KR101428143B1 - Zinc powder having good anti-corrosion property, manufacturing methdo for the same and steel sheet coated with said zinc powder - Google Patents
Zinc powder having good anti-corrosion property, manufacturing methdo for the same and steel sheet coated with said zinc powder Download PDFInfo
- Publication number
- KR101428143B1 KR101428143B1 KR1020110104713A KR20110104713A KR101428143B1 KR 101428143 B1 KR101428143 B1 KR 101428143B1 KR 1020110104713 A KR1020110104713 A KR 1020110104713A KR 20110104713 A KR20110104713 A KR 20110104713A KR 101428143 B1 KR101428143 B1 KR 101428143B1
- Authority
- KR
- South Korea
- Prior art keywords
- zinc powder
- compound
- triazole
- amino
- acid
- Prior art date
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 132
- 238000005260 corrosion Methods 0.000 title claims abstract description 59
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 38
- 239000010959 steel Substances 0.000 title claims abstract description 38
- 238000004519 manufacturing process Methods 0.000 title abstract description 5
- 230000007797 corrosion Effects 0.000 claims abstract description 58
- 239000011248 coating agent Substances 0.000 claims abstract description 47
- 238000000576 coating method Methods 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 23
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 21
- 239000011701 zinc Substances 0.000 claims abstract description 21
- 239000000843 powder Substances 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims description 41
- -1 phosphoric acid compound Chemical class 0.000 claims description 40
- 229920005989 resin Polymers 0.000 claims description 16
- 239000011347 resin Substances 0.000 claims description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 15
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 10
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- XGWWZKBCQLBJNH-UHFFFAOYSA-N 3-methylsulfanyl-1h-1,2,4-triazol-5-amine Chemical compound CSC1=NN=C(N)N1 XGWWZKBCQLBJNH-UHFFFAOYSA-N 0.000 claims description 6
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 6
- WITNHITXFVSWAF-UHFFFAOYSA-N P(O)(O)=O.NC1=NNC=N1 Chemical compound P(O)(O)=O.NC1=NNC=N1 WITNHITXFVSWAF-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 239000011787 zinc oxide Substances 0.000 claims description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 claims description 4
- 229910001424 calcium ion Inorganic materials 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- GGZHVNZHFYCSEV-UHFFFAOYSA-N 1-Phenyl-5-mercaptotetrazole Chemical compound SC1=NN=NN1C1=CC=CC=C1 GGZHVNZHFYCSEV-UHFFFAOYSA-N 0.000 claims description 3
- YGDVXSDNEFDTGV-UHFFFAOYSA-N 2-[6-[bis(carboxymethyl)amino]hexyl-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)CCCCCCN(CC(O)=O)CC(O)=O YGDVXSDNEFDTGV-UHFFFAOYSA-N 0.000 claims description 3
- QXTRPGAMVIONMK-UHFFFAOYSA-N 2-amino-5-ethyl-1,3,4-thiadiazole Chemical compound CCC1=NN=C(N)S1 QXTRPGAMVIONMK-UHFFFAOYSA-N 0.000 claims description 3
- GXIDNNRIWNVXTL-UHFFFAOYSA-N 5-[(4-propan-2-ylphenyl)methylidene]-1,3-thiazolidine-2,4-dione Chemical compound C1=CC(C(C)C)=CC=C1C=C1C(=O)NC(=O)S1 GXIDNNRIWNVXTL-UHFFFAOYSA-N 0.000 claims description 3
- VWRHSNKTSSIMGE-UHFFFAOYSA-N 5-ethylsulfanyl-1,3,4-thiadiazol-2-amine Chemical compound CCSC1=NN=C(N)S1 VWRHSNKTSSIMGE-UHFFFAOYSA-N 0.000 claims description 3
- JRLMMJNORORYPO-UHFFFAOYSA-N 5-phenyl-1,2-dihydro-1,2,4-triazole-3-thione Chemical compound N1C(S)=NC(C=2C=CC=CC=2)=N1 JRLMMJNORORYPO-UHFFFAOYSA-N 0.000 claims description 3
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- YRZBVIGIGZTWGT-UHFFFAOYSA-N [2-(diphosphonoamino)ethyl-phosphonoamino]phosphonic acid Chemical compound OP(O)(=O)N(P(O)(O)=O)CCN(P(O)(O)=O)P(O)(O)=O YRZBVIGIGZTWGT-UHFFFAOYSA-N 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 claims description 3
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 3
- 239000004317 sodium nitrate Substances 0.000 claims description 3
- 235000010344 sodium nitrate Nutrition 0.000 claims description 3
- GAAKVOJVCLLQAL-UHFFFAOYSA-N 1h-1,2,4-triazol-5-amine;1h-1,2,4-triazole Chemical compound C=1N=CNN=1.NC1=NC=NN1 GAAKVOJVCLLQAL-UHFFFAOYSA-N 0.000 claims description 2
- FSPKCGGKAVJAIN-UHFFFAOYSA-N P(O)(O)=O.N1N=CN=C1 Chemical compound P(O)(O)=O.N1N=CN=C1 FSPKCGGKAVJAIN-UHFFFAOYSA-N 0.000 claims description 2
- ZCIZIWRXZPZIDN-UHFFFAOYSA-N s-(1h-1,2,4-triazol-5-yl)thiohydroxylamine Chemical compound NSC=1N=CNN=1 ZCIZIWRXZPZIDN-UHFFFAOYSA-N 0.000 claims description 2
- JYRPXJDQMBHLOJ-UHFFFAOYSA-N 3h-1,3-benzothiazole-2-thione Chemical compound C1=CC=C2SC(S)=NC2=C1.C1=CC=C2SC(S)=NC2=C1 JYRPXJDQMBHLOJ-UHFFFAOYSA-N 0.000 claims 1
- SGIZECXZFLAGBW-UHFFFAOYSA-N 5-benzylidene-1,3-thiazolidine-2,4-dione Chemical compound S1C(=O)NC(=O)C1=CC1=CC=CC=C1 SGIZECXZFLAGBW-UHFFFAOYSA-N 0.000 claims 1
- FLEWVFQSJGZPJA-UHFFFAOYSA-N P(O)(O)=O.C(C1=CC=CC=C1)=C1N=NC(=N1)N.C(C1=CC=CC=C1)=NC1=NNC=N1 Chemical compound P(O)(O)=O.C(C1=CC=CC=C1)=C1N=NC(=N1)N.C(C1=CC=CC=C1)=NC1=NNC=N1 FLEWVFQSJGZPJA-UHFFFAOYSA-N 0.000 claims 1
- 239000008199 coating composition Substances 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 1
- 239000003973 paint Substances 0.000 abstract description 6
- 239000000049 pigment Substances 0.000 abstract description 6
- 239000000654 additive Substances 0.000 abstract description 4
- 230000000996 additive effect Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 21
- 239000002245 particle Substances 0.000 description 18
- 230000004048 modification Effects 0.000 description 16
- 238000012986 modification Methods 0.000 description 16
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000011247 coating layer Substances 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 230000000051 modifying effect Effects 0.000 description 11
- 239000010408 film Substances 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 229910021645 metal ion Inorganic materials 0.000 description 6
- 229910052761 rare earth metal Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- 229910001335 Galvanized steel Inorganic materials 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 3
- 239000010960 cold rolled steel Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000009501 film coating Methods 0.000 description 3
- 239000008397 galvanized steel Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- ARJGUVIAPHIKLE-UHFFFAOYSA-N 5-[(3,4-dimethoxyphenyl)methylidene]-1,3-thiazolidine-2,4-dione Chemical compound C1=C(OC)C(OC)=CC=C1C=C1C(=O)NC(=O)S1 ARJGUVIAPHIKLE-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- PQECORSGLNGPMR-UHFFFAOYSA-N O=C1NC(SC1)=O.C(C1=CC=CC=C1)=C1C(NC(S1)=O)=O Chemical compound O=C1NC(SC1)=O.C(C1=CC=CC=C1)=C1C(NC(S1)=O)=O PQECORSGLNGPMR-UHFFFAOYSA-N 0.000 description 2
- NLKWNJWBFQRZAE-UHFFFAOYSA-N P(O)(O)=O.P(O)(O)=O.P(O)(O)=O.N(P(O)(O)=O)(P(O)(O)=O)P(O)(O)=O Chemical compound P(O)(O)=O.P(O)(O)=O.P(O)(O)=O.N(P(O)(O)=O)(P(O)(O)=O)P(O)(O)=O NLKWNJWBFQRZAE-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 235000010288 sodium nitrite Nutrition 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- RVXGGSBRFNEABA-UHFFFAOYSA-N 1-phenyl-n-(1h-1,2,4-triazol-5-yl)methanimine Chemical compound C=1C=CC=CC=1C=NC1=NC=NN1 RVXGGSBRFNEABA-UHFFFAOYSA-N 0.000 description 1
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 1
- WZUUZPAYWFIBDF-UHFFFAOYSA-N 5-amino-1,2-dihydro-1,2,4-triazole-3-thione Chemical compound NC1=NNC(S)=N1 WZUUZPAYWFIBDF-UHFFFAOYSA-N 0.000 description 1
