JP2012052163A - Surface treatment solution, surface-treated steel sheet and method for producing the same - Google Patents
Surface treatment solution, surface-treated steel sheet and method for producing the same Download PDFInfo
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- JP2012052163A JP2012052163A JP2010193954A JP2010193954A JP2012052163A JP 2012052163 A JP2012052163 A JP 2012052163A JP 2010193954 A JP2010193954 A JP 2010193954A JP 2010193954 A JP2010193954 A JP 2010193954A JP 2012052163 A JP2012052163 A JP 2012052163A
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- Prior art keywords
- steel sheet
- surface treatment
- treatment liquid
- film
- treated
- Prior art date
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- Granted
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- 238000004381 surface treatment Methods 0.000 title claims abstract description 126
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 125
- 239000010959 steel Substances 0.000 title claims abstract description 125
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 238000000576 coating method Methods 0.000 claims abstract description 94
- 239000011248 coating agent Substances 0.000 claims abstract description 87
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 44
- 239000005011 phenolic resin Substances 0.000 claims abstract description 29
- 125000003277 amino group Chemical group 0.000 claims abstract description 22
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 22
- 229920003987 resole Polymers 0.000 claims abstract description 21
- 239000007788 liquid Substances 0.000 claims description 84
- 238000007747 plating Methods 0.000 claims description 26
- 229910052751 metal Inorganic materials 0.000 claims description 24
- 239000000049 pigment Substances 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 15
- 239000011134 resol-type phenolic resin Substances 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 12
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 9
- 230000003449 preventive effect Effects 0.000 claims description 8
- 239000003822 epoxy resin Substances 0.000 claims description 7
- 229910052752 metalloid Inorganic materials 0.000 claims description 7
- 229920000647 polyepoxide Polymers 0.000 claims description 7
- 229920000728 polyester Polymers 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 239000010410 layer Substances 0.000 abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 28
- 239000002344 surface layer Substances 0.000 abstract description 5
- 238000005260 corrosion Methods 0.000 description 19
- 230000007797 corrosion Effects 0.000 description 19
- 238000000034 method Methods 0.000 description 19
- -1 aluminate ions Chemical class 0.000 description 18
- 238000012360 testing method Methods 0.000 description 18
- 229910052782 aluminium Inorganic materials 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 150000002736 metal compounds Chemical class 0.000 description 12
- 230000002378 acidificating effect Effects 0.000 description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 10
- 229920005989 resin Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000003973 paint Substances 0.000 description 7
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- 239000000377 silicon dioxide Chemical group 0.000 description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 5
- 229910052804 chromium Inorganic materials 0.000 description 5
- 239000011651 chromium Substances 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 229910000838 Al alloy Inorganic materials 0.000 description 3
- 229920001342 Bakelite® Polymers 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000004606 Fillers/Extenders Substances 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 125000005372 silanol group Chemical class 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 2
- 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 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229910000861 Mg alloy Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000012784 inorganic fiber Substances 0.000 description 2
- 239000011490 mineral wool Substances 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
- 238000010422 painting Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 2
- 235000019832 sodium triphosphate Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 2
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical group [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 2
- 229910000165 zinc phosphate Inorganic materials 0.000 description 2
- FWLHAQYOFMQTHQ-UHFFFAOYSA-N 2-N-[8-[[8-(4-aminoanilino)-10-phenylphenazin-10-ium-2-yl]amino]-10-phenylphenazin-10-ium-2-yl]-8-N,10-diphenylphenazin-10-ium-2,8-diamine hydroxy-oxido-dioxochromium Chemical compound O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.Nc1ccc(Nc2ccc3nc4ccc(Nc5ccc6nc7ccc(Nc8ccc9nc%10ccc(Nc%11ccccc%11)cc%10[n+](-c%10ccccc%10)c9c8)cc7[n+](-c7ccccc7)c6c5)cc4[n+](-c4ccccc4)c3c2)cc1 FWLHAQYOFMQTHQ-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- NLSFWPFWEPGCJJ-UHFFFAOYSA-N 2-methylprop-2-enoyloxysilicon Chemical compound CC(=C)C(=O)O[Si] NLSFWPFWEPGCJJ-UHFFFAOYSA-N 0.000 description 1
- TZZGHGKTHXIOMN-UHFFFAOYSA-N 3-trimethoxysilyl-n-(3-trimethoxysilylpropyl)propan-1-amine Chemical compound CO[Si](OC)(OC)CCCNCCC[Si](OC)(OC)OC TZZGHGKTHXIOMN-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical group [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229910000677 High-carbon steel Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- 229910000954 Medium-carbon steel Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- RJDOZRNNYVAULJ-UHFFFAOYSA-L [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] RJDOZRNNYVAULJ-UHFFFAOYSA-L 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- QBLDFAIABQKINO-UHFFFAOYSA-N barium borate Chemical compound [Ba+2].[O-]B=O.[O-]B=O QBLDFAIABQKINO-UHFFFAOYSA-N 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZXPDYFSTVHQQOI-UHFFFAOYSA-N diethoxysilane Chemical compound CCO[SiH2]OCC ZXPDYFSTVHQQOI-UHFFFAOYSA-N 0.000 description 1
- MHJAJDCZWVHCPF-UHFFFAOYSA-L dimagnesium phosphate Chemical compound [Mg+2].OP([O-])([O-])=O MHJAJDCZWVHCPF-UHFFFAOYSA-L 0.000 description 1
- 229910000395 dimagnesium phosphate Inorganic materials 0.000 description 1
- ILLRQJVNDWDWBA-UHFFFAOYSA-K dimagnesium;phosphate Chemical group [Mg+2].[Mg+2].[O-]P([O-])([O-])=O ILLRQJVNDWDWBA-UHFFFAOYSA-K 0.000 description 1
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000012812 general test Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical group [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Chemical group 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- INJVFBCDVXYHGQ-UHFFFAOYSA-N n'-(3-triethoxysilylpropyl)ethane-1,2-diamine Chemical compound CCO[Si](OCC)(OCC)CCCNCCN INJVFBCDVXYHGQ-UHFFFAOYSA-N 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 1
- 239000002335 surface treatment layer Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000001038 titanium pigment Substances 0.000 description 1
- VMFOHNMEJNFJAE-UHFFFAOYSA-N trimagnesium;diphosphite Chemical group [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])[O-].[O-]P([O-])[O-] VMFOHNMEJNFJAE-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- AUTOISGCBLBLBA-UHFFFAOYSA-N trizinc;diphosphite Chemical group [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])[O-].[O-]P([O-])[O-] AUTOISGCBLBLBA-UHFFFAOYSA-N 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 description 1
Abstract
Description
本発明は、表面処理液、表面処理鋼板およびその製造方法に関する。 The present invention relates to a surface treatment liquid, a surface-treated steel sheet, and a method for producing the same.
