KR101182373B1 - Composition for metal surface treatment and method for preparing thereof - Google Patents
Composition for metal surface treatment and method for preparing thereof Download PDFInfo
- Publication number
- KR101182373B1 KR101182373B1 KR1020080108995A KR20080108995A KR101182373B1 KR 101182373 B1 KR101182373 B1 KR 101182373B1 KR 1020080108995 A KR1020080108995 A KR 1020080108995A KR 20080108995 A KR20080108995 A KR 20080108995A KR 101182373 B1 KR101182373 B1 KR 101182373B1
- Authority
- KR
- South Korea
- Prior art keywords
- composition
- surface treatment
- silica
- silane coupling
- coupling agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 104
- 238000004381 surface treatment Methods 0.000 title claims abstract description 65
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 63
- 239000002184 metal Substances 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims description 34
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 85
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 46
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 36
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 229910000831 Steel Inorganic materials 0.000 claims description 44
- 239000010959 steel Substances 0.000 claims description 44
- 239000011248 coating agent Substances 0.000 claims description 22
- 238000000576 coating method Methods 0.000 claims description 22
- 239000007769 metal material Substances 0.000 claims description 15
- -1 β-aminoethyl Chemical group 0.000 claims description 13
- 239000001993 wax Substances 0.000 claims description 12
- 239000008119 colloidal silica Substances 0.000 claims description 11
- 229910001335 Galvanized steel Inorganic materials 0.000 claims description 9
- 239000011247 coating layer Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 239000008397 galvanized steel Substances 0.000 claims description 9
- 239000000314 lubricant Substances 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000004698 Polyethylene Substances 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 229920000573 polyethylene Polymers 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 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 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical group CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 150000001785 cerium compounds Chemical class 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 150000003609 titanium compounds Chemical class 0.000 claims description 3
- 150000003682 vanadium compounds Chemical class 0.000 claims description 3
- 150000003755 zirconium compounds Chemical class 0.000 claims description 3
- 229910000838 Al alloy Inorganic materials 0.000 claims description 2
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 239000004203 carnauba wax Substances 0.000 claims description 2
- 235000013869 carnauba wax Nutrition 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 239000010960 cold rolled steel Substances 0.000 claims description 2
- 238000009713 electroplating Methods 0.000 claims description 2
- 125000003700 epoxy group Chemical group 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 229910021485 fumed silica Inorganic materials 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 2
- 239000012188 paraffin wax Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 239000011135 tin Substances 0.000 claims description 2
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 claims description 2
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- OWXLRKWPEIAGAT-UHFFFAOYSA-N [Mg].[Cu] Chemical compound [Mg].[Cu] OWXLRKWPEIAGAT-UHFFFAOYSA-N 0.000 claims 1
- MHKWSJBPFXBFMX-UHFFFAOYSA-N iron magnesium Chemical compound [Mg].[Fe] MHKWSJBPFXBFMX-UHFFFAOYSA-N 0.000 claims 1
- 230000007797 corrosion Effects 0.000 abstract description 30
- 238000005260 corrosion Methods 0.000 abstract description 30
- 238000003860 storage Methods 0.000 abstract description 9
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 7
- 239000011651 chromium Substances 0.000 abstract description 6
- 229910052804 chromium Inorganic materials 0.000 abstract description 6
- 239000000243 solution Substances 0.000 description 19
- 238000011156 evaluation Methods 0.000 description 10
- 230000000704 physical effect Effects 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 238000005461 lubrication Methods 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 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 4
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- 230000003666 anti-fingerprint Effects 0.000 description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 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 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- MFWFDRBPQDXFRC-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;vanadium Chemical compound [V].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MFWFDRBPQDXFRC-LNTINUHCSA-N 0.000 description 1
- YOBOXHGSEJBUPB-MTOQALJVSA-N (z)-4-hydroxypent-3-en-2-one;zirconium Chemical compound [Zr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O YOBOXHGSEJBUPB-MTOQALJVSA-N 0.000 description 1
- AIFLGMNWQFPTAJ-UHFFFAOYSA-J 2-hydroxypropanoate;titanium(4+) Chemical compound [Ti+4].CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O AIFLGMNWQFPTAJ-UHFFFAOYSA-J 0.000 description 1
- BDSSZTXPZHIYHM-UHFFFAOYSA-N 2-phenoxypropanoyl chloride Chemical compound ClC(=O)C(C)OC1=CC=CC=C1 BDSSZTXPZHIYHM-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 229910021551 Vanadium(III) chloride Inorganic materials 0.000 description 1
- 229910000611 Zinc aluminium Inorganic materials 0.000 description 1
- PGTXKIZLOWULDJ-UHFFFAOYSA-N [Mg].[Zn] Chemical compound [Mg].[Zn] PGTXKIZLOWULDJ-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- ZJLGIENOYTXSGX-UHFFFAOYSA-J aluminum silver disulfate Chemical compound [Al+3].[Ag+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZJLGIENOYTXSGX-UHFFFAOYSA-J 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- WJZHMLNIAZSFDO-UHFFFAOYSA-N manganese zinc Chemical compound [Mn].[Zn] WJZHMLNIAZSFDO-UHFFFAOYSA-N 0.000 description 1
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 1
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 1
- LYTNHSCLZRMKON-UHFFFAOYSA-L oxygen(2-);zirconium(4+);diacetate Chemical compound [O-2].[Zr+4].CC([O-])=O.CC([O-])=O LYTNHSCLZRMKON-UHFFFAOYSA-L 0.000 description 1
- GUSFEBGYPWJUSS-UHFFFAOYSA-N pentaazanium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O GUSFEBGYPWJUSS-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 1
- YJVLWFXZVBOFRZ-UHFFFAOYSA-N titanium zinc Chemical compound [Ti].[Zn] YJVLWFXZVBOFRZ-UHFFFAOYSA-N 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- HQYCOEXWFMFWLR-UHFFFAOYSA-K vanadium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[V+3] HQYCOEXWFMFWLR-UHFFFAOYSA-K 0.000 description 1
- 239000000080 wetting agent Substances 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
- C23C22/48—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 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/20—Use of solutions containing silanes
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
본 발명은 실란커플링제 및 실리카를 포함하되, 상기 실란커플링제에 함유된 규소 원자 및 실리카에 함유된 규소 원자의 중량비가 0.1 내지 0.5인 금속표면처리용 조성물 및 이의 제조방법에 관한 것이다. 본 발명에 의하면, 내열성, 전도성, 내식성, 가공성 및 용액의 저장 안정성이 우수하고, 크롬 및 용제를 함유하지 않는 친환경적인 금속표면처리용 조성물 및 이의 제조방법을 제공할 수 있다.The present invention relates to a silane coupling agent and a silica, wherein the weight ratio of the silicon atoms contained in the silane coupling agent and the silicon atoms contained in the silica is 0.1 to 0.5 and a composition for metal surface treatment and a method for producing the same. According to the present invention, it is possible to provide an environmentally friendly metal surface treatment composition which is excellent in heat resistance, conductivity, corrosion resistance, processability, and storage stability of a solution, and which does not contain chromium and a solvent, and a manufacturing method thereof.
