강판 표면처리용 조성물.
According to claim 1,
The composition further comprises (j) a solvent,
A composition for surface treatment of a ternary hot-dip galvanized steel sheet having a solid content of 5 to 20% by weight and the balance being a solvent.
상기 조성물은 보조용제를 더 포함하며,
상기 보조용제는 에틸알코올, 메틸알코올, 이소프로필 알코올, 1-메톡시-2-프로판올 및 2-부톡시에탄올로 이루어진 군에서 선택된 하나 이상을 전체 용제 중 20~40중량%로 포함하는 것인 삼원계 용융아연도금강판 표면처리용 조성물.
According to claim 10,
The composition further comprises an auxiliary solvent,
The auxiliary solvent includes 20 to 40% by weight of at least one selected from the group consisting of ethyl alcohol, methyl alcohol, isopropyl alcohol, 1-methoxy-2-propanol, and 2-butoxyethanol in an amount of 3-way A composition for surface treatment of hot-dip galvanized steel sheet.
상기 강판의 적어도 일면에 형성된 Zn-Mg-Al계 도금층; 및
상기 도금층 상에 형성된 표면처리 코팅층을 포함하며,
상기 표면처리 코팅층은 제 1항 내지 제 11항 중 어느 한 항의 조성물로 형성된 코팅층인 표면처리된 삼원계 용융아연도금강판.
grater;
a Zn-Mg-Al-based plating layer formed on at least one surface of the steel sheet; and
Including a surface treatment coating layer formed on the plating layer,
The surface treatment coating layer is a coating layer formed of the composition of any one of claims 1 to 11. Surface-treated ternary hot-dip galvanized steel sheet.
상기 Zn-Mg-Al계 도금층은 중량%로 마그네슘(Mg): 4.0~7.0%, 알루미늄(Al): 11.0~19.5%, 잔부 Zn 및 기타 불가피한 불순물을 포함하고,
하기 관계식 1을 만족하는 것을 특징으로 하는 표면처리된 삼원계 용융아연도금강판.
[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.)
According to claim 12,
The Zn-Mg-Al-based plating layer includes magnesium (Mg): 4.0 to 7.0%, aluminum (Al): 11.0 to 19.5%, the balance Zn and other unavoidable impurities in weight%,
Surface-treated ternary hot-dip galvanized steel sheet, characterized in that it satisfies the following relational expression 1.
[Relationship 1]
0.26 ≤ I(110)/I(103) ≤ 0.65
(In relational expression 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 X-ray diffraction of the (103) plane crystal for the MgZn 2 phase represents the integral strength.)
상기 표면처리 코팅층은 0.3~1.5㎛의 두께를 가지는 것인 표면처리된 삼원계 용융아연도금강판.
According to claim 12,
The surface treatment coating layer is a surface-treated ternary hot-dip galvanized steel sheet having a thickness of 0.3 ~ 1.5㎛.
상기 도금층 상에 제 1항 내지 제 11항 중 어느 한 항의 조성물을 코팅처리하는 단계; 및
상기 코팅처리된 강판을 건조처리하는 단계를 포함하는 표면처리된 삼원계 용융아연도금강판의 제조방법.
forming a Zn-Mg-Al-based plating layer by hot-dip galvanizing treatment on at least one surface of the steel sheet;
coating the composition of any one of claims 1 to 11 on the plating layer; and
A method of manufacturing a surface-treated ternary hot-dip galvanized steel sheet comprising the step of drying the coated steel sheet.
상기 조성물은 2.5~12.5㎛의 두께로 코팅처리하는 것인 표면처리된 삼원계 용융아연도금강판의 제조방법.
According to claim 15,
The method for producing a surface-treated ternary hot-dip galvanized steel sheet, wherein the composition is coated to a thickness of 2.5 to 12.5 μm.
상기 코팅처리는 바코팅, 롤코팅, 스프레이, 침적, 스프레이 스퀴징 및 침적 스퀴징으로 이루어진 군에서 선택된 어느 하나의 방법으로 행하는 것인 표면처리된 삼원계 용융아연도금강판의 제조방법.
According to claim 15,
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 dip squeezing.
상기 건조는 강판의 최종도달온도(PMT) 기준으로 40~200℃의 온도 범위에서 행해지는 것인 표면처리된 삼원계 용융아연도금강판의 제조방법.
According to claim 15,
The method of manufacturing a surface-treated ternary hot-dip galvanized steel sheet in which the drying is performed in a temperature range of 40 to 200 ° C based on the final temperature (PMT) of the steel sheet.
상기 건조는 열풍건조로 또는 유도가열로에서 행해지는 것인 표면처리된 삼원계 용융아연도금강판의 제조방법.
According to claim 15,
The method of manufacturing a surface-treated ternary hot-dip galvanized steel sheet, wherein the drying is performed in a hot air drying furnace or an induction heating furnace.
상기 열풍건조로는 내부 온도가 100~300℃로 유지되는 것인 표면처리된 삼원계 용융아연도금강판의 제조방법.
According to claim 19,
The method of manufacturing a surface-treated ternary hot-dip galvanized steel sheet in which the internal temperature is maintained at 100 to 300 ° C. in the hot air drying furnace.
상기 유도가열로는 1000~5000A의 전류가 인가되는 것인 표면처리된 삼원계 용융아연도금강판의 제조방법.
According to claim 19,
A method for producing a surface-treated ternary hot-dip galvanized steel sheet in which a current of 1000 to 5000 A is applied to the induction heating furnace.
상기 건조처리 후 공냉 또는 수냉시키는 단계를 더 포함하는 표면처리된 삼원계 용융아연도금강판의 제조방법.
According to claim 15,
The manufacturing method of the surface-treated ternary hot-dip galvanized steel sheet further comprising the step of air-cooling or water-cooling after the drying treatment.
상기 제조방법은 연속 공정으로 행해지며,
상기 연속 공정의 속도는 50~120mpm인 표면처리된 삼원계 용융아연도금강판의 제조방법.According to claim 15,
The manufacturing method is carried out as a continuous process,
The speed of the continuous process is a method for producing a surface-treated ternary hot-dip galvanized steel sheet of 50 to 120 mpm.
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- 2022-11-21 WO PCT/KR2022/018404 patent/WO2023101290A1/en unknown
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002069660A (en) | 2000-08-28 | 2002-03-08 | Nippon Parkerizing Co Ltd | Aqueous agent for metal surface treatment without including hexa-valent chromium and metal sheet surface-treated therewith |
| KR20040046347A (en) | 2002-11-27 | 2004-06-05 | 이덕진 | The trivalent chromate which contains no trace of hexavalent chrome nor any oxidizing agent |
| KR20050052215A (en) | 2003-11-29 | 2005-06-02 | 테크앤라이프 주식회사 | Chrom chromate coating solution to advance corrosion resistance of zinc galvanizing and manufacturing process of it |
| KR20060123628A (en) | 2004-03-03 | 2006-12-01 | 딥솔 가부시키가이샤 | Agent for reducing coating film overall friction coefficient for trivalent chromate treating solution, trivalent chromate treating solution and method for production thereof, and trivalent chromate coating film reduced in overall friction coefficient and method for production thereof |
| KR20090024450A (en) | 2007-09-04 | 2009-03-09 | 주식회사 에임하이글로벌 | Transparent film for preventing attachment of unwanted materials and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2023101290A1 (en) | 2023-06-08 |
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