従来、溶融めっき鋼板などを塗装原板として塗装鋼板を製造する場合、塗装前処理としてクロメート処理を行うのが一般的であった。塗料を塗布する前にクロメート処理を行うことで、塗膜密着性や耐水性、耐食性などを向上させることができる。 Conventionally, when a coated steel sheet is manufactured using a hot-dip plated steel sheet or the like as a coating original plate, it is common to perform a chromate treatment as a pretreatment for coating. By performing the chromate treatment before applying the paint, it is possible to improve coating film adhesion, water resistance, corrosion resistance, and the like.
しかしながら、近年になって、環境負荷の軽減が重視される傾向から、六価クロムを含有しない非クロム系の塗装前処理液の開発が盛んに進められている。非クロム系の塗装前処理液の多くは、水性有機樹脂や金属化合物などを水系溶媒に配合したものである（例えば、特許文献１〜５参照）。金属化合物は、防錆効果の向上を目的として配合されているが、アルカリ水溶液中では沈殿してしまうことが多い。したがって、通常は、金属化合物を含有する表面処理液は、酸性に調整されている。 In recent years, however, development of non-chromium coating pretreatment liquids that do not contain hexavalent chromium has been actively promoted because of the tendency to reduce the environmental burden. Many non-chromium coating pretreatment liquids are prepared by blending an aqueous organic resin, a metal compound, or the like in an aqueous solvent (see, for example, Patent Documents 1 to 5). The metal compound is blended for the purpose of improving the rust prevention effect, but often precipitates in an alkaline aqueous solution. Therefore, normally, the surface treatment liquid containing a metal compound is adjusted to be acidic.
また、金属化合物を含有しない非クロム系の塗装前処理液も開発されている（例えば、特許文献６、７参照）。特許文献６、７には、フェノール樹脂とシランカップリング剤とを水系溶媒に配合した、酸性の表面処理液が記載されている。 In addition, a non-chromium coating pretreatment liquid that does not contain a metal compound has been developed (see, for example, Patent Documents 6 and 7). Patent Documents 6 and 7 describe an acidic surface treatment liquid in which a phenol resin and a silane coupling agent are blended in an aqueous solvent.
上記の通り、従来の非クロム系の表面処理液（塗装前処理液）は、酸性のものがほとんどであった。酸性タイプの表面処理液は、金属基材に対するエッチング作用が強く、塗装原板からの金属の溶出量が多大である。したがって、酸性タイプの表面処理液を塗装原板の表面に塗布すると、塗装原板と表面処理皮膜との間に形成される反応層の厚みが増大しやすい。この反応層は、金属成分の含有率が高いため、柔軟性に乏しく、曲げや延伸、圧縮などの加工によりワレが発生しやすい。このような加工ワレが発生してしまうと、却って塗膜密着性、耐水性および耐食性が低下してしまうことになる。 As described above, most of the conventional non-chromium surface treatment liquids (pretreatment liquids for coating) are acidic. The acidic type surface treatment liquid has a strong etching action on the metal substrate, and a large amount of metal is eluted from the coating original plate. Therefore, when an acidic type surface treatment liquid is applied to the surface of the coating original plate, the thickness of the reaction layer formed between the coating original plate and the surface treatment film tends to increase. Since this reaction layer has a high content of the metal component, it is poor in flexibility, and cracking is likely to occur due to bending, stretching, compression, and the like. If such cracks occur, the coating film adhesion, water resistance and corrosion resistance will be reduced.
反応層の増大に起因する加工ワレを回避するためには、表面処理液の塗布量を少なくして反応層の増大を抑制すればよい。その一方で、表面処理液の塗布量が過少量の場合は、十分な膜厚の表面処理皮膜を形成することができず、塗膜密着性、耐水性および耐食性を十分に向上させることができない。 In order to avoid cracks caused by the increase in the reaction layer, the amount of the surface treatment solution applied may be reduced to suppress the increase in the reaction layer. On the other hand, when the coating amount of the surface treatment liquid is excessively small, a surface treatment film having a sufficient film thickness cannot be formed, and the coating film adhesion, water resistance and corrosion resistance cannot be sufficiently improved. .
このように、酸性タイプの表面処理液には、極めて狭い範囲で厳密に塗布量を制御しなければならず、使用しにくいという問題があった。 As described above, the acidic type surface treatment liquid has a problem that it is difficult to use since the coating amount must be strictly controlled within a very narrow range.
本発明は、かかる点に鑑みてなされたものであり、非クロム系の表面処理液（塗装前処理液）であって、加工ワレが発生しにくく、かつ塗膜密着性および耐水性が高い表面処理皮膜を容易に形成することができる表面処理液を提供することを目的とする。 The present invention has been made in view of the above points, and is a non-chromium-based surface treatment liquid (pre-treatment liquid for coating), which is less prone to processing cracks and has a high coating film adhesion and water resistance. It aims at providing the surface treatment liquid which can form a treatment film easily.
また、本発明は、塗膜密着性および耐水性が高い表面処理鋼板ならびにその製造方法を提供することを目的とする。 Another object of the present invention is to provide a surface-treated steel sheet having high coating film adhesion and water resistance and a method for producing the same.
本発明者は、水溶性レゾール型フェノール樹脂と、アミノ基またはエポキシ基を有するシランカップリング剤とを主成分とし、かつｐＨがアルカリ性の表面処理液を塗装原板に塗布することで、塗装原板に含まれるＡｌをも利用して塗膜密着性および耐食性に優れた表面処理皮膜を形成できることを見出し、さらに検討を加えて本発明を完成させた。 The present inventor applied a surface treatment solution having a water-soluble resol type phenolic resin and a silane coupling agent having an amino group or an epoxy group as a main component and an alkaline pH to the coating original plate. The present inventors have found that a surface-treated film excellent in coating film adhesion and corrosion resistance can be formed by using Al contained, and further studied and completed the present invention.
すなわち、本発明の第一は、以下の表面処理液に関する。
［１］水溶性レゾール型フェノール樹脂と、アミノ基またはエポキシ基を有するシランカップリング剤とを含有し、かつ金属成分を含有しない、ｐＨが８〜１３の水溶液である、Ａｌ含有めっき鋼板用の表面処理液。
［２］前記水溶性レゾール型フェノール樹脂と前記シランカップリング剤との質量比は、９０：１０〜４０：６０の範囲内である、［１］に記載の表面処理液。
That is, the first of the present invention relates to the following surface treatment liquid.
[1] For an Al-containing plated steel sheet, which is an aqueous solution containing a water-soluble resol-type phenolic resin and a silane coupling agent having an amino group or an epoxy group and containing no metal component and having a pH of 8 to 13. Surface treatment liquid.