금속표면처리, 비크롬, 금속화합물, 내열성, 환경친화 Metal surface treatment, non chrome, metal compound, heat resistance, environment friendly
Description
본 발명은 금속표면처리용 조성물 및 이의 제조방법에 관한 것이다.The present invention relates to a metal surface treatment composition and a method for producing the same.
일반적으로 아연으로 도금된 강철, 알루미늄 또는 스테인리스 등과 같은 금속재료는 건자재 및 자동차용 강판뿐만 아니라 가전제품용 금속자재 등에 대해 폭넓게 사용되고 있다.In general, metal materials such as zinc plated steel, aluminum, or stainless steel are widely used for metal materials for home appliances as well as construction materials and automotive steel sheets.
그러나 이들 금속은 쉽게 부식되거나 오염되기 때문에 이를 방지하기 위해서 금속재료의 표면에 일정한 코팅처리를 수행함으로써 금속재료에 내부식성 또는 내오염성의 기능을 부여하였다.However, since these metals are easily corroded or contaminated, a constant coating treatment on the surface of the metal material is performed to impart corrosion resistance or fouling resistance to the metal material.
종래 금속재료의 표면처리방법에는, 크로메이트처리, 윤활처리 또는 내지문 수지 처리 등이 이용되어 왔으며, 이 중에서 크로메이트처리는 저렴한 처리비용으로 강판에 우수한 내식성 및 도장성 등의 표면처리 특성을 부여하기 때문에 많이 이용되어 왔다.In the conventional method of surface treatment of metal materials, chromate treatment, lubrication treatment or anti-fingerprint treatment, etc. have been used. Among them, chromate treatment gives surface treatment characteristics such as excellent corrosion resistance and paintability to steel sheet at low processing cost. It has been used a lot.
그러나 상기 크로메이트처리에 사용되는 크롬은 대표적인 공해물질로서 인체 및 환경에 심각한 피해를 입힌다는 문제점이 있었는바, 전 세계적으로 크롬의 사용 을 규제하려는 조치가 이루어지고 있으며, 이에 따라 크롬의 사용은 곧 금지될 전망이다.However, chromium used in the chromate treatment has a problem that serious damage to human body and environment as a representative pollutant, and measures are being taken to regulate the use of chromium worldwide. It is expected to be.
따라서 이러한 크롬을 배제한 환경친화적인 표면처리방법으로서, 윤활처리 또는 내지문 처리 등에 대한 개발 및 방법도 다수 제안되고 있으나, 이와 같은 방법은 내식성 및 전도성 등에 취약한 문제점이 있으며, 특히 수지 등의 유기물이 함유됨에 따라 내열성에 큰 문제점이 있었다.Therefore, as an environmentally friendly surface treatment method excluding such chromium, a number of developments and methods for lubrication treatment or anti-fingerprint treatment have been proposed, but such a method has a problem of being vulnerable to corrosion resistance and conductivity, and especially contains organic substances such as resins. As a result, there was a big problem in heat resistance.
본 발명은 상술한 문제점을 해결하기 위하여 창출된 것으로서, 전도성, 가공성 및 내열성 등의 우수한 물성을 가지며, 친환경적인 금속표면처리용 조성물을 제공하는데 그 목적이 있다.The present invention has been made to solve the above problems, and has an object of providing an environmentally friendly composition for metal surface treatment having excellent physical properties such as conductivity, processability and heat resistance.
본 발명의 다른 목적은, 우수한 물성을 가지며, 친환경적인 금속표면처리용 조성물을 이용하여 표면 처리한 표면처리강판을 제공하는데 있다.Another object of the present invention is to provide a surface-treated steel sheet having excellent physical properties and surface treatment using an environmentally friendly metal surface treatment composition.
본 발명의 또 다른 목적은, 우수한 물성을 가지며, 친환경적인 금속표면처리용 조성물의 제조방법을 제공하는데 있다.Still another object of the present invention is to provide a method for preparing a composition for metal surface treatment, which has excellent physical properties.
본 발명의 또 다른 목적은, 용접성 및 도장밀착성 등이 향상되도록 우수한 물성을 가지며, 친환경적인 금속표면처리용 조성물을 이용한 금속재료의 표면처리방법을 제공하는데 있다.Still another object of the present invention is to provide a surface treatment method of a metal material using an environmentally friendly composition for metal surface treatment, which has excellent physical properties to improve weldability and paint adhesion.
본 발명은 상기 과제를 해결하기 위한 수단으로서, 실란커플링제 및 실리카를 포함하되, 상기 실란커플링제에 함유된 규소 원자 및 실리카에 함유된 규소 원자의 중량비가 0.1 내지 0.5인 금속표면처리용 조성물을 제공한다.The present invention is a means for solving the above problems, comprising a silane coupling agent and silica, the weight ratio of the silicon atoms contained in the silane coupling agent and the silicon atoms contained in the silica is 0.1 to 0.5 for the composition for metal surface treatment to provide.
또한, 본 발명은 상기 과제를 해결하기 위한 다른 수단으로서, 금속 강판; 및 상기 금속 강판의 일면 또는 양면에 형성되고 본 발명에 따른 금속표면처리용 조성물을 함유하는 코팅층을 포함하는 금속 재료를 제공한다.In addition, the present invention is another means for solving the above problems, a metal steel sheet; And a coating layer formed on one or both surfaces of the metal steel sheet and containing a composition for treating a metal surface according to the present invention.
또한, 본 발명은 상기 과제를 해결하기 위한 또 다른 수단으로서, a) 실란커플링제 및 실리카를 준비하는 단계; 및 b) 상기 실란커플링제에 함유된 규소 원자(Si) 및 실리카에 함유된 규소 원자(Si)의 중량비가 0.1 내지 0.5가 되도록 상기 실란커플링제 및 실리카를 혼합하는 단계를 포함하는 금속표면처리용 조성물의 제조방법을 제공한다.In addition, the present invention as another means for solving the above problems, a) preparing a silane coupling agent and silica; And b) mixing the silane coupling agent and silica so that the weight ratio of silicon atoms (Si) contained in the silane coupling agent and silicon atoms (Si) contained in the silica is 0.1 to 0.5. Provided are methods for preparing the composition.
아울러, 본 발명은 상기 과제를 해결하기 위한 또 다른 수단으로서, 본 발명에 따른 금속표면처리용 조성물을 강판에 도포하는 단계; 및 상기 조성물이 도포된 강판을 건조하는 단계를 포함하는 것을 특징으로 하는 금속재료의 표면처리방법을 제공한다.In addition, the present invention as another means for solving the above problems, the step of applying a composition for metal surface treatment according to the invention on a steel sheet; And it provides a surface treatment method of a metal material comprising the step of drying the steel sheet coated with the composition.