- QBQOOUMQVKQIQH-UHFFFAOYSA-N 5-methylsulfanyl-1h-1,2,4-triazole Chemical compound CSC=1N=CNN=1 QBQOOUMQVKQIQH-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- HYEHSVBJCQUMSI-UHFFFAOYSA-N C(C1=CC=CC=C1)=NC1(N=NC=N1)P(O)(=O)O.P(O)(O)=O.C(C1=CC=CC=C1)=NC1=NNC=N1 Chemical compound C(C1=CC=CC=C1)=NC1(N=NC=N1)P(O)(=O)O.P(O)(O)=O.C(C1=CC=CC=C1)=NC1=NNC=N1 HYEHSVBJCQUMSI-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Chemical class 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical class [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical class [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- PBYZZYRFIYWCGB-UHFFFAOYSA-N P(O)(O)=O.C(C1=CC=CC=C1)=C1N=NC(=N1)N Chemical compound P(O)(O)=O.C(C1=CC=CC=C1)=C1N=NC(=N1)N PBYZZYRFIYWCGB-UHFFFAOYSA-N 0.000 description 1
- CPPHBJHYOFTPHO-UHFFFAOYSA-N P(O)(O)=O.NC1=NNC=N1.P(O)(O)=O.N1N=CN=C1 Chemical compound P(O)(O)=O.NC1=NNC=N1.P(O)(O)=O.N1N=CN=C1 CPPHBJHYOFTPHO-UHFFFAOYSA-N 0.000 description 1
- RPCLNBNFLSDYGZ-UHFFFAOYSA-N P(O)(O)=O.[N+](=O)([O-])C1=CC=C(C=C2N=NC(=N2)N)C=C1 Chemical compound P(O)(O)=O.[N+](=O)([O-])C1=CC=C(C=C2N=NC(=N2)N)C=C1 RPCLNBNFLSDYGZ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- WLQXPAUZYVXSNE-UHFFFAOYSA-N [Ca].O[N+]([O-])=O Chemical compound [Ca].O[N+]([O-])=O WLQXPAUZYVXSNE-UHFFFAOYSA-N 0.000 description 1
- OWXLRKWPEIAGAT-UHFFFAOYSA-N [Mg].[Cu] Chemical compound [Mg].[Cu] OWXLRKWPEIAGAT-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- UMZZZCGXUOLFFT-UHFFFAOYSA-K cerium(3+);trinitrite Chemical compound [Ce+3].[O-]N=O.[O-]N=O.[O-]N=O UMZZZCGXUOLFFT-UHFFFAOYSA-K 0.000 description 1
- UNJPQTDTZAKTFK-UHFFFAOYSA-K cerium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ce+3] UNJPQTDTZAKTFK-UHFFFAOYSA-K 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229920000592 inorganic polymer Polymers 0.000 description 1
- MHKWSJBPFXBFMX-UHFFFAOYSA-N iron magnesium Chemical compound [Mg].[Fe] MHKWSJBPFXBFMX-UHFFFAOYSA-N 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- RAFRTSDUWORDLA-UHFFFAOYSA-N phenyl 3-chloropropanoate Chemical compound ClCCC(=O)OC1=CC=CC=C1 RAFRTSDUWORDLA-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/102—Metallic powder coated with organic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/14—Treatment of metallic powder
- B22F1/145—Chemical treatment, e.g. passivation or decarburisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
- C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2301/00—Metallic composition of the powder or its coating
- B22F2301/30—Low melting point metals, i.e. Zn, Pb, Sn, Cd, In, Ga
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Abstract
본 발명은 내식성이 우수한 코팅용 아연분말, 아연분말의 제조방법 및 아연분말 코팅강판에 관한 것으로서, 보다 상세하게는 내식성과 용접성을 확보하기 위하여 첨가하는 기타 첨가물을 최소화하여 코팅하여도 코팅층의 내식성과 용접성을 확보할 수 있는 안료로서 사용가능한 아연분말과 이러한 아연분말의 제조방법 및 아연분말이 코팅된 강판에 관한 것이다.
본 발명의 일구현례에 따르면, 별도의 추가 첨가제를 첨가하지 않거나 첨가를 최소화한 상태에서도 우수한 내식성과 용접성을 확보할 수 있는 도료용 아연계 분말이 제공된다.The present invention relates to a zinc powder for coating, a method for producing zinc powder, and a zinc powder coated steel sheet having excellent corrosion resistance, and more particularly, to a zinc powder coated steel sheet having excellent corrosion resistance and corrosion resistance, A zinc powder usable as a pigment capable of securing the weldability, a method of producing such a zinc powder, and a steel sheet coated with zinc powder.
According to one embodiment of the present invention, there is provided a zinc-based powder for a paint capable of securing excellent corrosion resistance and weldability even when no additional additive is added or the addition is minimized.
Description
본 발명은 내식성이 우수한 코팅용 아연분말, 아연분말의 제조방법 및 아연분말 코팅강판에 관한 것으로서, 보다 상세하게는 내식성과 용접성을 확보하기 위하여 첨가하는 기타 첨가물을 최소화하여 코팅하여도 코팅층의 내식성과 용접성을 확보할 수 있는 안료로서 사용가능한 아연분말과 이러한 아연분말의 제조방법 및 아연분말이 코팅된 강판에 관한 것이다.
The present invention relates to a zinc powder for coating, a method for producing zinc powder, and a zinc powder coated steel sheet having excellent corrosion resistance, and more particularly, to a zinc powder coated steel sheet having excellent corrosion resistance and corrosion resistance, A zinc powder usable as a pigment capable of securing the weldability, a method of producing such a zinc powder, and a steel sheet coated with zinc powder.
금속의 표면에는 다양한 이유로 금속 입자들이 코팅되는 경우가 많다. 특히 아연입자들은 내식성과 용접성을 향상시키기 위하여 많이 사용된다. 이러한 아연입자들의 특성에 관한 연구가 비특허문헌 [1]-[8]에 나타난 바와 같이 다양하게 이루어졌다.
Metal surfaces are often coated with metal particles for a variety of reasons. In particular, zinc particles are widely used to improve corrosion resistance and weldability. Studies on the properties of these zinc particles have been made variously as shown in Non-Patent Documents [1] - [8].
즉, 해양건축물 등이나 도로 교양 등을 보호하기 위하여 실시하는 소위 중(重) 방식 코팅용으로 아연입자를 유무기 고분자와 혼합하여 코팅하기도 하고, 자동차용 프리실드 강판 코팅용으로 내식성과 용접성을 동시에 향상시키기 위해 아연입자가 널리 이용되고 있다.
In other words, zinc particles can be mixed with organic and inorganic polymers for coating of so-called heavy coatings to protect marine buildings, roads, etc., and coating with corrosion resistance and weldability for automotive pre- Zinc grains are widely used to improve these properties.
프리실드 강판의 이용의 장점은 기존의 캐비티 왁스 스프레이를 강판이 겹쳐져서 용접되는 부위에 적용한 후 용접을 실시하는 방법의 문제점인 생산성 저하와 제조비용증가 문제를 해결할 수 있다는데 있다.
The advantage of the use of the pre-shielded steel sheet is that it can solve the problem of the decrease in the productivity and the increase in the manufacturing cost, which is a problem of the conventional method of applying the cavity wax spray to the welding spot where the steel sheet is overlapped and welded.
그런데, 이러한 아연분말이 함유된 코팅층을 이용할 때, 아연분말 단독 혼합으로는 코팅의 내식성을 향상시키는데 한계가 있기 때문에 여러가지 내식입자들을 함께 코팅층에 포함 시키려는 노력이 계속되고 있다. 이러한 내식입자를 포함시키는 방식은 내식입자 자체는 코팅의 방식성능을 향상시키는데 도움이 되지만, 코팅 자체의 물성을 훼손하는 문제점이 있다.
However, when the coating layer containing such a zinc powder is used, there is a limit to improve the corrosion resistance of the coating by the sole mixing of the zinc powder. Therefore, efforts have been made to include various corrosion resistant particles in the coating layer together. The method of incorporating such a corrosion-resistant particle is problematic in that although the corrosion-resistant particle itself helps improve the performance of the coating, the physical properties of the coating itself are impaired.
특히 이러한 방식이 자동차용 프리실드 강판 코팅에도 이용되는데, 이때 코팅은 일반 중 방식 코팅과 달리 용접성 확보를 위해 도막 두께가 10마이크로 이하로 박막코팅이 이용된다. 이러한 박막 코팅층에 내식성 및 용접성 더욱 향상을 위해 여러가지 입자를 포함시키게 되면, 코팅 자체의 물성을 심각하게 훼손하여 오히려 장기 내식성을 떨어뜨리는 요인으로 작용하게 되고, 기계적 물성도 훼손하게 된다.
Especially, this method is also applied to the pre-shielded steel sheet coating for automobile. Unlike the conventional type coating, the coating is thin film coated to a thickness of 10 microns or less to secure weldability. If such a thin film coating layer contains various particles for further improving the corrosion resistance and weldability, the physical properties of the coating itself may be seriously impaired, which may cause deterioration of long term corrosion resistance and impair mechanical properties.
예를 들면, 부식억제안료와 Fe2P 등과 같은 화합물을 아연계 도료에 함께 첨가하는 방법 등도 제안된바 있으나, 이러한 방법 역시 코팅층이 얇으면 아연분말이 함유된 아연계 도료의 기계적 특성을 열화시킨다는 문제가 있었다. 즉, 박막 아연계 도료의 코팅층은 통상 그 두께가 약 5㎛ 수준인 반면 첨가되는 안료 등의 입도가 수㎛에 달하기 때문에 이러한 조대한 입자들이 코팅층의 물성에 영향을 미치는 것이다. 뿐만 아니라, 입자크기에 비교적 자유로운 후막 코팅이라 하더라도 도료에 Fe2P 등과 같은 입자가 포함될 경우에는 코팅강판의 성형성에 열화되고 공구 마모 및 오염이 심해진다는 문제가 있다.