[2] The surface treatment liquid according to [1], wherein a mass ratio of the water-soluble resol type phenol resin and the silane coupling agent is in a range of 90:10 to 40:60.
本発明の第二は、以下の表面処理鋼板の製造方法に関する。
［３］めっき層中にＡｌを０.１７質量％以上含有し、かつめっき層表面から４ｎｍの厚み領域における全金属元素の原子数とＣを除く半金属元素の原子数との総和に対するＡｌの原子数の割合が０.２５以上である、Ａｌ含有めっき鋼板を準備するステップと；水溶性レゾール型フェノール樹脂と、アミノ基またはエポキシ基を有するシランカップリング剤とを含有し、かつ金属成分を含有しない、ｐＨが８〜１３の水溶液である表面処理液を準備するステップと；前記Ａｌ含有めっき鋼板に前記表面処理液を塗布し、乾燥させて、表面処理皮膜を形成するステップとを有する、表面処理鋼板の製造方法。
［４］前記表面処理液における前記水溶性レゾール型フェノール樹脂と前記シランカップリング剤との質量比は、９０：１０〜４０：６０の範囲内である、［３］に記載の表面処理鋼板の製造方法。
2nd of this invention is related with the manufacturing method of the following surface treatment steel plates.
[3] The content of Al in the plating layer is 0.17% by mass or more with respect to the sum of the number of atoms of all metal elements and the number of metalloid elements excluding C in a thickness region of 4 nm from the surface of the plating layer. A step of preparing an Al-containing plated steel sheet having an atomic ratio of 0.25 or more; a water-soluble resol type phenol resin, a silane coupling agent having an amino group or an epoxy group, and a metal component A step of preparing a surface treatment liquid not containing, an aqueous solution having a pH of 8 to 13; and applying the surface treatment liquid to the Al-containing plated steel sheet and drying to form a surface treatment film; Manufacturing method of surface-treated steel sheet.
[4] The surface-treated steel sheet according to [3], wherein a mass ratio of the water-soluble resol type phenolic resin and the silane coupling agent in the surface treatment liquid is in a range of 90:10 to 40:60. Production method.
本発明の第三は、以下の表面処理鋼板に関する。
［５］Ａｌ含有めっき鋼板に表面処理液を塗布し、乾燥させて、表面処理皮膜を形成することで得られる、表面処理鋼板であって：前記Ａｌ含有めっき鋼板は、めっき層中にＡｌを０.１７質量％以上含有し、かつめっき層表面から４ｎｍの厚み領域における全金属元素の原子数とＣを除く半金属元素の原子数との総和に対するＡｌの原子数の割合が０.２５以上であり；前記表面処理液は、水溶性レゾール型フェノール樹脂と、アミノ基またはエポキシ基を有するシランカップリング剤とを含有し、かつ金属成分を含有しない、ｐＨが８〜１３の水溶液である、表面処理鋼板。
［６］前記表面処理液における前記水溶性レゾール型フェノール樹脂と前記シランカップリング剤との質量比は、９０：１０〜４０：６０の範囲内である、［５］に記載の表面処理鋼板。
［７］前記表面処理皮膜の付着量は、１０〜３００ｍｇ／ｍ２の範囲内である、［５］または［６］に記載の表面処理鋼板。
［８］前記表面処理皮膜は、Ａｌを０.２原子％以上含有する、［５］〜［７］のいずれかに記載の表面処理鋼板。
［９］前記表面処理皮膜の上に、エポキシ樹脂またはポリエステルを含む塗膜をさらに有する、［５］〜［８］のいずれかに記載の表面処理鋼板。
［１０］前記塗膜は、防錆顔料を含有する、［９］に記載の表面処理鋼板。
The third of the present invention relates to the following surface-treated steel sheets.
[5] A surface-treated steel sheet obtained by applying a surface treatment liquid to an Al-containing plated steel sheet and drying to form a surface-treated film, wherein the Al-containing plated steel sheet contains Al in the plating layer. The ratio of the number of Al atoms to the total of the number of atoms of all metal elements and the number of metalloid elements excluding C in the thickness region of 4 nm from the plating layer surface is 0.15% by mass or more. The surface treatment liquid is an aqueous solution having a pH of 8 to 13 containing a water-soluble resol type phenol resin and a silane coupling agent having an amino group or an epoxy group and containing no metal component. Surface treated steel sheet.
[6] The surface-treated steel sheet according to [5], wherein a mass ratio of the water-soluble resol type phenolic resin and the silane coupling agent in the surface treatment liquid is in a range of 90:10 to 40:60.
[7] The surface-treated steel sheet according to [5] or [6], wherein the adhesion amount of the surface treatment film is in the range of 10 to 300 mg / m 2 .
[8] The surface-treated steel sheet according to any one of [5] to [7], wherein the surface-treated film contains Al in an amount of 0.2 atomic% or more.
[9] The surface-treated steel sheet according to any one of [5] to [8], further having a coating film containing an epoxy resin or polyester on the surface-treated film.
[10] The surface-treated steel sheet according to [9], wherein the coating film contains a rust preventive pigment.
本発明によれば、塗膜密着性および耐水性が高い表面処理鋼板を容易に製造することができる。本発明の表面処理鋼板は、例えば外装建材用のプレコート鋼板の塗装原板として有用である。 According to the present invention, a surface-treated steel sheet having high coating film adhesion and water resistance can be easily produced. The surface-treated steel sheet of the present invention is useful, for example, as a coating original sheet for a pre-coated steel sheet for exterior building materials.
１．表面処理液
本発明の表面処理液は、Ａｌ含有めっき鋼板に表面処理（塗装前処理）を行う際に使用する表面処理液であって、水溶性レゾール型フェノール樹脂と、アミノ基またはエポキシ基を有するシランカップリング剤とを含有する水溶液である。
1. Surface treatment liquid The surface treatment liquid of the present invention is a surface treatment liquid used when performing surface treatment (pre-coating treatment) on an Al-containing plated steel sheet, and comprises a water-soluble resol type phenol resin and an amino group or epoxy group. It is the aqueous solution containing the silane coupling agent which has.
本発明の表面処理液は、１）有機樹脂として水溶性レゾール型フェノール樹脂を含有すること、２）アミノ基またはエポキシ基を有するシランカップリング剤を含有すること、３）ｐＨが８〜１３の範囲内であること、４）金属成分を含有しないこと、を主たる特徴とする。 The surface treatment liquid of the present invention includes 1) a water-soluble resol type phenol resin as an organic resin, 2) a silane coupling agent having an amino group or an epoxy group, and 3) a pH of 8 to 13. The main characteristics are that it is within the range and 4) contains no metal component.