상술한 바와 같은 본 발명의 금속표면처리용 조성물 및 이를 도포한 표면처리강판은 내열성, 전도성, 내식성, 가공성 및 용액의 저장안정성이 우수할 뿐 아니라 크롬 및 용제를 함유하지 않기 때문에 친환경적이라는 장점이 있다.As described above, the composition for treating the metal surface of the present invention and the surface-treated steel sheet coated with the same are excellent in heat resistance, conductivity, corrosion resistance, processability, storage stability of solution, and do not contain chromium and solvents. .
또한, 본 발명의 금속표면처리용 조성물의 제조방법 및 금속표면처리용 조성물을 이용한 금속재료의 표면처리방법에 의하면, 우수한 물성 및 친환경성을 나타내는 금속표면처리용 조성물을 제조할 수 있을 뿐 아니라 이를 이용하여 금속재료의 표면처리작업 시에 요구되는 용접성 및 도장 밀착성 등도 함께 향상시킬 수 있다.In addition, according to the manufacturing method of the metal surface treatment composition and the surface treatment method of the metal material using the metal surface treatment composition of the present invention, it is possible to prepare a metal surface treatment composition exhibiting excellent physical properties and environmental friendliness, By using this method, weldability and paint adhesion required for the surface treatment of metal materials can be improved.
본 발명은 실란커플링제 및 실리카를 포함하되, 상기 실란커플링제에 함유된 규소 원자(Si) 및 실리카에 함유된 규소 원자(Si)의 중량비가 0.1 내지 0.5인 금속표면처리용 조성물에 관한 것이다.The present invention relates to a metal surface treatment composition comprising a silane coupling agent and silica, wherein the weight ratio of silicon atoms (Si) contained in the silane coupling agent and silicon atoms (Si) contained in the silica is 0.1 to 0.5.
이하, 본 발명의 금속표면처리용 조성물에 대하여 보다 상세하게 설명한다.Hereinafter, the composition for metal surface treatment of this invention is demonstrated in detail.
상기한 바와 같이, 본 발명의 금속표면처리용 조성물은 실란커플링제 및 실리카를 포함하되, 상기 실란커플링제에 함유된 규소 원자 및 실리카에 함유된 규소 원자의 중량비가 0.1 내지 0.5인 것이 바람직하며, 0.2 내지 0.4인 것이 보다 바람직하다.As described above, the composition for metal surface treatment of the present invention includes a silane coupling agent and silica, but the weight ratio of the silicon atoms contained in the silane coupling agent and the silicon atoms contained in the silica is preferably 0.1 to 0.5, It is more preferable that it is 0.2-0.4.
실란커플링제에 함유된 규소 원자 및 실리카에 함유된 규소 원자의 중량비가 0.1 미만인 경우, 도막의 가교도가 떨어져 내식성 및 밀착성의 개선효과가 떨어진다는 문제점이 있으며, 0.5를 초과하는 경우, 유기물의 함량이 많아짐에 따라 내열성이 떨어지고, 가교도가 지나치게 증가하여 용액의 안정성이 떨어질 뿐 아니라 코팅성도 떨어진다는 문제점이 있다.When the weight ratio of the silicon atoms contained in the silane coupling agent and the silicon atoms contained in the silica is less than 0.1, there is a problem in that the degree of crosslinking of the coating film is lowered and the effect of improving corrosion resistance and adhesion is lowered. As the number increases, the heat resistance is decreased, and the degree of crosslinking is excessively increased, thereby decreasing the stability of the solution as well as the coating property.
삭제delete
상기 실란커플링제는 소재와의 밀착성 및 내식성 등을 향상시켜주는 물질로서, 예를 들면, 에폭시기 또는 아미노기로부터 선택된 하나 이상의 관능기를 가지 는 실란커플링제 및 이들의 가수분해 축합물로 이루어진 군으로부터 선택된 하나 이상일 수 있다.The silane coupling agent is a material for improving adhesion and corrosion resistance with a material, for example, one selected from the group consisting of a silane coupling agent having at least one functional group selected from an epoxy group or an amino group and hydrolyzed condensates thereof. It may be abnormal.
여기서, 실란커플링제의 가수분해 축합물이란, 실란커플링제를 가수분해 중합시킨 실란커플링제의 올리고머를 말한다.Here, the hydrolysis-condensation product of a silane coupling agent means the oligomer of the silane coupling agent which hydrolyzed and polymerized the silane coupling agent.
보다 구체적인 예를 들면, 상기 실란커플링제는 γ-아미노프로필트리에톡시실란, γ-글리시독시프로필트리메톡시실란, γ-메타글리옥시프로필트리메톡시실란, N-(β-아미노에틸)-γ-아미노프로필메틸디메톡시실란, N-(β-아미노에틸)-γ-아미노프로필트리메톡시실란, γ-글리시독시프로필트리에톡시실란, γ-글리시독시프로필메틸디메톡시실란, 2-(3,4-에폭시시클로헥실)에틸트리메톡시실란으로 이루어진 군으로부터 선택된 하나 이상인 것이 바람직하다.As a more specific example, the silane coupling agent is γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, It is preferably at least one selected from the group consisting of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.
다만, 상기 실란커플링제가 상기 예시된 것에 한정되는 것은 아니고, 본 발명의 목적에 따라 소재와의 밀착성 및 내식성 등을 향상시켜주는 실란커플링제 및 이들의 혼합물은 모두 포함할 수 있다.However, the silane coupling agent is not limited to those exemplified above, and may include all of the silane coupling agents and mixtures thereof to improve the adhesion and the corrosion resistance with the material according to the object of the present invention.
한편, 상기 실리카는 본 발명에 따른 금속표면처리용 조성물의 가공성 및 내식성 향상시키는 역할을 하며, 예를 들면, 콜로이달 실리카, 흄드 실리카 또는 이들의 혼합물일 수 있다.On the other hand, the silica serves to improve the processability and corrosion resistance of the metal surface treatment composition according to the present invention, for example, may be colloidal silica, fumed silica or a mixture thereof.
여기서, 상기 실리카는 평균입경 5 내지 15nm의 콜로이달 실리카인 것이 바람직하다.Here, the silica is preferably colloidal silica having an average particle diameter of 5 to 15nm.
콜로이달 실리카의 평균입경은 소재의 종류 및 조도 등에 따라 달라질 수 있으나, 상기 콜로이달 실리카의 평균입경이 15nm를 초과하는 경우, 소재에 대한 베 리어(barrier) 효과가 떨어져 내식성 향상을 기대하기 어렵다는 문제점이 있고, 5nm 미만인 경우, 콜로이달 실리카의 가격이 크게 상승하여 경제적인 효과가 감소된다.The average particle diameter of the colloidal silica may vary depending on the type and roughness of the material, but when the average particle diameter of the colloidal silica exceeds 15 nm, it is difficult to expect improvement in corrosion resistance due to a barrier effect on the material. In the case of less than 5 nm, the price of colloidal silica is greatly increased and the economic effect is reduced.