For example, a method of adding a corrosion-inhibiting pigment and a compound such as Fe2P to a zinc-based paint has been proposed. However, this method also has a problem that if the coating layer is thin, the mechanical properties of zinc-based paint containing zinc powder deteriorate there was. That is, the thickness of the coating layer of the thin film zinc-based coating is usually about 5 μm, while the particle size of the added pigment reaches a few micrometers, so that these coarse particles influence the physical properties of the coating layer. In addition, even if a thick film coating having a relatively large particle size is included, if the paint contains particles such as Fe2P, the formability of the coated steel sheet is deteriorated and the tool wear and contamination are increased.
본 발명의 일구현례에 따르면, 별도의 추가 첨가제를 첨가하지 않거나 첨가를 최소화한 상태에서도 우수한 내식성과 용접성을 확보할 수 있는 도료용 아연계 분말이 제공된다.
According to one embodiment of the present invention, there is provided a zinc-based powder for a paint capable of securing excellent corrosion resistance and weldability even when no additional additive is added or the addition is minimized.
본 발명의 또하나의 구현례에 따르면, 상기 아연계 분말을 제조할 수 있는 한가지 바람직한 제조방법이 제공된다.
According to another embodiment of the present invention, one preferred method of producing the zinc-based powder is provided.
본 발명의 또다른 하나의 구현례에 따르면, 상기 아연계 분말을 포함한 코팅층이 형성된 코팅강판이 제공된다.
According to another embodiment of the present invention, there is provided a coated steel sheet in which a coating layer containing the zinc-based powder is formed.
본 발명의 한가지 구현례에 따른 아연계 분말은 인산계 화합물, 포스폰산계 화합물, 카르복실기 함유 화합물, 아졸계 화합물 및 유기아민계 화합물 중 1종 이상의 화합물에 의해 표면개질된 내식성이 우수한 코팅용 아연분말이다.
The zinc-based powder according to one embodiment of the present invention is a zinc powder for coating which is surface-modified with at least one compound selected from a phosphoric acid compound, a phosphonic acid compound, a carboxyl group-containing compound, an azole compound and an organic amine compound to be.
이때, 상기 인산계 화합물은 하기 화학식1을 충족하는 것이 바람직하다.At this time, it is preferable that the phosphate compound satisfies the following formula (1).
단, 여기서 R 및 R'은 각각 독립적으로 수소, C1 -30의 알킬 혹은 사이클로 알킬, 또는 치환되거나 비치환된 페닐을 나타낸다.
However, where R and R 'are each independently hydrogen, alkyl or cycloalkyl of C 1 -30 alkyl, or a substituted or unsubstituted phenyl shows a beach.
또한, 상기 포스포산계 화합물은 아미노트리스 (메틸렌포스폰산) (aminotris(methylenephosphonic acid)), 에틸렌디아민 테트라(메틸렌 포스폰산)(ethylenediamine tetra(methylene phosphonic acid)), 니트릴로-트리스-포스폰산(nitrilo-tris-phosphonic acid), 글리신-N,N-디(메틸렌 포스폰산)(glycine-N,N-di(methylene phosphonic acid)), 이미노-N,N-디아세틱-N-메틸렌 포스폰산(imino-N,N-diacetic-N-methylene phosphonic acid), 에틸렌디아민 테트라포스폰산(ethylenediamine tetraphosphonic acid) 및 하이드록시에탄 1,1'-디포스폰산(hydroxyethane 1,1'-diphosphonic acid)으로 이루어진 군으로부터 선택된 하나 이상인 것이 유리하다.
Also, the above-mentioned phosphonic acid compound may be selected from the group consisting of aminotris (methylenephosphonic acid), ethylenediamine tetra (methylene phosphonic acid), nitrilo-tris-phosphonic acid -tris-phosphonic acid, glycine-N, N-di (methylene phosphonic acid), imino-N, N-diacetic-N-methylenephosphonic acid ( imino-N, N-diacetic-N-methylene phosphonic acid, ethylenediamine tetraphosphonic acid and hydroxyethane 1,1'-diphosphonic acid. ≪ / RTI >
또한, 상기 카르복실기 함유 화합물은 헥사메틸렌디아민 테트라아세트산(hexamethylenediamine tetraacetic acid), 디에틸렌티아민-N,N,N',N",N"-펜타아세트산(diethylenetiamine-N,N,N',N",N"-pentaacetic acid) 및 니트릴로-트리스-아세트산(nitrilo-tris-acetic acid)으로 이루어진 군으로부터 선택된 하나 이상인 것이 바람직하다.
Also, the carboxyl group-containing compound may be at least one selected from the group consisting of hexamethylenediamine tetraacetic acid, diethylenetiamine-N, N, N ', N ", N "-pentacetic acid- N "-pentaacetic acid, and nitrilo-tris-acetic acid.
그리고, 상기 아졸계 화합물은 2-아미노-5-에틸티오-1,3,4,-티아디아졸(2-amino-5-ethylthio-1,3,4-thiadiazole), 2-아미노-5-에틸-1,3,4-티아디아졸(2-amino-5-ethyl-1,3,4-thiadiazole), 5-(페닐)-4h-1,2,4-트리아졸-3-티올(5-(phenyl)-4H-1,2,4-triazole-3-thiole), 5-벤질이덴-2,4-디옥소테트라하이드로-1,3-티아졸(5-benzylidene-2,4-dioxotetrahydro-1,3-thiazole), 5-(4'-이소프로필벤질이덴)-2,4-디옥소테트라하이드로-1,3-티아졸(5-(4'-isopropylbenzylidene)-2,4-dioxotetrahydro-1,3-thiazole), 5-(3'-테닐리덴)-2,4-디옥소테트라하이드로-1,3-티아졸(5-(3'-thenylidene)-2,4-dioxotetrahydro-1,3-thiazole), 5-(3',4'-디메톡시벤질리덴)-2,4-디옥소테트라하이드로-1,3-티아졸(5-(3',4'-dimetoxybenzylidene)-2,4-dioxotetrahydro-1,3-thiazole), 5-머캅토-1 페닐=테트라졸(5-mercapto-1 phenyl-tetrazole), 2-머캅토벤조티아졸(2-mercaptobenzothiazole), 3-벤질리덴 아미노 1,2,4-트리아졸 포스포네이트(3-benzylidene amino 1,2,4-triazole phosphonate), 3-시나밀레덴 아미노 1,2,4-트리아졸 포스포네이트((3-cinnamyledene amino 1,2,4-triazole phosphonate), 3-살리실알리덴 아미노 1,2,4-트리아졸 포스포네이트(3-salicylalidene amino 1,2,4-triazole phosphonate), 3-파라니트로 벤질리덴 아미노 1,2,4-트리아졸 포스포네이트(3-paranitro benzylidene amino 1,2,4-triazole phosphonate), 1,2,4-트리아졸 3-아미노 1,2,4-트리아졸(1,2,4-triazole 3-amino 1,2,4-triazole), 3-아미노 머캅토 1,2,4-트리아졸(3-amino mercapto 1,2,4-triazole), 3-아미노 5-메틸티오 1,2,4-트리아졸(3-amino 5-methylthio 1,2,4-triazole) 및 세틸 트리메틸 암모늄 브로마이드(cetyl trimethyl ammonium bromide)로 이루어진 군으로부터 선택된 하나 이상인 것이 유리하다.
The azole compound may be 2-amino-5-ethylthio-1,3,4-thiadiazole, 2-amino-5- Ethyl-1,3,4-thiadiazole, 5- (phenyl) -4h-1,2,4-triazole-3-thiol ( 5- (phenyl) -4H-1,2,4-triazole-3-thiole, 5-benzylidene- 2, 4-dioxotetrahydro-1,3-thiazole -dioxotetrahydro-1,3-thiazole, 5- (4'-isopropylbenzylidene) -2,4-dioxotetrahydro-1,3-thiazole, 4-dioxotetrahydro-1,3-thiazole, 5- (3'-tenylidene) -2,4-dioxotetrahydro-1,3-thiazole 1,3-thiazole), 5- (3 ', 4'-dimethoxybenzylidene) -2,4-dioxotetrahydro-1,3-thiazole (5- dimethoxybenzylidene) -2,4-dioxotetrahydro-1,3-thiazole, 5-mercapto-1 phenyl-tetrazole, 2-mercaptobenzothiazole, 3-benzylideneamino 1,2,4-triazole phosphone 3-benzylidene amino 1,2,4-triazole phosphonate, 3-cinnamyledene amino 1,2,4-triazole phosphonate, 3 - 3-salicylalidene amino 1,2,4-triazole phosphonate, 3-panitrobenzylideneamino 1,2,4-triazole phosphonate 3-amino-1,2,4-triazole phosphonate, 1,2,4-triazole 3-amino 1,2,4- 4-triazole, 3-aminomercapto 1,2,4-triazole, 3-amino 5-methylthio 1,2,4-triazole (3- amino 5-methylthio 1,2,4-triazole, and cetyl trimethyl ammonium bromide.
삭제delete
또한, 상기 유기아민계 화합물은 암모니아, 소듐 하이드록사이드, 포타슘 하이드록사이드, 칼슘 하이드록사이드, N,N-디메틸에탄올아민, 트리에탄올아민, 디에탄올아민 및 몰포린으로 이루어진 군으로부터 선택된 하나 이상인 것이 바람직하다.
The organic amine compound is at least one selected from the group consisting of ammonia, sodium hydroxide, potassium hydroxide, calcium hydroxide, N, N-dimethylethanolamine, triethanolamine, diethanolamine and morpholine desirable.