［フェノール樹脂］
本発明の表面処理液は、有機樹脂としてヒドロキシ基（ヒドロキシアルキル基を含む）を多数有する水溶性レゾール型フェノール樹脂を含有する。後述するように、水溶性レゾール型フェノール樹脂は、硬化する際にヒドロキシ基を介してシランカップリング剤およびアルミン酸イオンとも結合して、塗膜密着性および耐水性に優れる強固かつ緻密な皮膜を形成する。
[Phenolic resin]
The surface treatment liquid of the present invention contains a water-soluble resol type phenol resin having a large number of hydroxy groups (including hydroxyalkyl groups) as an organic resin. As will be described later, the water-soluble resol-type phenolic resin is bonded with a silane coupling agent and aluminate ions through a hydroxy group when cured, thereby forming a strong and dense film excellent in coating film adhesion and water resistance. Form.
水溶性レゾール型フェノール樹脂は、フェノールやビスフェノールＡなどのフェノール類とホルムアルデヒドなどのアルデヒド類とをアルカリ触媒の存在下で縮合反応させることで得られる。 The water-soluble resol type phenol resin is obtained by subjecting phenols such as phenol and bisphenol A and aldehydes such as formaldehyde to a condensation reaction in the presence of an alkali catalyst.
水溶性レゾール型フェノール樹脂の数平均分子量は、１２０〜１０００の範囲内が好ましく、１５０〜５００の範囲内が特に好ましい。また、レゾール型フェノール樹脂は、ベンゼン核１核あたりのメチロール基の平均数が０.３〜２.５個の範囲内のものが好ましく、０.５〜２.０個の範囲内のものがより好ましい。上記要件を満たすレゾール型フェノール樹脂を使用することで、塗膜密着性および耐水性に優れる強固かつ緻密な皮膜を形成することができる。このようなレゾール型フェノール樹脂の市販品としては、スミライトレジンＰＲ−５０７８１（住友ベークライト株式会社）、レヂトップＰＬ−４６６７（群栄化学工業株式会社）などが挙げられる。 The number average molecular weight of the water-soluble resol type phenol resin is preferably in the range of 120 to 1000, particularly preferably in the range of 150 to 500. The resol type phenolic resin preferably has an average number of methylol groups per benzene nucleus in the range of 0.3 to 2.5, preferably in the range of 0.5 to 2.0. More preferred. By using a resol-type phenolic resin that satisfies the above requirements, a strong and dense film excellent in coating film adhesion and water resistance can be formed. Examples of such commercially available resol-type phenolic resins include Sumilite Resin PR-50781 (Sumitomo Bakelite Co., Ltd.), Resitop PL-4667 (Gunei Chemical Industry Co., Ltd.), and the like.
［シランカップリング剤］
本発明の表面処理液は、アミノ基またはエポキシ基を有するシランカップリング剤を含有する。表面処理液中においては、シランカップリング剤のアルコキシ基は加水分解されてシラノール基の状態で存在している。後述するように、シランカップリング剤は、シラノール基を介して塗装原板表面、フェノール樹脂およびアルミン酸イオンと結合する。また、シランカップリング剤は、アミノ基またはエポキシ基を介して、表面処理皮膜の上に形成される塗膜を構成する有機樹脂（例えば、エポキシ樹脂やポリエステルなど）とも結合する。結果として、アミノ基またはエポキシ基を有するシランカップリング剤は、フェノール樹脂やアルミン酸イオンなどと共に塗膜密着性および耐水性に優れる強固かつ緻密な皮膜を形成する。
[Silane coupling agent]
The surface treatment liquid of the present invention contains a silane coupling agent having an amino group or an epoxy group. In the surface treatment liquid, the alkoxy group of the silane coupling agent is hydrolyzed and exists in the form of a silanol group. As will be described later, the silane coupling agent binds to the surface of the coating original plate, the phenol resin, and aluminate ions via a silanol group. Moreover, a silane coupling agent couple | bonds with organic resin (for example, epoxy resin, polyester, etc.) which comprises the coating film formed on a surface treatment film through an amino group or an epoxy group. As a result, a silane coupling agent having an amino group or an epoxy group forms a strong and dense film excellent in coating film adhesion and water resistance together with a phenol resin and aluminate ions.
シランカップリング剤の種類は、アミノ基またはエポキシ基を有するものであれば特に限定されない。アミノ基を有するシランカップリング剤の例には、３−アミノプロピルトリメトキシシラン、３−アミノプロピルトリエトキシシラン、Ｎ−（２−アミノエチル）−３−アミノプロピルメチルジメトキシシラン、Ｎ−（２−アミノエチル）−３−アミノプロピルトリメトキシシラン、Ｎ−（２−アミノエチル）−３−アミノプロピルトリエトキシシラン、ビス（３−（トリメトキシシリル）プロピル）アミンなどが含まれる。エポキシ基を有するシランカップリング剤の例には、３−グリシドキシプロピルトリメトキシシラン、３−グリシドキシプロピルトリエトキシシラン、３−グリシドキシプロピルメチルジメトキシシラン、３−グリシドキシプロピルメチルジエトキシシラン、２−（３，４−エポキシシクロヘキシル）エチルトリメトキシシランなどが含まれる。 The kind of silane coupling agent is not particularly limited as long as it has an amino group or an epoxy group. Examples of the silane coupling agent having an amino group include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2 -Aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, bis (3- (trimethoxysilyl) propyl) amine and the like. Examples of silane coupling agents having an epoxy group include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyl Examples include diethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.
水溶性レゾール型フェノール樹脂とアミノ基またはエポキシ基を有するシランカップリング剤との質量比は、９０：１０〜４０：６０の範囲内が好ましい。質量比がこれらの範囲外の場合、塗膜密着性および／または耐水性が不十分な皮膜となるおそれがある。 The mass ratio of the water-soluble resol type phenol resin and the silane coupling agent having an amino group or an epoxy group is preferably in the range of 90:10 to 40:60. When the mass ratio is outside these ranges, there is a possibility that the film has insufficient coating adhesion and / or water resistance.
［表面処理液のｐＨ］
本発明の表面処理液は、ｐＨが８〜１３の範囲内であること、すなわちアルカリ性であることを一つの特徴とする。
[PH of surface treatment solution]
One feature of the surface treatment solution of the present invention is that the pH is in the range of 8 to 13, that is, it is alkaline.