다만, 상기 실리카도 상기 예시된 것에 한정되는 것은 아니고, 본 발명의 목적에 따라 가공성 및 내식성을 향상시킬 수 있는 실리카는 모두 포함할 수 있다.However, the silica is not limited to those exemplified above, and may include all silicas capable of improving processability and corrosion resistance according to the object of the present invention.
한편, 본 발명에 따른 금속표면처리용 조성물은 pH가 3 내지 6인 것이 바람직하고, 3.5 내지 5인 것이 보다 바람직하며, 4.0 내지 4.5인 것이 더욱 바람직하고, 4.1 내지 4.5인 것이 특히 바람직하다.On the other hand, the composition for metal surface treatment according to the present invention preferably has a pH of 3 to 6, more preferably 3.5 to 5, still more preferably 4.0 to 4.5, particularly preferably 4.1 to 4.5.
상기 조성물의 pH가 3 내지 6을 벗어나는 경우, 용액의 경화가 촉진되어 용액의 수명이 단축될 수 있다.When the pH of the composition is outside the range of 3 to 6, curing of the solution may be accelerated to shorten the life of the solution.
따라서 상기 조성물의 pH를 상기 수치범위로 조절하기 위한 첨가제를 첨가할 수 있는데, 상기 첨가제의 구체적인 예를 들면, 상기 조성물의 pH를 낮추기 위한 것으로서, 인산 또는 일인산암모늄을 사용할 수 있으며, 상기 조성물의 pH를 올리기 위한 것으로서, 삼인산암모늄 또는 묽은 암모니아수를 사용할 수 있다.Therefore, it is possible to add an additive for adjusting the pH of the composition to the numerical range, specific examples of the additive, as to lower the pH of the composition, it can be used phosphoric acid or ammonium monophosphate, As for raising the pH, ammonium triphosphate or dilute ammonia water can be used.
또한, 본 발명에 따른 금속표면처리용 조성물은 바나듐 화합물, 지르코늄 화합물, 티타늄 화합물, 알루미늄 화합물 및 세륨 화합물로 이루어진 군으로부터 선택된 1종 이상의 금속화합물을 추가로 포함하는 것이 바람직하다.In addition, the composition for metal surface treatment according to the present invention preferably further comprises at least one metal compound selected from the group consisting of vanadium compounds, zirconium compounds, titanium compounds, aluminum compounds and cerium compounds.
상기 금속화합물은 본 발명에 따른 금속표면처리용 조성물의 내식성을 개선하기 위한 것으로서, 구체적인 예를 들면, 상기 바나듐 화합물은 산화 바나듐, 암모늄메타바나데이트, 바나듐옥시아세틸아세토네이트, 바나듐아세틸아세토네이트 또 는 3염화바나듐일 수 있고, 상기 지르코늄 화합물은 질산지르코닐, 아세트산지르코닐, 탄산지르코닐암모늄 또는 지르코늄아세틸아세토네이트일 수 있고, 상기 티타늄 화합물은 황산 티타닐 또는 티탄락테이트일 수 있으며, 상기 알루미늄 화합물은 황산알루미늄 또는 질산알루미늄일 수 있고, 세륨 화합물은 질산세륨일 수 있다.The metal compound is to improve the corrosion resistance of the metal surface treatment composition according to the present invention, for example, the vanadium compound is vanadium oxide, ammonium metavanadate, vanadium oxyacetylacetonate, vanadium acetylacetonate or May be vanadium trichloride, the zirconium compound may be zirconyl nitrate, zirconyl acetate, zirconyl ammonium carbonate or zirconium acetylacetonate, the titanium compound may be titanyl sulfate or titanium lactate, the aluminum compound Silver aluminum sulfate or aluminum nitrate, and the cerium compound may be cerium nitrate.
다만, 본 발명에 따른 금속화합물이 상기 예시된 금속화합물에 한정되는 것은 아니고, 본 발명의 목적에 따라 금속표면처리용 조성물의 내식성을 향상시킬 수 있는 다양한 금속화합물이 이에 포함될 수 있다.However, the metal compound according to the present invention is not limited to the above exemplified metal compound, and various metal compounds capable of improving the corrosion resistance of the metal surface treatment composition according to the object of the present invention may be included therein.
나아가, 본 발명에 따른 금속표면처리용 조성물은 상기 실란커플링제 5 내지 15 중량부, 실리카 5 내지 10 중량부, 및 금속화합물 0.5 내지 3 중량부를 포함하는 것이 바람직하다.Furthermore, the metal surface treatment composition according to the present invention preferably contains 5 to 15 parts by weight of the silane coupling agent, 5 to 10 parts by weight of silica, and 0.5 to 3 parts by weight of the metal compound.
상기 실란커플링제가 5 중량부 미만인 경우, 밀착성 및 내식성과 같은 물성향상 효과가 나타나기 어려우며, 15 중량부를 초과하는 경우, 내열성은 감소하고, 용액 안정성이 저하되며 내식성과 같은 물성향상 효과도 증가하지 않으므로 비경제적이다.When the silane coupling agent is less than 5 parts by weight, it is difficult to exhibit the effect of improving physical properties such as adhesion and corrosion resistance, and when it exceeds 15 parts by weight, the heat resistance is decreased, the solution stability is lowered, and the effect of improving the physical properties such as corrosion resistance is not increased. It is uneconomical.
또한, 상기 실리카가 5 중량부 미만인 경우, 물성향상 효과가 부족하며 10 중량부를 초과하는 경우, 도막이 지나치게 강고해져 가공 시 부숴지기 쉽고 이로 인해 도막에 스크래치가 발생되어 내식성이 저하된다는 문제점이 있다.In addition, when the silica is less than 5 parts by weight, the effect of improving the physical properties is insufficient, if it exceeds 10 parts by weight, the coating film is too hard to break during processing, thereby causing scratches on the coating film has a problem of lowering the corrosion resistance.
나아가, 상기 금속화합물이 0.5 중량부 미만인 경우, 내식성을 충분히 향상시킬 수 없으며, 3 중량부를 초과하는 경우, 수성의 금속표면처리용 조성물의 용해도가 떨어지고 용액의 저장안정성이 악화될 수 있다.Furthermore, when the metal compound is less than 0.5 parts by weight, the corrosion resistance may not be sufficiently improved, and when the metal compound is more than 3 parts by weight, the solubility of the aqueous metal surface treatment composition may be degraded and the storage stability of the solution may deteriorate.
한편, 본 발명에 따른 금속표면처리용 조성물은 가공성 향상 및 자기 윤활성 부여를 위한 윤활제를 추가로 포함할 수 있다.On the other hand, the composition for treating the metal surface according to the present invention may further include a lubricant for improving workability and imparting self-lubrication.