또한, 상기 아연분말로는 상기 1 종 이상의 화합물 외에 제2족 금속이온 또는 희토류 금속을 더 포함하는 화합물에 의해 표면개질된 것이 사용될 수 있다.
The zinc powder may be one that is surface-modified with a compound further comprising a Group II metal ion or a rare earth metal in addition to the one or more compounds.
또한, 상기 1 종 이상의 화합물 외에 아연 산화물 또는 질산 나트륨의 화합물을 더 포함하는 화합물에 의해 표면개질된 것일 수 있다.
Further, it may be surface-modified with a compound further comprising a compound of zinc oxide or sodium nitrate in addition to the above-mentioned one or more compounds.
본 발명의 또한가지 구현례에 따른 아연분말의 제조방법은 인산계 화합물, 포스폰산계 화합물, 카르복실기 함유 화합물, 아졸계 화합물 및 유기아민계 화합물 중 1종 이상의 화합물이 첨가된 용액을 준비하는 단계; 상기 용액에 아연분말을 첨가하여 반응시키는 단계; 및 상기 반응된 아연분말을 회수하는 단계를 포함하는 것을 특징으로 한다.
According to still another embodiment of the present invention, there is provided a method for preparing a zinc powder, comprising: preparing a solution to which at least one compound selected from the group consisting of a phosphate compound, a phosphonic acid compound, a carboxyl group-containing compound, an azole compound and an organic amine compound is added; Adding zinc powder to the solution and reacting; And recovering the reacted zinc powder.
본 발명의 또한가지 구현례에 따른 아연분말 코팅강판은 상술한 아연분말과 수지가 혼합된 코팅제가 코팅된 것일 수 있다.
The zinc powder coated steel sheet according to further embodiments of the present invention may be coated with the above-mentioned zinc powder and resin mixed coating agent.
상술한 바와 같이, 본 발명의 구현례에 따르면 표면 개질된 아연분말이 도료에 첨가됨으로써 내식성의 획기적으로 향상시킴은 물론이고, 용접성까지 확보할 수 있다는 효과를 가진다.
As described above, according to the embodiment of the present invention, the surface-modified zinc powder is added to the coating material, thereby remarkably improving the corrosion resistance and securing the weldability.
도 1은 본 발명의 몇몇 구현례에 따른 아연분말을 깊이에 따른 성분 프로파일을 XPS 기법에 의해 분석한 결과를 나타낸 그래프,
도 2는 표면개질하지 않은 아연분말과 본 발명에 따라서 표면개질한 아연분말을 포함하는 코팅제를 강판의 표면에 코팅한 후의 부식시험결과를 나타내는 주사전자현미경 관찰사진,
도 3은 표면개질을 실시하지 않은 아연분말의 부식시험결과,
도 4는 발명예1~4의 조건으로 제조한 아연분말에 대하여 부식시험한 결과,
도 5는 표면개질하지 않은 아연분말과 본 발명의 구현례에 따라서 표면개질한 아연분말을 포함하는 코팅제를 강판의 표면에 코팅한 후 ASTM B117법에 의해 부식시험한 결과를 나타내는 주사전자현미경 관찰사진, 그리고
도 6은 발명예5 및 6의 조건으로 제조한 아연분말에 대하여 부식시험한 결과로서 a는 발명예5의 결과를 b는 발명예6의 결과를 나타낸다, 그리고
도 7은 발명예6, 7에 따라서 표면개질한 아연분말을 포함하는 코팅제를 강판의 표면에 코팅한 후 ASTM B117법에 의해 부식시험한 결과를 나타내는 주사전자현미경 관찰사진이다.FIG. 1 is a graph showing the results of analyzing the composition profile of a zinc powder according to depth according to some embodiments of the present invention by XPS technique; FIG.
2 is a scanning electron microscope photograph showing the result of corrosion test after coating the surface of a steel sheet with a coating agent comprising a surface-unmodified zinc powder and a surface-modified zinc powder according to the present invention,
3 shows the corrosion test results of the zinc powder without surface modification,
Fig. 4 shows the results of corrosion test on zinc powder prepared under the conditions of Inventive Examples 1 to 4,
FIG. 5 is a scanning electron microscope photograph showing the result of corrosion test according to ASTM B117 after coating the surface of a steel sheet with a coating agent containing a surface-modified zinc powder and a surface-modified zinc powder according to an embodiment of the present invention , And
6 shows the result of corrosion test on the zinc powder produced under the conditions of inventive examples 5 and 6, wherein a shows the result of Inventive example 5, b shows the result of Inventive example 6, and
FIG. 7 is a scanning electron microscope photograph showing the results of corrosion test according to the ASTM B117 method after coating the surface of a steel sheet with a coating agent containing a surface-modified zinc powder according to Examples 6 and 7 of the present invention.
이하, 본 발명을 상세하게 설명한다.
Hereinafter, the present invention will be described in detail.
본 발명의 발명자들은 상술한 종래기술의 문제점을 파악하고, 아연분말이 포함된 도료에 별도의 첨가물을 추가하는 것 보다는 아연분말의 표면을 개질할 경우 내식성 향상과 용접성 확보는 물론이고, 공구마모나 오염등의 문제도 야기하지 않는다는 사실을 발견하고 본 발명에 이르게 되었다.
The inventors of the present invention have been made aware of the problems of the prior art described above and have found that when the surface of a zinc powder is modified rather than adding an additive to a coating containing zinc powder, Contamination, and the like, and arrived at the present invention.
즉, 본 발명의 바람직한 한가지 구현례에 따르면, 표면이 개질된 아연분말이 제공된다. 상기 아연분말은 아연을 주성분으로 하는 분말로서 아연이 80중량% 이상 포함된 것이라면 어떠한 것도 사용가능하다. 이때, 입도가 과다하게 클 경우에는 코팅층의 두께가 두꺼워 질 수 있으므로 상기 아연분말의 최대 입도(구상당직경)은 도막의 두께보다는 작은 것이 바람직하고, 10mm 이하인 것이 더욱 바람직하다. 입도가 작을수록 표면적이 증가하여 내식성능이 향상될 수 있으므로 아연분말의 입도 하한은 특별히 제한하지 않는다. 특히, 박막 코팅의 경우에는 가능한한 작은 입도의 아연분말을 사용하는 것이 바람직하나 본 발명에서는 코팅의 종류를 박막과 후막을 가리지 않으므로 상술한 범위로 아연분말의 입도를 정한다.
That is, according to one preferred embodiment of the present invention, surface-modified zinc powder is provided. The zinc powder is a powder containing zinc as a main component and any powder may be used as long as it contains at least 80% by weight of zinc. At this time, if the particle size is excessively large, the thickness of the coating layer may become thick, so that the maximum particle size (spherical equivalent diameter) of the zinc powder is preferably smaller than the thickness of the coating film, and more preferably 10 mm or less. As the particle size is smaller, the surface area is increased and the corrosion resistance can be improved. Therefore, the lower limit of the particle size of the zinc powder is not particularly limited. Particularly, in the case of the thin film coating, it is preferable to use zinc powder having a small particle size as much as possible. In the present invention, since the kind of the coating is not limited to the thin film and the thick film, the particle size of the zinc powder is determined within the range described above.
상기 아연분말은 그 자체로도 우수한 내식성을 가지는 것이므로 금속의 표면에 코팅될 경우 내식성 확보가 용이하다. 이때, 분말의 내식성을 보다 향상시키기 위해서 아연의 표면을 개질처리하는 것이 바람직하다. 이러한 표면개질로서 아연 분말의 내식성은 더욱 향상될 수 있으며, 이러한 아연분말을 포함하는 도료가 금속에 코팅되면 금속의 내식성능이 향상되는 것이다.
Since the zinc powder itself has excellent corrosion resistance, it is easy to ensure corrosion resistance when coated on the surface of metal. At this time, in order to further improve the corrosion resistance of the powder, it is preferable to modify the surface of the zinc. Such surface modification can further improve the corrosion resistance of the zinc powder, and when the coating including the zinc powder is coated on the metal, the corrosion resistance of the metal is improved.
아연분말의 표면개질은 인산계 화합물, 포스폰산계 화합물, 카르복실기 함유 화합물, 아졸계 화합물 및 유기아민계 화합물 중 1종 이상의 화합물로 실시하는 것이 바람직하다. 따라서, 본 발명의 일구현례에 따른 아연분말은 표면에 상술한 화합물을 포함하는 아연분말인 것이다. 특히, 본 발명에서 일컫는 개질이라 함은 코팅의 일종으로서, 아연분말의 표면에 상술한 성분들이 화학적으로 결합된 것을 의미하며, 그 한가지 일례로서 도 1에 도시한 형태의 성분 프로파일을 나타내는 경우를 들 수 있다. 도면에서 볼 수 있듯이, 단순히 아연분말의 표면을 물리적으로 커버하고 있는 것이 아니라, 아연분말의 표면과 화학적으로 결합하여 농도 구배를 가지고 있음을 확인할 수 있다. 도 1에서 (a)는 개질전의 아연분말을 나타내며, (b), (c), (d) 및 (d)는 본 발명의 개별 구현례에 따라서 표면을 개질한 아연분말을 나타낸다.