まず、アルカリ性の表面処理液は、酸性の表面処理液に比べてエッチング作用が弱い。したがって、アルカリ性の表面処理液をＡｌ含有めっき鋼板の表面に塗布した場合、Ａｌ含有めっき鋼板と表面処理皮膜との間に形成される反応層の厚みが過剰に増大することはない。結果として、アルカリ性の表面処理液は、酸性の表面処理液に比べて加工ワレが生じにくい表面処理皮膜を形成することができる。 First, an alkaline surface treatment liquid has a weaker etching action than an acidic surface treatment liquid. Therefore, when the alkaline surface treatment liquid is applied to the surface of the Al-containing plated steel sheet, the thickness of the reaction layer formed between the Al-containing plated steel sheet and the surface treatment film does not increase excessively. As a result, the alkaline surface treatment liquid can form a surface treatment film that is less prone to processing cracking than the acidic surface treatment liquid.
また、アルカリ性の表面処理液をＡｌ含有めっき鋼板の表面に塗布した場合、めっき層表層のＡｌ（酸化物または水酸化物）は、アルミン酸イオン（Ａｌ（ＯＨ）４ −）となって表面処理液に溶解する。アルミン酸イオンは、塗装原板表面、フェノール樹脂およびシランカップリング剤と結合して、塗膜密着性および耐水性に優れる強固かつ緻密な皮膜を形成することができる。 In addition, when an alkaline surface treatment solution is applied to the surface of the Al-containing plated steel sheet, Al (oxide or hydroxide) on the surface of the plating layer becomes aluminate ions (Al (OH) 4 − ). Dissolve in the liquid. The aluminate ions can form a strong and dense film excellent in coating film adhesion and water resistance by binding to the surface of the coating original plate, the phenol resin and the silane coupling agent.
一方で、酸性の表面処理液をＡｌ含有めっき鋼板の表面に塗布した場合は、めっき層表層のＡｌは、アルミニウムイオン（Ａｌ３＋）となって表面処理液に溶解する。アルミニウムイオンは、シラノール基やヒドロキシ基と結合しないため、皮膜中においても単独で存在するものと考えられる。このように皮膜中に単独で存在するＡｌは、水分が皮膜中に浸透してきたときに水和または溶解しやすく、水分の浸入を促進するため、皮膜の耐湿性を顕著に低下させてしまう。 On the other hand, when an acidic surface treatment liquid is applied to the surface of the Al-containing plated steel sheet, Al on the plating layer surface layer becomes aluminum ions (Al 3+ ) and dissolves in the surface treatment liquid. Since aluminum ions do not bind to silanol groups or hydroxy groups, it is considered that aluminum ions exist alone in the film. As described above, Al present alone in the film is easily hydrated or dissolved when moisture penetrates into the film, and promotes the ingress of moisture, so that the moisture resistance of the film is significantly reduced.
以上のように、表面処理液をアルカリ性とすることで、１）反応層の厚みの増大を抑制して、加工ワレが生じにくい表面処理皮膜を形成することができ、かつ２）めっき層表層のＡｌも利用して、塗膜密着性および耐水性に優れる強固かつ緻密な皮膜を形成することができる。 As described above, by making the surface treatment solution alkaline, 1) it is possible to suppress an increase in the thickness of the reaction layer, and to form a surface treatment film that is unlikely to cause cracks. 2) Al can also be used to form a strong and dense film excellent in coating film adhesion and water resistance.
［金属成分］
本発明の表面処理液は、金属成分を含有しないことを一つの特徴とする。前述の通り、従来の表面処理液は、酸性であり、かつ防錆効果が期待される金属化合物（例えば、Ｔｉ化合物やＺｒ化合物など）を含有するものがほとんどであった。しかしながら、本発明の表面処理液を使用した場合、塗膜密着性および耐水性に優れた強固かつ緻密な表面処理皮膜が形成されることから、金属化合物を配合しなくても十分な耐食性を実現することができる。また、アルカリ性の水溶液中では、金属化合物が沈殿してしまうことが多いため、本発明の表面処理液に金属化合物を配合すると、表面処理液の保存安定性が低下してしまうおそれもある。したがって、本発明の表面処理液には、金属化合物を配合しないことが好ましい。
[Metal component]
One feature of the surface treatment liquid of the present invention is that it does not contain a metal component. As described above, most of the conventional surface treatment liquids are acidic and contain a metal compound (for example, a Ti compound or a Zr compound) that is expected to have an antirust effect. However, when the surface treatment liquid of the present invention is used, a strong and dense surface treatment film excellent in coating film adhesion and water resistance is formed, so that sufficient corrosion resistance is realized without adding a metal compound. can do. In addition, since the metal compound often precipitates in an alkaline aqueous solution, when the metal compound is added to the surface treatment liquid of the present invention, the storage stability of the surface treatment liquid may be reduced. Therefore, it is preferable not to add a metal compound to the surface treatment liquid of the present invention.
後述するように、本発明の表面処理液を用いて作製した表面処理鋼板の耐食性をさらに向上させたい場合は、表面処理皮膜の上に形成する下塗り塗膜に防錆顔料を配合すればよい。 As will be described later, when it is desired to further improve the corrosion resistance of the surface-treated steel sheet produced using the surface treatment liquid of the present invention, a rust preventive pigment may be blended in the undercoat film formed on the surface-treated film.
［表面処理液の調製方法］
本発明の表面処理液の調製方法は、特に限定されない。たとえば、アミノ基またはエポキシ基を有するシランカップリング剤の水溶液に、所定量の水溶性レゾール型フェノール樹脂を添加し、水で所望の濃度まで希釈すればよい。表面処理液中の固形分の濃度は、特に限定されず、塗布方法や希望する粘度、付着量などに応じて適宜設定すればよい。通常、表面処理液中の固形分の濃度は、０.１〜１５質量％程度である。
[Method for preparing surface treatment solution]
The method for preparing the surface treatment liquid of the present invention is not particularly limited. For example, a predetermined amount of a water-soluble resol type phenol resin may be added to an aqueous solution of a silane coupling agent having an amino group or an epoxy group, and diluted with water to a desired concentration. The concentration of the solid content in the surface treatment liquid is not particularly limited, and may be set as appropriate according to the application method, desired viscosity, adhesion amount, and the like. Usually, the concentration of the solid content in the surface treatment liquid is about 0.1 to 15% by mass.
次に説明するように、従来のクロメート処理の代わりに、本発明の表面処理液を用いて表面処理（塗装前処理）を行うことで、塗装原板の表面に塗膜密着性および耐水性に優れた表面処理皮膜を形成することができる。 As described below, surface treatment (pre-painting treatment) is performed using the surface treatment liquid of the present invention instead of the conventional chromate treatment, thereby providing excellent coating film adhesion and water resistance on the surface of the coating original plate. A surface treatment film can be formed.