상기 윤활제는 예를 들면, 수용성 파라핀왁스, 올레핀왁스, 카나우바왁스, 폴리에틸렌왁스 및 폴리테트라플루오로에틸렌왁스로 이루어진 군으로부터 선택된 1종 이상일 수 있으며, 바람직하게는 폴리에틸렌왁스 및 폴리테트라플루오로에틸렌왁스의 혼합물을 사용하는 것이 바람직하다.The lubricant may be, for example, at least one selected from the group consisting of water-soluble paraffin wax, olefin wax, carnauba wax, polyethylene wax and polytetrafluoroethylene wax, preferably polyethylene wax and polytetrafluoroethylene wax. Preference is given to using mixtures of these.
또한, 상기 윤활제는 금속표면처리용 조성물에 1 내지 3 중량부로 함유되는 것이 바람직하다.In addition, the lubricant is preferably contained in 1 to 3 parts by weight of the metal surface treatment composition.
상기 윤활제의 함량이 1 중량부 미만인 경우, 코팅도막의 윤활작용이 일어나지 못하므로 가공 및 성형성의 향상효과가 충분하지 못하며, 3 중량부를 초과하는 경우, 더 이상의 윤활효과가 발휘되지 않으므로 내식성 등의 요구성능 및 용액의 안정성이 저하될 수 있다는 문제가 있다.When the content of the lubricant is less than 1 part by weight, the lubrication action of the coating film does not occur, so the effect of improving the workability and formability is not sufficient, and when the amount is more than 3 parts by weight, no further lubrication effect is exerted. There is a problem that performance and stability of the solution may be degraded.
한편, 본 발명에 따른 금속표면처리용 조성물은 물, 알코올, 에스테르 및 에테르로 이루어진 군으로부터 선택된 1종 이상의 용제를 추가로 포함할 수 있다.On the other hand, the composition for metal surface treatment according to the present invention may further include one or more solvents selected from the group consisting of water, alcohols, esters and ethers.
즉, 본 발명에 따른 금속표면처리용 조성물은 상기와 같은 용제를 추가로 포함하는 수성 표면처리 조성물인 것이 바람직하며, 이와 같은 용제를 추가로 포함함에 따라 도막의 조막성 향상과 함께 견고한 도막을 형성할 수 있다.That is, the composition for metal surface treatment according to the present invention is preferably an aqueous surface treatment composition further comprising such a solvent, and by further including such a solvent to form a solid coating film with improved film forming properties of the coating film. can do.
나아가, 필요한 경우, 상기 금속표면처리용 조성물은 물성 향상을 위하여 경화제, 소포제 또는 웨팅제 등과 같은 첨가제를 추가로 포함할 수 있다.Furthermore, if necessary, the metal surface treatment composition may further include an additive such as a curing agent, an antifoaming agent or a wetting agent to improve physical properties.
상기와 같은 조성으로 이루어진 본 발명에 따른 금속표면처리 조성물은 강판 에 우수한 내열성, 전도성, 내식성, 가공성 및 용액의 저장 안정성을 부여하며, 크롬을 함유하지 않기 때문에 친환경적이라는 장점이 있다.The metal surface treatment composition according to the present invention having the composition as described above has an excellent heat resistance, conductivity, corrosion resistance, processability, and storage stability of the solution to the steel sheet, and does not contain chromium.
또한, 본 발명은 상기한 바와 같은 금속 강판; 및 상기 금속 강판의 일면 또는 양면에 형성되고 본 발명에 따른 금속표면처리용 조성물을 함유하는 코팅 층을 포함하는 금속재료에 관한 것이다.In addition, the present invention is a metal steel sheet as described above; And a coating layer formed on one or both surfaces of the metal steel sheet and containing a composition for metal surface treatment according to the present invention.
여기서, 금속 강판은 자동차 재료, 가전제품, 건축재료 등의 용도로 이용되는 금속, 특정적으로 철판 등의 금속을 의미하는 것으로서, 이러한 목적으로 당업계에서 통상적으로 사용되는 강판이라면 어떠한 것이라도 무방하지만, 바람직하게는 냉연강판; 아연도금 강판, 아연니켈 도금강판, 아연철 도금강판, 아연티탄 도금강판, 아연마그네슘 도금강판, 아연망간 도금강판, 아연알루미늄 도금강판 등의 아연계 전기도금 강판; 용융도금강판; 알루미늄 도금강판; 또한 이들 도금층에 이종금속 또는 불순물로서, 예를 들면, 코발트, 몰리브덴, 텅스텐, 니켈, 티탄, 알루미늄, 망간, 철, 마그네슘, 주석, 동 등을 함유한 도금 강판; 또한 이들 도금층에 실리카, 알루미나 등의 무기물을 분산시킨 도금강판; 또는 실리콘, 동, 마그네슘, 철, 망간, 티탄, 아연 등을 첨가한 알루미늄 합금판; 또는 인산염이 도포된 아연도금강판; 또는 열연강판을 사용할 수 있고, 필요에 따라 상기 도금 중에 2종류 이상을 순차적으로 처리한 다층 도금판을 사용할 수 있다.Here, the metal steel plate means a metal used for the purpose of automobile materials, home appliances, building materials, and the like, specifically metal such as iron plate, and any steel sheet commonly used in the art for this purpose may be used. Preferably, cold rolled steel sheet; Zinc-based electroplating steel sheets such as galvanized steel sheet, zinc nickel plated steel sheet, galvanized steel sheet, zinc titanium plated steel sheet, zinc magnesium plated steel sheet, zinc manganese plated steel sheet and zinc aluminum plated steel sheet; Hot-dip galvanized steel sheet; Aluminum plated steel sheet; Further, plated steel sheets containing, as the dissimilar metals or impurities in these plating layers, for example, cobalt, molybdenum, tungsten, nickel, titanium, aluminum, manganese, iron, magnesium, tin, copper, and the like; Further, plated steel sheet in which inorganic materials such as silica and alumina are dispersed in these plating layers; Or an aluminum alloy plate containing silicon, copper, magnesium, iron, manganese, titanium, zinc or the like; Or galvanized steel sheet coated with phosphate; Alternatively, a hot rolled steel sheet may be used, and a multilayer plated sheet obtained by sequentially treating two or more kinds during the plating may be used as necessary.
또한, 상기 금속표면처리용 조성물이 함유된 코팅 층을 금속 강판에 도포하는 방법은 롤코우터법, 샤워스퀴즈법, 침적법 또는 스프레이법 등을 이용할 수 있 다.In addition, a method of applying the coating layer containing the metal surface treatment composition to a metal sheet may be a roll coater method, a shower squeeze method, a deposition method or a spray method.
상기한 바와 같이, 본 발명에 따른 금속표면처리 조성물을 함유하는 코팅 층을 포함하는 금속 재료는 크로메이트를 함유하지 않으므로 인체에 무해하며, 환경오염의 위험성을 줄일 수 있다는 장점이 있다.As described above, the metal material including the coating layer containing the metal surface treatment composition according to the present invention does not contain chromate, so it is harmless to the human body and has an advantage of reducing the risk of environmental pollution.