The surface modification of the zinc powder is preferably carried out with at least one of a phosphoric acid compound, a phosphonic acid compound, a carboxyl group-containing compound, an azole compound and an organic amine compound. Thus, the zinc powder according to an embodiment of the present invention is a zinc powder containing the above-described compound on its surface. In particular, the modification referred to in the present invention is a kind of coating, which means that the above-mentioned components are chemically bonded to the surface of the zinc powder. One example of such a modification is a component profile of the form shown in FIG. 1 . As can be seen from the figure, it can be seen that the surface of the zinc powder is not physically covered but chemically bonded to the surface of the zinc powder to have a concentration gradient. 1 (a) shows the zinc powder before reforming, and (b), (c), (d) and (d) show the surface modified zinc powder according to an embodiment of the present invention.
상기 아연분말의 표면개질에 사용되는 화합물(이하, 간략히 '표면개질용 화합물'이라고도 함)은 철, 알루미늄 또는 아연과 같은 금속 표면에 안정한 내식성 막을 형성하기 때문에 이들의 내식성을 더욱 향상시켜준다. 이때, 상기 화합물들은 아연분말의 표면에 막을 형성하면 될 뿐, 그 중량적인 비율제한은 특별히 하지 않는다.
The compound used for surface modification of the zinc powder (hereinafter, simply referred to as 'surface modifying compound') forms a stable corrosion-resistant film on the surface of metal such as iron, aluminum or zinc, thereby further improving the corrosion resistance thereof. At this time, the compounds only need to form a film on the surface of the zinc powder, and the weight ratio thereof is not particularly limited.
여기서, 인산계 화합물은 그 종류를 제한하지 않고 모두 본 발명에서 사용가능하나, 하기 화학식 1로 표시되는 것이 보다 바람직하다.
Here, the phosphoric acid compound is not limited in its kind but can be used in the present invention, but it is more preferably represented by the following general formula (1).
[화학식 1][Chemical Formula 1]
단, 여기서 R 및 R'은 각각 독립적으로 수소, C1 -30의 알킬 혹은 사이클로 알킬, 또는 치환되거나 비치환된 페닐을 나타낸다.
However, where R and R 'are each independently hydrogen, alkyl or cycloalkyl of C 1 -30 alkyl, or a substituted or unsubstituted phenyl shows a beach.
또한, 포스포산계 화합물로는 아미노트리스 (메틸렌포스폰산) (aminotris(methylenephosphonic acid)), 에틸렌디아민 테트라(메틸렌 포스폰산)(ethylenediamine tetra(methylene phosphonic acid)), 니트릴로-트리스-포스폰산(nitrilo-tris-phosphonic acid), 글리신-N,N-디(메틸렌 포스폰산)(glycine-N,N-di(methylene phosphonic acid)), 이미노-N,N-디아세틱-N-메틸렌 포스폰산(imino-N,N-diacetic-N-methylene phosphonic acid), 에틸렌디아민 테트라포스폰산(ethylenediamine tetraphosphonic acid) 및 하이드록시에탄 1,1'-디포스폰산(hydroxyethane 1,1'-diphosphonic acid)으로 이루어진 군으로부터 선택된 하나 이상인 것이 보다 바람직하다.
Examples of the phosphoric acid-based compound include aminotris (methylenephosphonic acid), ethylenediamine tetra (methylene phosphonic acid), nitrilo-tris-phosphonic acid -tris-phosphonic acid, glycine-N, N-di (methylene phosphonic acid), imino-N, N-diacetic-N-methylenephosphonic acid ( imino-N, N-diacetic-N-methylene phosphonic acid, ethylenediamine tetraphosphonic acid and hydroxyethane 1,1'-diphosphonic acid. Is more preferable.
또한, 카르복실기 함유 화합물로는 헥사메틸렌디아민 테트라아세트산(hexamethylenediamine tetraacetic acid), 디에틸렌티아민-N,N,N',N",N"-펜타아세트산(diethylenetiamine-N,N,N',N",N"-pentaacetic acid) 및 니트릴로-트리스-아세트산(nitrilo-tris-acetic acid)으로 이루어진 군으로부터 선택된 하나 이상을 사용하는 것이 보다 바람직하다.
Examples of the carboxyl group-containing compound include hexamethylenediamine tetraacetic acid, diethylenetiamine-N, N, N ', N'', N "-pentacetic acid (N, N' N "-pentaacetic acid, and nitrilo-tris-acetic acid) is more preferably used.
또한, 아졸계 화합물로는 2-아미노-5-에틸티오-1,3,4,-티아디아졸(2-amino-5-ethylthio-1,3,4-thiadiazole), 2-아미노-5-에틸-1,3,4-티아디아졸(2-amino-5-ethyl-1,3,4-thiadiazole), 5-(페닐)-4h-1,2,4-트리아졸-3-티올(5-(phenyl)-4H-1,2,4-triazole-3-thiole), 5-벤질이덴-2,4-디옥소테트라하이드로-1,3-티아졸(5-benzylidene-2,4-dioxotetrahydro-1,3-thiazole), 5-(4'-이소프로필벤질이덴)-2,4-디옥소테트라하이드로-1,3-티아졸(5-(4'-isopropylbenzylidene)-2,4-dioxotetrahydro-1,3-thiazole), 5-(3'-테닐리덴)-2,4-디옥소테트라하이드로-1,3-티아졸(5-(3'-thenylidene)-2,4-dioxotetrahydro-1,3-thiazole), 5-(3',4'-디메톡시벤질리덴)-2,4-디옥소테트라하이드로-1,3-티아졸(5-(3',4'-dimetoxybenzylidene)-2,4-dioxotetrahydro-1,3-thiazole), 5-머캅토-1 페닐=테트라졸(5-mercapto-1 phenyl-tetrazole), 2-머캅토벤조티아졸(2-mercaptobenzothiazole), 3-벤질리덴 아미노 1,2,4-트리아졸 포스포네이트(3-benzylidene amino 1,2,4-triazole phosphonate), 3-시나밀레덴 아미노 1,2,4-트리아졸 포스포네이트((3-cinnamyledene amino 1,2,4-triazole phosphonate), 3-살리실알리덴 아미노 1,2,4-트리아졸 포스포네이트(3-salicylalidene amino 1,2,4-triazole phosphonate), 3-파라니트로 벤질리덴 아미노 1,2,4-트리아졸 포스포네이트(3-paranitro benzylidene amino 1,2,4-triazole phosphonate), 1,2,4-트리아졸 3-아미노 1,2,4-트리아졸(1,2,4-triazole 3-amino 1,2,4-triazole), 3-아미노 머캅토 1,2,4-트리아졸(3-amino mercapto 1,2,4-triazole), 3-아미노 5-메틸티오 1,2,4-트리아졸(3-amino 5-methylthio 1,2,4-triazole) 및 세틸 트리메틸 암모늄 브로마이드(cetyl trimethyl ammonium bromide)로 이루어진 군으로부터 선택된 하나 이상을 사용하는 것이 보다 바람직하다.
Examples of the azole compound include 2-amino-5-ethylthio-1,3,4-thiadiazole, 2-amino-5- Ethyl-1,3,4-thiadiazole, 5- (phenyl) -4h-1,2,4-triazole-3-thiol ( 5- (phenyl) -4H-1,2,4-triazole-3-thiole, 5-benzylidene- 2, 4-dioxotetrahydro-1,3-thiazole -dioxotetrahydro-1,3-thiazole, 5- (4'-isopropylbenzylidene) -2,4-dioxotetrahydro-1,3-thiazole, 4-dioxotetrahydro-1,3-thiazole, 5- (3'-tenylidene) -2,4-dioxotetrahydro-1,3-thiazole 1,3-thiazole), 5- (3 ', 4'-dimethoxybenzylidene) -2,4-dioxotetrahydro-1,3-thiazole (5- dimethoxybenzylidene) -2,4-dioxotetrahydro-1,3-thiazole, 5-mercapto-1 phenyl-tetrazole, 2-mercaptobenzothiazole, 3-benzylideneamino 1,2,4-triazole phosphonate (3 -benzylidene amino 1,2,4-triazole phosphonate), 3-cinnamylenedene amino 1,2,4-triazole phosphonate, 3-salicyl phosphonate, 3-salicylalidene amino 1,2,4-triazole phosphonate, 3-panitrobenzylideneamino 1,2,4-triazole phosphonate (3- paranitro benzylidene amino 1,2,4-triazole phosphonate, 1,2,4-triazole 3-amino 1,2,4-triazole ), 3-amino mercapto 1,2,4-triazole, 3-amino 5-methylthio 1,2,4-triazole (3-amino 5- methylthio-1,2,4-triazole, and cetyl trimethyl ammonium bromide. It is more preferable to use at least one selected from the group consisting of methylthio, 1,2,4-triazole and cetyl trimethyl ammonium bromide.
삭제delete
상기 유기아민계 화합물로서는 N,N-디메틸에탄올아민, 트리에탄올아민, 디에탄올아민 및 몰포린으로 이루어진 군으로부터 선택된 하나 이상일 수 있다.
The organic amine compound may be at least one selected from the group consisting of N, N-dimethylethanolamine, triethanolamine, diethanolamine and morpholine.
상술한 본 발명의 일구현례에 따른 아연분말은 다른 첨가물 없이도 충분한 내식성을 발현시킬 수 있기 때문에, 용접성에 특별한 악영향을 미치지 않는다.
The zinc powder according to one embodiment of the present invention described above can exhibit sufficient corrosion resistance even without other additives, so that the weldability is not adversely affected.