２．表面処理鋼板の製造方法
本発明の表面処理鋼板の製造方法は、１）塗装原板としてＡｌ含有めっき鋼板を準備する第１のステップと、２）本発明の表面処理液を準備する第２のステップと、３）Ａｌ含有めっき鋼板の表面に本発明の表面処理液を塗布して表面処理皮膜を形成する第３のステップとを含む。以下、各ステップについて説明する。
2. Manufacturing method of surface-treated steel sheet The manufacturing method of the surface-treated steel sheet of the present invention includes 1) a first step of preparing an Al-containing plated steel sheet as a coating original sheet, and 2) a second step of preparing the surface treatment liquid of the present invention. And 3) a third step of forming a surface treatment film by applying the surface treatment liquid of the present invention to the surface of the Al-containing plated steel sheet. Hereinafter, each step will be described.
［第１のステップ］
第１のステップでは、塗装原板としてＡｌ含有めっき鋼板を準備する。
[First step]
In the first step, an Al-containing plated steel sheet is prepared as a coating original sheet.
本発明の表面処理鋼板の製造方法では、めっき層表層に含まれるＡｌの一部をアルミン酸イオン（Ａｌ（ＯＨ）４ −）として表面処理液中に溶解させ、このアルミン酸イオンも利用して表面処理皮膜を形成する。したがって、塗装原板としては、１）めっき層中にＡｌを０.１７質量％以上含有し、かつ２）めっき層表面から４ｎｍの厚み領域（表面酸化皮膜に相当する）における全金属元素の原子数とＣを除く半金属元素の原子数との総和に対するＡｌの原子数の割合「Ａｌの原子数／（全金属元素の原子数＋Ｃを除く半金属元素の原子数）」が０.２５以上であるＡｌ含有めっき鋼板を使用する。 In the method for producing a surface-treated steel sheet of the present invention, a part of Al contained in the surface layer of the plating layer is dissolved in the surface treatment solution as aluminate ions (Al (OH) 4 − ), and the aluminate ions are also used. A surface treatment film is formed. Therefore, as the coating original plate, 1) Al contained 0.17% by mass or more in the plating layer, and 2) Number of atoms of all metal elements in the thickness region (corresponding to the surface oxide film) of 4 nm from the plating layer surface. And the ratio of the number of Al atoms to the sum of the number of atoms of the metalloid elements excluding C and the number of atoms of Al / (number of atoms of all metal elements + number of atoms of metalloid elements excluding C) is 0.25 or more A certain Al-containing plated steel sheet is used.
めっき層全体のＡｌの濃度は、ＪＩＳ Ｈ０４０１に記載のヘキサメチレンテトラミン法によってめっき層を溶解した後、点滴ろ紙法による検量線法を用いて溶解液の蛍光Ｘ線分析を行うことで測定することができる。Ｚｎを含有しない溶融Ａｌめっき鋼板については、ＪＩＳ Ｈ８６７２に記載の水酸化ナトリウム法でめっき層を溶解すればよい。また、めっき層表層のＡｌの原子数の割合は、Ｘ線光電子分光分析装置（ＸＰＳ）を用いることで測定することができる。ＸＰＳ分析は、Ｘ線源をＭｇ Ｋα線、取り出し角を４５°として行うことが好ましい。この条件でＸＰＳ分析を行った場合、光電子が基材から放出される深さは０〜４ｎｍとなる。 The concentration of Al in the entire plating layer should be measured by dissolving the plating layer by the hexamethylenetetramine method described in JIS H0401, and then performing fluorescent X-ray analysis of the solution using a calibration curve method using a drip filter paper method. Can do. For a hot-dip Al-plated steel sheet not containing Zn, the plating layer may be dissolved by the sodium hydroxide method described in JIS H8672. Moreover, the ratio of the number of Al atoms in the surface layer of the plating layer can be measured by using an X-ray photoelectron spectrometer (XPS). The XPS analysis is preferably performed with the X-ray source being Mg Kα ray and the extraction angle being 45 °. When XPS analysis is performed under these conditions, the depth at which photoelectrons are emitted from the substrate is 0 to 4 nm.
塗装原板として使用できるＡｌ含有めっき鋼板の例としては、溶融Ｚｎ−０.２質量％Ａｌ合金めっき鋼板や、溶融Ｚｎ−４質量％Ａｌ合金めっき鋼板、溶融Ｚｎ−６質量％Ａｌ−３質量％Ｍｇ合金めっき鋼板、溶融Ｚｎ−５５質量％Ａｌ合金めっき鋼板、溶融Ａｌ−９質量％Ｓｉ合金めっき鋼板などが挙げられる。Ａｌを含有するめっき浴を用いて溶融めっきを行うと、Ａｌはめっき層の表面に濃化する。したがって、Ａｌ含有量が比較的少ない溶融Ｚｎ−０.２質量％Ａｌ合金めっき鋼板や、溶融Ｚｎ−４質量％Ａｌ合金めっき鋼板、溶融Ｚｎ−６質量％Ａｌ−３質量％Ｍｇ合金めっき鋼板などにおいても、溶融めっき浴から引き上げた鋼帯の冷却速度や冷却条件を管理することにより、めっき層表面から４ｎｍの厚み領域における全金属元素の原子数とＣを除く半金属元素の原子数との総和に対するＡｌの原子数の割合を０.２５以上とすることができる。 Examples of the Al-containing plated steel sheet that can be used as a coating original sheet include a molten Zn-0.2 mass% Al alloy-plated steel sheet, a molten Zn-4 mass% Al alloy-plated steel sheet, a molten Zn-6 mass% Al-3 mass%. Examples thereof include a Mg alloy-plated steel sheet, a molten Zn-55 mass% Al alloy-plated steel sheet, and a molten Al-9 mass% Si alloy-plated steel sheet. When hot dipping is performed using a plating bath containing Al, Al is concentrated on the surface of the plating layer. Therefore, a molten Zn-0.2 mass% Al alloy plated steel sheet having a relatively low Al content, a molten Zn-4 mass% Al alloy plated steel sheet, a molten Zn-6 mass% Al-3 mass% Mg alloy plated steel sheet, etc. Also, by controlling the cooling rate and cooling conditions of the steel strip pulled up from the hot dipping bath, the number of atoms of all metal elements in the thickness region of 4 nm from the plating layer surface and the number of atoms of semi-metal elements excluding C The ratio of the number of Al atoms to the sum can be 0.25 or more.
Ａｌ含有めっき鋼板の下地鋼としては、低炭素鋼や中炭素鋼、高炭素鋼、合金鋼などが使用される。加工性が必要とされる場合は、低炭素Ｔｉ添加鋼、低炭素Ｎｂ添加鋼などの深絞り用鋼板が下地鋼として好ましい。 As the base steel of the Al-containing plated steel sheet, low carbon steel, medium carbon steel, high carbon steel, alloy steel or the like is used. When workability is required, steel sheets for deep drawing such as low carbon Ti-added steel and low carbon Nb-added steel are preferred as the base steel.