아울러, 상기 코팅 층의 건조 후 부착량은 0.5 내지 1.5 g/㎡인 것이 바람직하다.In addition, the adhesion amount after drying of the coating layer is preferably 0.5 to 1.5 g / ㎡.
여기서, 상기 코팅 층의 건조 후 부착량이 0.5 g/㎡ 미만인 경우, 내식성 및 가공성 등이 감소될 우려가 있고, 1.5 g/㎡을 초과하면 전도성, 용접성 및 도장의 밀착성이 떨어질 우려가 있다.Here, when the coating amount after drying of the coating layer is less than 0.5 g / ㎡, there is a fear that the corrosion resistance and workability, etc. are reduced, and if it exceeds 1.5 g / ㎡ there is a fear that the adhesion, weldability and adhesion of the coating is inferior.
또한, 본 발명은 a) 실란커플링제 및 실리카를 준비하는 단계; 및 b) 상기 실란커플링제에 함유된 규소 원자(Si) 및 실리카에 함유된 규소 원자(Si)의 중량비가 0.1 내지 0.5가 되도록 상기 실란커플링제 및 실리카를 혼합하는 단계를 포함하는 금속표면처리용 조성물의 제조방법에 관한 것이다.In addition, the present invention comprises the steps of a) preparing a silane coupling agent and silica; And b) mixing the silane coupling agent and silica so that the weight ratio of silicon atoms (Si) contained in the silane coupling agent and silicon atoms (Si) contained in the silica is 0.1 to 0.5. It relates to a method for preparing the composition.
단계 b)는 c) 상기 실란커플링제와 실리카를 교반하여 점도가 8.0 내지 10.0 cps인 혼합물을 제조하는 단계; 및 d) 상기 혼합물을 냉각하는 단계를 포함할 수 있다.Step b) c) stirring the silane coupling agent and silica to prepare a mixture having a viscosity of 8.0 to 10.0 cps; And d) cooling the mixture.
즉, 상기 실란커플링제와 실리카를 교반하여 가교 반응시키고, 상기 실란커플링제와 실리카를 혼합한 혼합물의 점도가 8.0 내지 10.0 cps가 될 때까지 교반을 지속하는 것이 바람직하며, 9.0 내지 10.0 cps가 될 때까지 교반을 지속하는 것이 보다 바람직하다.That is, it is preferable that the crosslinking reaction is carried out by stirring the silane coupling agent and silica, and the stirring is continued until the viscosity of the mixture of the silane coupling agent and the silica becomes 8.0 to 10.0 cps, and becomes 9.0 to 10.0 cps. It is more preferable to continue stirring until it is.
여기서, 상기 혼합물의 점도가 10.0 cps를 초과한 후에 냉각을 시키게 되면, 용액의 점도를 제어하기가 어려워 용액의 안정성 및 코팅성이 열화될 우려가 있으며, 상기 혼합물의 점도가 8.0 cps 미만인 경우에 냉각을 시키게 되면, 용액의 가교가 불충분하여 내식성 등의 효과를 기대하기 어렵다.In this case, when the cooling is performed after the viscosity of the mixture exceeds 10.0 cps, it is difficult to control the viscosity of the solution, which may deteriorate the stability and coating property of the solution. When the viscosity of the mixture is lower than 8.0 cps, the cooling is performed. If it is, the crosslinking of the solution is insufficient and it is difficult to expect the effect such as corrosion resistance.
또한, e) 단계 d)에서 냉각된 혼합물의 pH를 3 내지 6으로 제어하는 단계를 추가로 포함하는 것이 바람직하다.It is also preferred to further comprise e) controlling the pH of the mixture cooled in step d) to 3-6.
나아가, f) 단계 e)에서 pH가 제어된 혼합물에 금속화합물 또는 윤활제를 포함하는 첨가제를 추가로 첨가하는 단계; 및 g) 단계 f)에서 얻어진 혼합물의 pH를 3 내지 6으로 제어하는 단계를 추가로 포함하는 것이 바람직하다.Furthermore, f) further adding an additive comprising a metal compound or a lubricant to the pH controlled mixture in step e); And g) controlling the pH of the mixture obtained in step f) to 3-6.
여기서, 상기 혼합물의 pH는 상술한 바와 같이, 3.5 내지 5로 제어하는 것이 보다 바람직하며, 나아가 4.0 내지 4.5인 것이 더욱 바람직하고, 4.1 내지 4.5인 것이 특히 바람직하다.As described above, the pH of the mixture is more preferably controlled to 3.5 to 5, more preferably 4.0 to 4.5, and particularly preferably 4.1 to 4.5.
뿐만 아니라, 본 발명은 상기 금속표면처리용 조성물을 강판에 도포하는 단계; 및 상기 조성물이 도포된 강판을 건조하는 단계를 포함하는 것을 특징으로 하는 금속재료의 표면처리방법에 관한 것이다.In addition, the present invention comprises the steps of applying the metal surface treatment composition to a steel sheet; And it relates to a surface treatment method of a metal material comprising the step of drying the steel sheet coated with the composition.
여기서, 상기 조성물은 0.5 내지 1.5 g/㎡의 건조 도막량으로 도포되는 것이 바람직하다.Here, the composition is preferably applied in a dry coating amount of 0.5 to 1.5 g / ㎡.
상기 코팅 층의 건조 도막량이 0.5 g/㎡ 미만인 경우, 내식성 및 가공성 등 이 감소될 우려가 있고, 1.5 g/㎡을 초과하면 전도성, 용접성 및 도장의 밀착성이 떨어질 우려가 있다.When the dry coating amount of the coating layer is less than 0.5 g / m 2, corrosion resistance and workability may be reduced, and when the dry coating film amount is more than 1.5 g / m 2, conductivity, weldability, and adhesion of paint may be deteriorated.
또한, 건조 온도는 80 내지 200℃인 것이 바람직하다.Moreover, it is preferable that drying temperature is 80-200 degreeC.
여기서, 상기 조성물을 코팅하고, 소부 시에 건조 온도가 80℃ 미만인 경우, 경화가 잘 이루어지지 않으므로 충분한 도막 형성이 이루어지지 않을 수 있다는 문제점이 있고, 200℃를 초과하는 경우에는 건조 후 금속재료의 냉각이 용이하지 않고, 도막의 탄화 발생 등과 같은 도막성분 결합의 변형으로 인해 전반적인 성능감소가 나타날 수 있다는 문제점이 있다.Here, when the composition is coated and the drying temperature is less than 80 ° C. at the time of baking, there is a problem that hardening is not performed well and thus sufficient coating film formation may not be achieved. Cooling is not easy, and there is a problem that the overall performance may be reduced due to deformation of the coating film component bond such as carbonization of the coating film.