상술한 형태로 표면이 개질된 아연분말은 그 자체로도 우수한 내식성과 용접성을 가지나, 상기 표면개질용 화합물에 주기율표상 제2족 금속이온 또는 희토류 금속이온 등을 추가로 첨가하는 것이 보다 바람직하다. 즉, 도 2에 도시한 바와 같이 아무런 개질처리하지 않은 아연분말로 코팅한 경우(a)에 비하여 상술한 형태로 표면을 개질(도면은 인산계 수용액으로 표면개질한 경우를 나타냄)한 경우(여기서, 인산계 수용액으로는 인산 2-에틸헥시 에테르를 사용하였다)(b)가 우수한 내식성을 나타내고 있었으며, 또한 제2족 금속이온의 하나인 Ca 이온을 추가로 첨가한 경우(c)가 보다 양호한 내식성을 나타낸다. 즉, 시편 표면 사진으로부터 볼 때 (a)의 경우는 붉은 녹이 시편 전체에 발생한 것에 비하여, (b), (c)로 갈수록 녹 발생정도는 감소함을 확인할 수 있으며, 아래의 주사전자현미경 사진을 통해 보면 (a)의 코팅표면에 균열이 발생한 반면 (b), (c)는 균열이 발생하지 않음을 알 수 있다. 이는 개질층 전체에 상기 제2족 금속이온이 존재하고 그 금속이온이 상술한 표면개질용 화합물과 함께 더욱 견고한 개질층을 만들기 때문인 것으로 추정된다.
The surface-modified zinc powder in the above-described form has excellent corrosion resistance and weldability per se, but it is more preferable to add a Group II metal ion, a rare earth metal ion, or the like to the surface modifying compound. That is, as shown in Fig. 2, when the surface is modified in the above-described manner (when the surface is modified with a phosphoric acid aqueous solution) compared to (a) in the case of coating with the unmodified zinc powder , And phosphoric acid 2-ethylhexyether was used as the phosphoric acid aqueous solution.) (B) exhibited excellent corrosion resistance. Further, when Ca ions as one of the Group 2 metal ions were further added, (c) Corrosion resistance. From the photographs of the specimen surface, it can be seen that the rust generation decreases in (a) to (b) and (c) compared to the case where red rust occurs in the entire specimen. (B) and (c) show that no cracks are generated in the coating surface of (a). This is presumed to be because the second group metal ion exists in the entire modified layer and the metal ion makes a more rigid modified layer together with the above-mentioned surface modifying compound.
상기 제2족 금속이온으로는 Mg, Ca, Sr 등을 사용하는 것이 보다 바람직하며, 희토류 금속이온으로는 Ce, La 등을 사용하는 것이 보다 바람직하다. 이들은 표면에 형성된 막을 경화시키는 작용을 하는 것으로서 형성된 부동태 막이 견고하게 존재하도록 한다.
As the second group metal ion, Mg, Ca, Sr or the like is more preferably used, and as the rare earth metal ion, Ce, La or the like is more preferably used. These act to harden the film formed on the surface, so that the formed passive film is firmly present.
기타, 반응속도를 제어하거나 반응결과 생성되는 수소를 제거하거나 슬러리의 형성을 제어하기 위하여 아연 산화물 또는 질산 나트륨 등의 화합물이 더 포함될 수 있다. 이들 화합물은 상기 표면개질용 화합물의 중량대비 30중량% 이하로 포함될 수 있다.
Other compounds such as zinc oxide or sodium nitrate may be further added to control the reaction rate or to remove hydrogen generated as a result of the reaction or to control the formation of the slurry. These compounds may be contained in an amount of 30% by weight or less based on the weight of the surface modifying compound.
상술한 본 발명의 유리한 아연분말은 수지에 혼합되어 강판코팅제로 사용될 수 있다. 강판코팅제에 포함되는 상기 수지는 강판 코팅에 사용되는 종래의 수지 종류라면 어떠한 것이라도 사용가능하나, 보다 바람직하게는 에스테르 수지, 우레탄 수지, 아크릴 수지 및 올레핀 수지로 이루어진 군으로부터 선택된 하나 이상을 사용할 수 있다.
The advantageous zinc powder of the present invention can be mixed with a resin and used as a steel sheet coating agent. The resin included in the steel sheet coating agent can be any conventional resin used for coating steel sheet, but more preferably one or more selected from the group consisting of an ester resin, a urethane resin, an acrylic resin and an olefin resin can be used have.
이때, 수지 중 아연분말은 전체 강판코팅제 100 중량부에 대하여 5 내지 60중량부 포함되는 것이 바람직한데, 이는 아연분말의 양이 너무 적을 경우에는 충분한 내식효과를 기대하기 어렵기 때문이며, 반대로 아연분말의 양이 너무 많을 경우에는 부착이 불량할 뿐만 아니라 코팅층에 균열 등을 야기할 우려가 있기 때문이다.
At this time, it is preferable that the zinc powder in the resin is included in an amount of 5 to 60 parts by weight with respect to 100 parts by weight of the whole steel sheet coating agent. If the amount of zinc powder is too small, it is difficult to expect sufficient corrosion resistance. On the other hand, If the amount is too large, there is a fear that not only the adhesion is poor but also the coating layer is cracked.
이러한 강판코팅제는 코팅후 경화된 후 수지와 아연분말로 구성되는데, 경화후의 아연분말의 비율은 10~60부피% 수준으로 변화한다.
Such a steel plate coating agent is composed of resin and zinc powder after curing after coating, and the ratio of zinc powder after curing changes to 10 to 60 volume% level.
이러한 수지는 금속의 표면에 코팅될 경우, 금속의 내식성을 크게 향상시킬 수 있다. 수지가 코팅됨으로써 내식성 향상의 효과를 얻을 수 있는 금속은 금속종류라면 모두 사용가능한 것으로서, 그 대상을 특별히 제한하지 않는다. 다만, 보다 바람직한 효과를 거둘 수 있는 금속으로서는 강(steel)을 들 수 있으며, 강판과 같이 판재나 시트 형태로 제공된 강의 표면에 코팅하는 것이 보다 바람직하다. 이러한 강판으로서는, 냉연강판, 아연도금강판, 아연계 전기도금강판, 용융아연도금강판, 알루미늄도금강판, 기타 코발트, 몰리브덴, 텅스텐, 니켈, 티탄, 알루미늄, 망간, 철 마그네슘, 주석, 동 또는 이들의 혼합물인 불순물 또는 이종금속을 함유한 도금층을 가지는 도금강판, 실리콘, 동 마그네슘, 철, 망간, 티탄, 아연 또는 이들의 혼합물을 첨가한 알루미늄 합금도금강판; 인산염이 도포된 아연도금강판; 냉연강판; 및 열연강판 중에서 선택될 수 있다.
When such a resin is coated on the surface of a metal, the corrosion resistance of the metal can be greatly improved. The metal that can obtain the effect of improving the corrosion resistance by coating the resin is not particularly limited as long as it is a metal. However, as a metal that can have a more preferable effect, steel is exemplified, and it is more preferable to coat the surface of the steel provided in the form of a sheet material or a sheet like a steel sheet. Examples of such steel sheets include cold-rolled steel sheets, galvanized steel sheets, galvanized electroplated steel sheets, hot-dip galvanized steel sheets, aluminum-coated steel sheets and other cobalt, molybdenum, tungsten, nickel, titanium, aluminum, manganese, iron magnesium, A plated steel sheet having a plating layer containing a dopant or a dissimilar metal which is a mixture, an aluminum alloy plated steel sheet to which silicon, copper magnesium, iron, manganese, titanium, zinc or a mixture thereof is added; Galvanized steel plates coated with phosphate; Cold rolled steel sheets; And a hot-rolled steel sheet.
다음으로, 상술한 본 발명의 유리한 아연분말을 제조하는 방법에 대하여 설명한다.
Next, a method for producing the advantageous zinc powder of the present invention will be described.
우선, 표면개질은 본 발명의 유리한 표면개질용 화합물을 첨가한 용액을 준비하는 단계로부터 시작된다. 이때, 상기 용액 중 화합물의 양은 화합물의 종류별로 조금씩 상이할 수 있으나, 각 표면개질용 화합물의 몰 농도의 총합이 0.1~1M이 되도록 첨가되는 것이 바람직하다. 화합물의 양이 너무 적을 경우에는 충분한 표면개질 효과를 얻을 수 없어 바람직하지 아니하며, 반대로 화합물의 양이 너무 많을 경우에는 기대치 이상으로 표면개질제가 부착되여 불리하기 때문이다. 용매로서는 물을 사용할 수 있으며, 알코올 등도 사용할 수 있다.
First, surface modification begins with preparing a solution to which an advantageous surface modifying compound of the present invention is added. At this time, the amount of the compound in the solution may be slightly different depending on the kind of the compound, but it is preferably added so that the total molar concentration of each surface modifying compound is 0.1 to 1 M. If the amount of the compound is too small, a sufficient surface modifying effect can not be obtained, which is undesirable. On the contrary, when the amount of the compound is too large, the surface modifying agent adheres to the expected value or more. As the solvent, water can be used, and alcohol and the like can also be used.
또한, 상기 표면개질용 화합물이 첨가된 용액의 pH는 7~11로 조절하는 것이 바람직하다. 즉, 산성에서 처리할 경우에는 아연입자가 쉽게 해리되어 버리기 때문에 상기 pH는 7 이상인 것이 바람직하며, 충분한 반응성을 확보하기 위하여 11 이하의 범위로 제한한다. 통상은 상기 표면개질용 화합물의 첨가만으로도 충분하겠으나, 통상 사용되는 산이나 염기 등의 pH 조절제를 사용하여 추가조절하는 경우도 배제하지 않는다.