［第２のステップ］
第２のステップでは、上述の本発明の表面処理液を準備する。
[Second step]
In the second step, the above-described surface treatment liquid of the present invention is prepared.
前述の通り、本発明の表面処理液の調製方法は、特に限定されない。たとえば、アミノ基またはエポキシ基を有するシランカップリング剤の水溶液に、所定量の水溶性レゾール型フェノール樹脂を添加し、水で所望の濃度まで希釈すればよい。 As described above, the method for preparing the surface treatment liquid of the present invention is not particularly limited. For example, a predetermined amount of a water-soluble resol type phenol resin may be added to an aqueous solution of a silane coupling agent having an amino group or an epoxy group, and diluted with water to a desired concentration.
［第３のステップ］
第３のステップでは、第２のステップで準備した本発明の表面処理液を、第１のステップで準備したＡｌ含有めっき鋼板（塗装原板）の表面に塗布し、乾燥させて、表面処理皮膜を形成する。このとき、Ａｌ含有めっき鋼板の片面のみに表面処理皮膜を形成してもよいし、両面に表面処理皮膜を形成してもよい。
[Third step]
In the third step, the surface treatment liquid of the present invention prepared in the second step is applied to the surface of the Al-containing plated steel plate (painted original plate) prepared in the first step, and dried to form a surface treatment film. Form. At this time, the surface treatment film may be formed only on one surface of the Al-containing plated steel sheet, or the surface treatment film may be formed on both surfaces.
表面処理液の塗布方法は、特に限定されず、プレコート鋼板の製造に使用されている方法から適宜選択すればよい。そのような塗布方法の例には、ロールコート法、フローコート法、カーテンフロー法、スプレー法、浸漬法などが含まれる。 The method for applying the surface treatment liquid is not particularly limited, and may be appropriately selected from methods used for manufacturing precoated steel sheets. Examples of such a coating method include a roll coating method, a flow coating method, a curtain flow method, a spray method, a dipping method, and the like.
表面処理液の塗布量は、特に限定されないが、乾燥させた後の付着量が１０〜３００ｍｇ／ｍ２の範囲内（膜厚が２〜５０ｎｍの範囲内）となる量であることが好ましい。付着量が１０ｍｇ／ｍ２未満の場合、塗膜密着性および耐水性を十分に向上させることができない。一方、付着量が３００ｍｇ／ｍ２超の場合、膜厚の増大に伴って加工時に皮膜の凝集破壊が発生しやすくなり、表面処理皮膜の効果が低下してしまうおそれがある。 The coating amount of the surface treatment liquid is not particularly limited, but it is preferable that the adhesion amount after drying is in the range of 10 to 300 mg / m 2 (the film thickness is in the range of 2 to 50 nm). When the adhesion amount is less than 10 mg / m 2 , the coating film adhesion and water resistance cannot be sufficiently improved. On the other hand, when the adhesion amount is more than 300 mg / m 2 , cohesive failure of the film tends to occur during processing as the film thickness increases, and the effect of the surface treatment film may be reduced.
表面処理液の乾燥温度は、水溶性レゾール型フェノール樹脂を硬化させることができれば特に限定されず、例えば４０〜２３０℃程度であればよい。 The drying temperature of the surface treatment liquid is not particularly limited as long as the water-soluble resol type phenol resin can be cured, and may be, for example, about 40 to 230 ° C.
Ａｌ含有めっき鋼板の表面にアルカリ性の表面処理液を塗布すると、めっき層表層のＡｌ（酸化物および水酸化物）は、アルミン酸イオン（Ａｌ（ＯＨ）４ −）となり表面処理液中に溶解する。したがって、塗布された表面処理液中には、ヒドロキシ基を有する水溶性レゾール型フェノール樹脂、アミノ基またはエポキシ基とヒドロキシ基とを有するシランカップリング剤、およびヒドロキシ基を有するアルミン酸イオンが溶解している。 When an alkaline surface treatment liquid is applied to the surface of the Al-containing plated steel sheet, Al (oxide and hydroxide) on the surface of the plating layer becomes aluminate ions (Al (OH) 4 − ) and dissolves in the surface treatment liquid. . Therefore, in the applied surface treatment solution, a water-soluble resol type phenol resin having a hydroxy group, a silane coupling agent having an amino group or an epoxy group and a hydroxy group, and an aluminate ion having a hydroxy group are dissolved. ing.
次いで、４０〜２３０℃程度で塗布した表面処理液を乾燥させると、水溶性レゾール型フェノール樹脂が硬化するとともに、シランカップリング剤およびアルミン酸イオンはフェノール樹脂を架橋する。また、水溶性レゾール型フェノール樹脂、シランカップリング剤およびアルミン酸イオンは、めっき層表層にも結合する。すなわち、水溶性レゾール型フェノール樹脂のヒドロキシ基、シランカップリング剤のヒドロキシ基、アルミン酸イオンのヒドロキシ基およびめっき層表層のヒドロキシ基が互いに脱水縮合して、表面処理皮膜が形成される。 Next, when the surface treatment liquid applied at about 40 to 230 ° C. is dried, the water-soluble resol type phenol resin is cured, and the silane coupling agent and aluminate ions crosslink the phenol resin. Further, the water-soluble resol type phenol resin, the silane coupling agent and the aluminate ions are also bonded to the surface layer of the plating layer. That is, the hydroxy group of the water-soluble resol type phenol resin, the hydroxy group of the silane coupling agent, the hydroxy group of the aluminate ion and the hydroxy group of the plating layer surface are dehydrated and condensed to form a surface treatment film.
このようにして形成された表面処理皮膜は、皮膜を構成する各成分がめっき層表層に脱水縮合しているため、Ａｌ含有めっき鋼板（塗装原板）に強固に密着している（塗膜密着性の向上）。また、皮膜を構成する各成分が互いに脱水縮合しているため、強固かつ緻密な皮膜を形成している（耐湿性の向上）。さらに、シランカップリング剤のアミノ基またはエポキシ基は、表面処理皮膜（塗装前処理皮膜）の上に形成される塗膜を構成する有機樹脂（例えば、エポキシ樹脂やポリエステル）と脱水縮合して強固に結合することができる（塗膜密着性の向上）。 The surface treatment film thus formed is firmly adhered to the Al-containing plated steel sheet (painted original sheet) because each component constituting the film is dehydrated and condensed on the surface of the plated layer (coating adhesion) Improvement). Moreover, since each component which comprises a membrane | film | coat mutually carries out dehydration condensation, the strong and precise | minute film | membrane is formed (improvement of moisture resistance). Furthermore, the amino group or epoxy group of the silane coupling agent is strongly dehydrated and condensed with an organic resin (for example, epoxy resin or polyester) that forms the coating film formed on the surface treatment film (pre-coating film). (Coating film adhesion is improved).