이하, 하기 실시예를 통하여 본 발명을 보다 상세하게 설명하고자 한다. 다만, 본 발명이 하기 실시예에 의해 제한되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the present invention is not limited by the following examples.
[실시예 1]Example 1
반응 용기에 γ-글리시독시프로필트리메톡시실란 125g과 평균입경이 5.5nm인 콜로이달 실리카를 배합하여 혼합액을 준비하고, 상기 혼합액 내에 규소 원자(Si)의 함량이 0.2 중량부가 되도록 하여 교반 혼합하였다.125 g of γ-glycidoxy propyltrimethoxysilane and colloidal silica having an average particle diameter of 5.5 nm were mixed in a reaction vessel to prepare a mixed liquid, and the mixture was stirred to make the content of silicon atoms (Si) 0.2 parts by weight. It was.
상기 혼합액의 점도가 9.5 cps가 된 후, 냉각수를 가동하여 용액의 온도가 40℃로 떨어뜨리고, 상기 혼합액을 포함하는 수성 표면처리 조성물의 총량이 900g이 되도록 물을 투입한 후 인산을 이용하여 pH를 4.3으로 조정하였다.After the viscosity of the mixed solution was 9.5 cps, the cooling water was started to drop the temperature of the solution to 40 ° C., and water was added so that the total amount of the aqueous surface treatment composition containing the mixed solution was 900 g, followed by pH using phosphoric acid. Was adjusted to 4.3.
이어서 상기 수성 표면처리 조성물에 황산알루미늄 10g 및 폴리에틸렌 왁스 20g을 첨가하고, 상기 조성물의 총량이 1000g이 되도록 물을 더 투입한 후 최종 pH 가 4.3이 되도록 1인산암모늄을 첨가하여 1시간 동안 교반함으로써 수성 표면처리 조성물을 제조하였다.Subsequently, 10 g of aluminum sulfate and 20 g of polyethylene wax were added to the aqueous surface treatment composition, water was further added so that the total amount of the composition was 1000 g, and then aqueous ammonium phosphate was added and stirred for 1 hour so that the final pH was 4.3. A surface treatment composition was prepared.
이와 같이 제조된 수성 표면처리 조성물을 도금 부착량의 편면 기준이 20g/㎡인 전기아연도금강판에 건조 도막량이 1.0g/㎡가 되도록 바코팅하고 강판온도가 150℃가 될 때까지 건조한 후 공랭하여 표면 처리된 아연도금강판을 준비하였다. The aqueous surface treatment composition thus prepared was bar-coated on an electrogalvanized steel sheet having a surface coating weight of 20 g / m 2 so that the dry coating amount was 1.0 g / m 2, and dried until the steel sheet temperature reached 150 ° C., followed by air cooling. The treated galvanized steel sheet was prepared.
[실시예 2~5 및 비교예 1~4][Examples 2-5 and Comparative Examples 1-4]
실시예 2 내지 5 및 비교예 1 내지 4는, 실란커플링제의 종류 및 첨가량, 실란커플링제와 콜로이달 실리카의 혼합액 내에 함유된 규소 원자의 함량, 실란커플링제와 콜로이달 실리카의 혼합액의 최종 점도, 금속화합물과 윤활제의 종류 및 첨가량, 소부 온도 및 건조 도막량, 용액의 pH를 하기 표 1에 기재한 바와 같이 변경한 것을 제외하고는 실시예 1과 동일한 방법으로 수성 표면처리 조성물을 제조하고, 이를 이용하여 표면 처리된 아연도금강판을 준비하였다.Examples 2 to 5 and Comparative Examples 1 to 4, the type and amount of the silane coupling agent, the content of silicon atoms contained in the mixture of the silane coupling agent and colloidal silica, the final viscosity of the mixture of the silane coupling agent and colloidal silica , An aqueous surface treatment composition was prepared in the same manner as in Example 1, except that the type and amount of the metal compound and the lubricant, the baking temperature and the dry coating amount, and the pH of the solution were changed as shown in Table 1 below. Using this, a surface-treated galvanized steel sheet was prepared.
(cps)Viscosity
(cps)
온도(℃)dry
Temperature (℃)
도막량
(g/㎡)dry
Coating amount
(g / m 2)
커플링제Silane
Coupling agent
화합물metal
compound
시
예room
city
Yes
C2(1.0)C1 (1.0)
C2 (1.0)
A2(7.5)A1 (5.0)
A2 (7.5)
교
예ratio
School
Yes
주) 탈이온수 첨가량 : 잔량Note) Deionized water addition amount: remaining amount
A : 실란화합물 A: Silane Compound
A1 : γ-글리시독시프로필트리메톡시실란A1: gamma-glycidoxypropyltrimethoxysilane
A2 : γ-아미노프로필트리에톡시실란A2: gamma-aminopropyltriethoxysilane
A3 : N-(β-아미노에틸)-γ-아미노프로필메틸디메톡시실란 A3: N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane
A4 : γ-글리시독시프로필메틸디메톡시실란 A4: γ-glycidoxypropylmethyldimethoxysilane
B : 금속화합물B: metal compound
B1 : 황산알루미늄B1: aluminum sulfate
B2 : 질산세륨B2: cerium nitrate
B3 : 암모늄메타바나데이트B3: ammonium metavanadate
B4 : 이소프로필티타네이트B4: isopropyl titanate
C : 윤활제C: lubricant
C1 : 폴리에틸렌왁스C1: Polyethylene Wax
C2 : 폴리테트라플루오로에틸렌왁스C2: polytetrafluoroethylene wax
상기와 같은 조건에 따라 제조된 수성 표면처리 조성물을 이용하여 코팅이 이루어진 실시예 1 내지 5 및 비교예 1 내지 4의 강판에 대하여 내열성, 전도성, 내식성, 가공성 및 용액저장안정성을 평가하였다.The heat resistance, conductivity, corrosion resistance, processability and solution storage stability of the steel sheets of Examples 1 to 5 and Comparative Examples 1 to 4, which were coated using the aqueous surface treatment composition prepared according to the conditions described above, were evaluated.
[실험예][Experimental Example]
1. 내열성 테스트1. Heat resistance test
상기 실시예 1 내지 5 및 비교예 1 내지 4에 따라 표면 처리된 강판을 250℃의 온도에서 30분간 방치한 후, 전후의 색차변화를 측정하고, 색차변화의 정도에 따라 하기와 같이 분류하였다.After the steel sheets surface-treated according to Examples 1 to 5 and Comparative Examples 1 to 4 were left at a temperature of 250 ° C. for 30 minutes, the color difference before and after was measured, and classified according to the degree of color difference change.