The pH of the solution to which the surface modifying compound is added is preferably adjusted to 7 to 11. That is, in the case of acid treatment, the zinc particles easily dissociate, so that the pH is preferably 7 or more, and is limited to 11 or less in order to ensure sufficient reactivity. Normally, the addition of the above-mentioned surface modifying compound alone is sufficient, but further adjustment using a pH adjusting agent such as a commonly used acid or base is not excluded.
또한, 상기 용액에는 주기율표상 제2족 금속이온 또는 희토류 금속이온 등이 추가로 첨가될 수 있다. 이때, 충분한 첨가효과를 얻기 위하여 상기 제2족 금속이온 또는 희토류 금속이온 등은 이들이 포함된 화합물 기준으로 용액 1000g당 300g이하의 비율로 첨가되는 것이 바람직하다. 과다하게 첨가될 경우에는 표면에 스케일 층이 형성 되어 아연분말의 전기적인 특성을 훼손하여 용접성등에 악영향을 미칠 수 있다. 상기 제2족 금속이온 또는 희토류 금속이온 등은 어떠한 형태로도 첨가될 수 있으나, 몇가지 예를 들면 수산화물(hydroxide), 아질산염(nitrite), 질산염(nitrate) 등의 형태로 첨가될 수 있고, 보다 구체적으로는 수산화 칼슘(Calcium hydroxide), 칼슘 아질산염(Calcium nitrite), 질산칼슘(Calcium nitrate), 수산화 세륨(Cerium hydroxide), 세륨 아질산염(Cerium nitrite), 질산세륨(Cerium nitrate) 등의 형태로 첨가될 수 있다.
Further, the solution may further contain a Group II metal ion, a rare earth metal ion, or the like in the periodic table. At this time, in order to obtain a sufficient addition effect, it is preferable that the Group 2 metal ion, the rare earth metal ion and the like are added at a ratio of 300 g or less per 1000 g of the solution based on the compound containing them. If it is added in an excessive amount, a scale layer may be formed on the surface, thereby damaging the electrical characteristics of the zinc powder and adversely affecting the weldability and the like. The second group metal ion or rare earth metal ion may be added in any form, but may be added in the form of a hydroxide, nitrite, or nitrate. May be added in the form of calcium hydroxide, calcium nitrite, calcium nitrate, cerium hydroxide, cerium nitrite, cerium nitrate and the like. have.
이후, 상기 용액에 아연분말을 첨가하는 단계가 후속한다. 아연분말을 첨가할 때 원활한 반응을 위하여 용액을 교반할 수도 있다. 상기 아연분말은 용액속에 적어도 1시간 이상 체류하도록 하여 충분한 반응이 일어나도록 할 필요가 있다. 아연분말의 체류시간은 길어도 상관없으나, 시간이 길어져도 더이상 효과가 증가하지 않을 뿐만 아니라 공정시간을 길게하는 요인이 될 수도 있으므로 상기 아연분말의 체류시간은 48시간 이하로 한정한다. 이와 같은 과정에 의하여 아연분말의 표면은 개질된다.
This is followed by the step of adding zinc powder to the solution. When the zinc powder is added, the solution may be stirred for smooth reaction. It is necessary that the zinc powder is allowed to stay in the solution for at least 1 hour or more to cause sufficient reaction to occur. The residence time of the zinc powder may be long, but the longer the time is, the longer the effect is not increased and the longer the process time may become, so the residence time of the zinc powder is limited to 48 hours or less. The surface of the zinc powder is modified by this process.
상기 표면개질된 아연분말은 이후 용액과 분리되어 회수된다. 아연분말의 분리는 통상의 용액중 고상 분리법이라면 어떠한 것이라도 사용가능하다. 다만, 몇가지 예를 든다면, 여과법이나 원심분리법 등을 사용할 수 있다.
The surface-modified zinc powder is then recovered separately from the solution. Separation of the zinc powder can be carried out in any conventional solid-phase separation method. However, filtration, centrifugation, etc. can be used for some examples.
따라서, 본 발명은 표면개질용 화합물이 첨가된 용액을 준비하는 단계; 상기 용액에 아연분말을 첨가하여 반응시키는 단계; 및 상기 반응된 아연분말을 회수하는 단계를 포함한다.
Accordingly, the present invention provides a method for preparing a surface modification solution, comprising: preparing a solution to which a surface modifying compound is added; Adding zinc powder to the solution and reacting; And recovering the reacted zinc powder.
이후 회수된 아연분말은 건조과정을 더 거칠 수 있다. 건조는 통상의 건조방법이라면 어떠한 것이라도 사용할 수 있으며, 특히 본 발명에서 유리하게 사용될 수 있는 방법으로서 일정한 온도로 유지되는 항온조 또는 오븐에 상기 아연분말을 장입하여 분말이 건조되도록 하는 방법을 들 수 있다.
The recovered zinc powder may then be subjected to a further drying step. The drying can be carried out in any conventional drying method. In particular, as a method which can be advantageously used in the present invention, there is a method of charging the zinc powder into a thermostat or an oven maintained at a constant temperature to dry the powder .
이하, 실시예를 통하여 본 발명을 설명한다. 다만, 본 발명의 실시예는 본 발명을 구체화하여 예시하기 위한 것일 뿐 본 발명의 권리범위를 제한하기 위한 것이 아니라는 점에 유의할 필요가 있다. 본 발명의 권리범위는 특허청구범위에 기재된 사항과 이로부터 합리적으로 유추되는 사항에 의하여 결정되는 것이기 때문이다.
Hereinafter, the present invention will be described by way of examples. It should be noted, however, that the embodiments of the present invention are intended to illustrate the present invention only and not to limit the scope of the present invention. And the scope of the present invention is determined by the matters described in the claims and the matters reasonably deduced therefrom.
(실시예)(Example)
하기 표 1에 도시한 조건으로 용액을 준비하고 아연분말을 상기 용액에 첨가한 후 용액을 24시간 동안 교반시키면서 반응을 유도하였다. 아연분말은 SB 케미컬(대한민국)제를 사용하였으며, 그 평균입도가 5㎛를 나타내고 있었다.
The solution was prepared under the conditions shown in Table 1 below, the zinc powder was added to the solution, and the solution was stirred for 24 hours to induce the reaction. The zinc powder was manufactured by SB Chemical (Korea), and the average particle size thereof was 5 탆.
단, 여기서 아연산화물은 삼전화학(주)(Samchun pure chemical Co. Ltd., Korea)의 제품을 사용하였으며, 아질산나트륨은 일본의 간토 화학(Kanto Chemical Co., Ltd)의 제품을 사용하였으며, 질산칼슘은 대정화금(Daejung Chemicals & Metals co., Ltd., Korea)의 제품을, 그리고 인산 2-에틸헥시 에스테르와 아미노트리메틸렌 포스폰산은 모두 도쿄 케미컬 인더스트리(Tokyo Chemical Industry Co., Ltd., Japan)의 제품을 이용하였다.
Here, the zinc oxide was a product of Samchun Pure Chemical Co., Ltd., sodium nitrite was manufactured by Kanto Chemical Co., Ltd., and nitric acid Calcium is a product of Daejung Chemicals & Metals Co., Ltd., Korea. Phosphoric acid 2-ethylhexyester and aminotrimethylenephosphonic acid are both manufactured by Tokyo Chemical Industry Co., Ltd. , Japan) were used.
상술한 과정에 의해 표면이 개질된 아연분말을 여과하여 용액으로부터 분리하였으며, 이후 100℃로 유지되는 항온조에서 건조하여 표면이 개질된 아연분말을 얻었다. 100℃ 이상에서 처리 할 경우 개질된 표면물질의 물성을 변화시킬 우려가 있다.
The surface-modified zinc powder was separated from the solution by filtration by the above-described procedure, and then dried in a thermostat maintained at 100 ° C to obtain a surface-modified zinc powder. There is a possibility that the physical properties of the modified surface material may be changed when the treatment is carried out at 100 占 폚 or more.
상기 방법으로 표면개질된 아연분말들과의 비교를 위하여 상기 발명예와 동일하되 다만 용액에 의한 표면개질을 실시하지 않은 아연분말도 함께 그 부식성능을 비교하였다.
For comparison with the surface-modified zinc powders by the above-mentioned method, the corrosion performance of the zinc powder which is the same as that of the above-described embodiment but not surface-modified by solution was also compared.
도 3에 표면개질을 실시하지 않은 아연분말의 부식시험결과를 나타내었다. 부식시험은 염수 분무(salt spray)(5% NaCl 용액, 270 분) → 건조 (35% RH, 40℃, 90분)으로 이루어지는 과정을 4사이클 반복하는 과정으로 수행하였다. 도면에서 (a)는 부식시험 전의 아연분말을 주사전자현미경(SEM)으로 관찰한 결과를 나타내며, (b)는 부식시험후의 아연분말을 주사전자현미경(SEM)으로 관찰한 나타낸다. 도면에서 볼 수 있듯이, 부식으로 인하여 아연분말의 원형이 매우 급격하게 훼손되었음을 알 수 있다. 이러한 아연분말을 도료로 사용할 경우 도료의 방식성능이 빨리 열화되어 버리는 문제가 있을 수 있다.
Fig. 3 shows the corrosion test results of the zinc powder without surface modification. The corrosion test was carried out by repeating 4 cycles of a salt spray (5% NaCl solution, 270 minutes) → drying (35% RH, 40 ° C, 90 minutes). In the figure, (a) shows the result of observation of the zinc powder before the corrosion test with a scanning electron microscope (SEM), and (b) shows the zinc powder after the corrosion test with a scanning electron microscope (SEM). As can be seen from the figure, it can be seen that the prototype of the zinc powder was very rapidly damaged due to corrosion. If such a zinc powder is used as a coating material, the performance of the coating material may be deteriorated quickly.
반면 발명예1~4의 조건으로 제조한 아연분말에 대하여 동일한 조건으로 부식시험한 결과인 도 4(도면에서 a, b, c, d는 각각 발명예1, 2, 3, 4를 나타낸다)에서 확인할 수 있듯이, 본 발명의 조건으로 표면개질한 아연분말은 부식시험후에도 원형을 거의 그대로 유지하고 있음을 확인할 수 있다. 따라서, 이러한 아연분말을 도료로 사용할 경우 우수한 내식성능을 유지할 수 있음을 알 수 있다.
On the other hand, FIG. 4 (a, b, c, and d in the drawings show inventive examples 1, 2, 3 and 4, respectively), which is a result of corrosion test under the same conditions for the zinc powder produced under the conditions of Inventive Examples 1 to 4 As can be seen, it can be confirmed that the zinc powder surface-modified under the conditions of the present invention retains almost the original shape even after the corrosion test. Therefore, it can be seen that excellent corrosion resistance can be maintained when such a zinc powder is used as a paint.
도 1에 각 아연분말의 표면을 XPS 분석한 결과를 나타내었다. 도면에서 a는 표면개질처리하지 않은 아연분말을 분석한 결과를 나타내며, b, c, d, e는 각각 발명예1, 2, 3, 4의 아연분말을 분석한 결과를 나타낸다. 도면에서 볼 수 있듯이, 표면개질처리하지 않은 아연분말의 경우(a)에 비하여 표면개질처리하지 않은 아연분말의 표면에는 본발명의 유리한 조건을 충족하도록 각종 화합물이 형성되어 표면개질층을 형성함으로써 아연분말의 내식성을 향상시켰기 때문에 상술한 결과가 얻어진 것으로 판단된다. 상기 표면개질층의 두께는 60~90nm를 나타내고 있었다.
FIG. 1 shows the results of XPS analysis of the surface of each zinc powder. In the figure, a represents the result of analyzing the zinc powder not subjected to the surface modification treatment, and b, c, d and e represent the results of analysis of the zinc powders of Examples 1, 2, 3 and 4, respectively. As shown in the drawing, in the case of the zinc powder not subjected to the surface modification treatment, various compounds were formed on the surface of the zinc powder not subjected to the surface modification treatment to form the surface modification layer to satisfy the advantageous condition of the present invention, It was judged that the above-mentioned results were obtained because the corrosion resistance of the powder was improved. The thickness of the surface modification layer was 60 to 90 nm.
상술한 각 아연분말을 수지에 혼합하여 강판코팅제를 제조하였다. 이때, 수지로는 에스테르 수지를 사용하였으며, 경화 후 전체 강판 코팅 층 100 부피비에 대하여 40부피부(PVC-pigment volume concentration)가 되도록 아연분말을 혼합하였다.
Each of the above zinc powders was mixed with a resin to prepare a steel sheet coating agent. At this time, an ester resin was used as a resin, and zinc powder was mixed so as to have a PVC-pigment volume concentration of 40 parts per 100 parts by volume of the whole steel sheet coating layer after curing.
상술한 강판코팅제를 냉연강판의 표면에 코팅한 후 ASTM B117법에 의해 부식시험한 결과를 도 5에 나타내었다. 도면에서 a, b, c, d, e는 각각 순서대로 표면개질처리 하지 않은 아연분말과 발명예1, 2, 3, 4의 아연분말을 혼합하여 제조한 강판코팅제를 코팅한 경우를 나타낸다. 도면에서 확인할 수 있듯이, 표면개질처리한 경우가 더욱 우수한 내식성능을 나타내고 있음을 확인할 수 있었다. 특히, 발명예2와 발명예4는 발명예1과 발명예3에 비하여 제2족 원소인 칼슘을 더 첨가한 경우인데, 내식성이 더욱 우수함을 확인할 수 있었다.
Fig. 5 shows the result of corrosion test by ASTM B117 method after coating the above-mentioned steel sheet coating agent on the surface of the cold-rolled steel sheet. In the figure, a, b, c, d, and e indicate cases in which a steel plate coating prepared by mixing a zinc powder not subjected to surface modification treatment with zinc powder of Inventive Examples 1, 2, 3 and 4 is coated sequentially. As can be seen from the figure, it was confirmed that the surface modification treatment exhibited better corrosion resistance. Particularly, Inventive Example 2 and Inventive Example 4 were obtained by further adding calcium as a Group 2 element in comparison with Inventive Examples 1 and 3, and it was confirmed that corrosion resistance is further superior.
또한, 도 6에 발명예5(a)와 발명예6(b)에 의해 제조된 아연분말에 대하여 상기와 동일한 방식으로 부식시험한 결과를 나타내었다. 도면에서 볼 수 있듯이, 발명예5 및 발명예6에 의해 제조된 아연분말은 부식시험에 의해서도 그 표면이 원형을 유지하고 있음을 확인할 수 있다.
6 shows the result of corrosion test of the zinc powder produced in Examples 5 (a) and 6 (b) in the same manner as described above. As can be seen from the figure, it can be confirmed that the zinc powder produced by Inventive Example 5 and Inventive Example 6 retains its original shape even by the corrosion test.
또한, 도 7에는 발명예5(a)와 발명예6(b)에 의해 제조된 아연분말을 수지에 혼합하여 강판코팅제를 제조하였다. 이때, 수지로는 에스테르 수지를 사용하였으며, 경화 후 전체 강판 코팅 층 100 부피비에 대하여 40부피부(PVC-pigment volume concentration)가 되도록 아연분말을 혼합하여 강판코팅제를 제조하고 이를 강판표면에 코팅한 후 ASTM B117법에 의해 부식시험한 결과를 나타내었다.
7, a steel sheet coating agent was prepared by mixing the zinc powder produced in Inventive Examples 5 (a) and 6 (b) with a resin. At this time, an ester resin was used as a resin, and a steel sheet coating agent was prepared by mixing zinc powder so as to have a PVC-pigment volume concentration of 40 parts by volume per 100 parts by volume of the whole steel sheet coating layer after curing, The result of corrosion test according to ASTM B117 method is shown.
이 경우 역시 상술한 발명예1~4와 유사한 수준의 내식성을 가지고 있음을 확인할 수 있었다.
In this case, it was also confirmed that it has a corrosion resistance similar to that of Examples 1 to 4 described above.
따라서, 본 발명의 유리한 효과를 확인할 수 있었다.Therefore, the advantageous effects of the present invention can be confirmed.
Claims (11)
[화학식 1]
단, 여기서 R 및 R'은 각각 독립적으로 수소, C1 -30의 알킬 혹은 사이클로 알킬, 또는 치환되거나 비치환된 페닐을 나타낸다.2. The zinc powder for coating according to claim 1, wherein the phosphate compound satisfies the following formula (1).
[Chemical Formula 1]
However, where R and R 'are each independently hydrogen, alkyl or cycloalkyl of C 1 -30 alkyl, or a substituted or unsubstituted phenyl shows a beach.
상기 용액에 아연분말을 첨가하여 반응시키는 단계; 및
상기 반응된 아연분말을 회수하는 단계를 포함하는 내식성이 우수한 코팅용 아연분말의 제조방법.At least one compound selected from a phosphoric acid compound, a phosphonic acid compound, a carboxyl group-containing compound, an azole compound and an organic amine compound; And a Ca ion;
Adding zinc powder to the solution and reacting; And
And recovering the reacted zinc powder. ≪ Desc / Clms Page number 19 >
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4352899A (en) * | 1980-04-05 | 1982-10-05 | Sakai Chemical Industry Co., Ltd. | Coating composition for metal-substrate |
| KR20050016237A (en) * | 2003-08-15 | 2005-02-21 | 가부시끼가이샤 호우덴 세이미쯔 가꼬 겐쿠쇼 | Chromium-free metal surface treatment agent |
| KR20090096728A (en) * | 2006-12-21 | 2009-09-14 | 어드밴스드 테크놀러지 머티리얼즈, 인코포레이티드 | Liquid cleaner for the removal of post-etch residues |
| KR20100108104A (en) * | 2009-03-27 | 2010-10-06 | 주식회사 포스코 | Nano-capsule containing corrosion inhibitor, method for preparing the same, composition comprising the same, and surface treated steel sheet therewith |
-
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4352899A (en) * | 1980-04-05 | 1982-10-05 | Sakai Chemical Industry Co., Ltd. | Coating composition for metal-substrate |
| KR20050016237A (en) * | 2003-08-15 | 2005-02-21 | 가부시끼가이샤 호우덴 세이미쯔 가꼬 겐쿠쇼 | Chromium-free metal surface treatment agent |
| KR20090096728A (en) * | 2006-12-21 | 2009-09-14 | 어드밴스드 테크놀러지 머티리얼즈, 인코포레이티드 | Liquid cleaner for the removal of post-etch residues |
| KR20100108104A (en) * | 2009-03-27 | 2010-10-06 | 주식회사 포스코 | Nano-capsule containing corrosion inhibitor, method for preparing the same, composition comprising the same, and surface treated steel sheet therewith |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190021746A (en) * | 2017-08-23 | 2019-03-06 | 한양대학교 에리카산학협력단 | Method for manufacturing a aqueous paint composition, and aqueous paint composition using same |
| KR102024429B1 (en) | 2017-08-23 | 2019-09-23 | 한양대학교 에리카산학협력단 | Method for manufacturing a aqueous paint composition, and aqueous paint composition using same |
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