○ : 색차변화(ΔE) 3 미만○: color difference change (ΔE) less than 3
△ : 색차변화(ΔE) 3 내지 5Δ: color difference change (ΔE) 3 to 5
× : 색차변화(ΔE) 5 초과×: color difference change (ΔE) 5 exceeded
2. 전도성 테스트2. Conductivity test
표면전기저항측정기(미츠비시화학㈜, 로레스타EP)를 이용하여 시험판 표면의 전기저항치를 측정하고, 표면전기저항값에 따라 하기와 같이 분류하였다.The electrical resistance value of the surface of the test plate was measured using a surface electrical resistance measuring instrument (Mitsubishi Chemical Co., Ltd., Loresta EP), and classified according to the surface electrical resistance value as follows.
○ : 표면전기저항값이 1Ω 이하○: Surface electrical resistance value is 1Ω or less
△ : 표면전기저항값이 1Ω 초과하는 경우가 간혹있음△: Surface electrical resistance value sometimes exceeds 1Ω
× : 표면전기저항값이 1Ω 초과×: Surface electrical resistance value is over 1Ω
3. 내식성 테스트3. Corrosion Resistance Test
5%의 식염수를 35℃에서 피도물의 표면에 분무하고, 72시간 후의 백녹의 정도를 3 수준으로 평가하고, 평가 기준은 하기와 같이 분류하였다. 이 경우, 평가는 평면부에 대해서만 실시하였다.5% saline was sprayed on the surface of the workpiece at 35 ° C, and the degree of white rust after 72 hours was evaluated at three levels, and evaluation criteria were classified as follows. In this case, evaluation was performed only about the flat part.
○ : 부식이 전혀 없거나 아주 조금 백녹 발생(부식면적이 평가면적의 5% 이내)○: No corrosion or very slight white rust (corrosion area within 5% of the evaluation area)
△ : 약간 백녹 발생(부식면적이 평가면적의 5-10% 이내)(Triangle | delta): Slightly white rust generate | occur | produces 5-10% of the evaluation area.
× : 다소 또는 많은 백녹 발생(부식면적이 평가면적의 10% 이상)×: Some or more white rust occurs (corrosion area of more than 10% of the evaluation area)
4. 가공성 테스트4. Machinability Test
트리보미터(Tribometer) 시험기를 이용하여 0.25㎏f/㎟의 하중에서 10회 왕복 후 시험편의 표면을 육안으로 관찰하여 평가하였다. 평가기준은 하기와 같다. The surface of the test piece was visually evaluated after reciprocating 10 times at a load of 0.25 kgf / mm 2 using a Tribometer tester. Evaluation criteria are as follows.
○ : 흑화발생이 거의 없음○: almost no blackening
△ : 평가부위에서 부분적으로 흑화 발생△: blackening partially occurs in the evaluation site
× : 평가부위 전면 흑화 발생×: Blackening of entire evaluation site
5. 저장안정성 테스트5. Storage stability test
상기 제조한 수성 표면처리 조성물 용액을 40℃의 항온장치 내에서 2개월간 저장한 후 조성물의 점도상승, 분리, 침전 등의 상태를 관찰하였다. 평가기준은 하기와 같다. The aqueous surface treatment composition solution prepared above was stored for 2 months in an incubator at 40 ° C., and then the state of viscosity increase, separation, and precipitation of the composition was observed. Evaluation criteria are as follows.
○ : 조성물의 변화가 인정되지 않는다. (Circle): The change of a composition is not recognized.
× : 조성물의 점도상승, 분리 또는 침전 등의 변화가 인정된다. X: Changes in viscosity increase, separation or precipitation of the composition are recognized.
상기와 같은 다양한 물성 테스트에 따른 평가결과를 하기 표 2에 요약하였다. 하기 표 2를 참고하면, 본 발명에 의한 수성 표면처리 조성물을 표면 처리하여 코팅된 실시예 1 내지 5의 강판의 경우에는 내열성, 내식성, 가공성, 내열성 및 용액의 저장안정성이 모두 우수하게 나타났으며, 특히 가공성이 우수하게 나타났다.Evaluation results according to the various physical property tests as described above are summarized in Table 2 below. Referring to Table 2 below, in the case of the steel sheets of Examples 1 to 5 coated with the surface treatment composition of the present invention, the heat resistance, corrosion resistance, processability, heat resistance, and storage stability of the solution were all excellent. In particular, the processability was excellent.
그러나, 실란커플링제와 실리카의 혼합액 내에서 규소 원자의 함량이 본 발명의 금속표면처리용 조성물에 따른 규소 원자의 함량 범위를 벗어나서 보다 많이 함유된 비교예 1의 조성물로 코팅된 강판은 내열성 및 용액의 저장안정성이 열위하였다.However, the steel sheet coated with the composition of Comparative Example 1 in which the content of the silicon atoms in the mixed solution of the silane coupling agent and the silica was outside the content range of the silicon atoms according to the metal surface treatment composition of the present invention is heat-resistant and solution The storage stability of was inferior.
또한 금속화합물을 포함하지 않은 비교예 2의 조성물로 코팅된 강판은 내식성에 있어서 다소 부족한 면이 나타났고, 실란커플링제와 콜로이달 실리카를 혼합한 혼합액의 최종 점도가 본 발명의 금속표면처리용 조성물에 따른 혼합액의 점도 범위에 이르기 전에 교반을 중단하고 냉각시킨 비교예 3의 조성물로 코팅된 강판 및 본 발명의 금속표면처리용 조성물의 pH 범위를 벗어나서 보다 높은 pH값을 나타낸 비교예 4의 조성물로 코팅된 강판의 경우, 내식성이 불충분하게 나타났으며, 특히, 비교예 4의 조성물로 코팅된 강판은 용액의 저장안정성도 열위한 것으로 나타났다.In addition, the steel sheet coated with the composition of Comparative Example 2, which does not contain a metal compound, appeared to be somewhat insufficient in corrosion resistance, and the final viscosity of the mixed solution in which the silane coupling agent and the colloidal silica was mixed was the composition for metal surface treatment of the present invention. To the composition of Comparative Example 4 showing a higher pH value outside the pH range of the steel sheet and the composition for a metal surface treatment of the present invention coated with the composition of Comparative Example 3 was stopped and cooled before reaching the viscosity range of the mixed solution according to the present invention. In the case of the coated steel sheet, the corrosion resistance was insufficient, and in particular, the steel sheet coated with the composition of Comparative Example 4 was also found to be inferior in storage stability of the solution.
시
예room
city
Yes
교
예ratio
School
Yes
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| JP2005298837A (en) | 2004-04-06 | 2005-10-27 | Kansai Paint Co Ltd | Metal surface treatment composition and metal plate using the same |
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|---|---|---|---|---|
| KR100447599B1 (en) | 2001-12-21 | 2004-09-07 | 주식회사 포스코 | Chromium-Free Surface Treatment Composition for Galvanized Steel |
| JP2005298837A (en) | 2004-04-06 | 2005-10-27 | Kansai Paint Co Ltd | Metal surface treatment composition and metal plate using the same |
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| KR20100049944A (en) | 2010-05-13 |
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