以上のように、本発明の表面処理鋼板の製造方法によれば、六価クロムを使用せずに、塗膜密着性および耐水性に優れた表面処理鋼板を製造することができる。 As described above, according to the method for producing a surface-treated steel sheet of the present invention, a surface-treated steel sheet having excellent coating film adhesion and water resistance can be produced without using hexavalent chromium.
本発明の製造方法で形成された表面処理鋼板（以下「本発明の表面処理鋼板」ともいう）では、表面処理皮膜は、通常、Ａｌを０.２原子％以上含有している。表面処理皮膜中のＡｌの含有比率は、Ｘ線光電子分光分析装置（ＸＰＳ）を用いて表面処理皮膜の表面から測定することができる。 In the surface-treated steel sheet formed by the production method of the present invention (hereinafter also referred to as “surface-treated steel sheet of the present invention”), the surface-treated film usually contains 0.2 atomic% or more of Al. The content ratio of Al in the surface treatment film can be measured from the surface of the surface treatment film using an X-ray photoelectron spectrometer (XPS).
３．塗装鋼板
本発明の表面処理鋼板の表面処理皮膜（塗装前処理皮膜）の上に塗膜を形成することで、塗膜密着性および耐水性に優れた塗装鋼板を製造することができる。
3. Painted steel sheet By forming a coating film on the surface-treated film (pre-coating film) of the surface-treated steel sheet of the present invention, a coated steel sheet having excellent coating film adhesion and water resistance can be produced.
塗膜は、１層であってもよいし、２層以上であってもよい。通常は、下塗り塗膜と上塗り塗膜の２層からなる。 The coating film may be a single layer or two or more layers. Usually, it consists of two layers, an undercoat and a topcoat.
塗膜は、公知の方法で形成されうる。たとえば、ベースとなる有機樹脂を含む塗料を本発明の表面処理鋼板の表面に塗布し、焼き付ければよい。塗料の塗布方法は、特に限定されず、プレコート鋼板の製造に使用されている方法から適宜選択すればよい。塗布方法の例には、ロールコート法、フローコート法、カーテンフロー法、スプレー法などが含まれる。焼き付け条件は、例えば、到達板温１５０〜２７０℃で３０〜１２０秒間焼き付ければよい。 The coating film can be formed by a known method. For example, a paint containing an organic resin as a base may be applied to the surface of the surface-treated steel sheet of the present invention and baked. The coating method of the paint is not particularly limited, and may be appropriately selected from the methods used for producing the precoated steel sheet. Examples of the coating method include a roll coating method, a flow coating method, a curtain flow method, and a spray method. The baking conditions may be, for example, baking at an ultimate plate temperature of 150 to 270 ° C. for 30 to 120 seconds.
塗膜を構成する有機樹脂の種類は、特に限定されず、必要な性質に応じて公知の有機樹脂から適宜選択すればよい。たとえば、下塗り塗膜と上塗り塗膜を形成する場合、エポキシ樹脂またはポリエステルをベースとする下塗り塗膜を形成し、その上にポリエステル、フッ素樹脂またはアクリル樹脂をベースとする上塗り塗膜を形成すればよい。表面処理皮膜のすぐ上に形成される塗膜（上記の例では下塗り塗膜）を、エポキシ樹脂またはポリエステルをベースとする塗膜とすることで、表面処理皮膜への密着性をより向上させることができる。 The kind of organic resin which comprises a coating film is not specifically limited, What is necessary is just to select suitably from well-known organic resin according to a required property. For example, when forming an undercoating film and an overcoating film, if an undercoating film based on an epoxy resin or polyester is formed, and an overcoating film based on a polyester, fluororesin or acrylic resin is formed thereon, Good. To improve the adhesion to the surface treatment film by making the coating film (undercoat film in the above example) formed immediately above the surface treatment film into a coating film based on epoxy resin or polyester. Can do.
本発明の表面処理鋼板の表面処理皮膜には、金属化合物からなる防錆顔料が含有されていない。したがって、塗装鋼板の耐食性をさらに向上させる観点からは、塗膜（特に、下塗り塗膜）に、防錆顔料を配合することが好ましい。環境負荷の低減という本発明の目的を考慮すると、塗膜に配合する防錆顔料としては、六価クロムを含有しない防錆顔料が好ましい。そのような防錆顔料の例には、リン酸亜鉛、亜リン酸亜鉛、リン酸亜鉛マグネシウム、リン酸マグネシウム、亜リン酸マグネシウム、シリカ、カルシウムイオン交換シリカ、リン酸ジルコニウム、トリポリリン酸２水素アルミニウム、酸化亜鉛、リンモリブデン酸亜鉛、メタホウ酸バリウムなどが含まれる。 The surface-treated film of the surface-treated steel sheet of the present invention does not contain a rust preventive pigment made of a metal compound. Therefore, from the viewpoint of further improving the corrosion resistance of the coated steel sheet, it is preferable to add a rust preventive pigment to the coating film (particularly, the undercoat coating film). Considering the object of the present invention of reducing the environmental load, a rust preventive pigment not containing hexavalent chromium is preferable as the rust preventive pigment to be blended in the coating film. Examples of such rust preventive pigments include zinc phosphate, zinc phosphite, magnesium magnesium phosphate, magnesium phosphate, magnesium phosphite, silica, calcium ion exchanged silica, zirconium phosphate, aluminum dihydrogen tripolyphosphate. Zinc oxide, zinc phosphomolybdate, barium metaborate, and the like.
また、塗膜には、着色顔料や、パール顔料、メタリック顔料、体質顔料を配合してもよい。着色顔料の例には、酸化チタン、カーボンブラック、酸化クロム、酸化鉄、ベンガラ、チタンイエロー、コバルトブルー、コバルトグリーン、アニリンブラック、フタロシアニンブルーなどが含まれる。メタリック顔料の例には、アルミやステンレス、ニッケルなどの金属粉が含まれる。体質顔料の例には、硫酸バリウム、酸化チタン、シリカ、炭酸カルシウムなどが含まれる。 Moreover, you may mix | blend a color pigment, a pearl pigment, a metallic pigment, and an extender with a coating film. Examples of the color pigment include titanium oxide, carbon black, chromium oxide, iron oxide, bengara, titanium yellow, cobalt blue, cobalt green, aniline black, phthalocyanine blue and the like. Examples of metallic pigments include metal powders such as aluminum, stainless steel and nickel. Examples of extender pigments include barium sulfate, titanium oxide, silica, calcium carbonate and the like.
さらに、塗膜には、塗膜硬度および耐摩耗性を向上させる観点または塗膜表面に凹凸を付与し外観を向上させる観点から、鱗片状無機質添加材や無機質繊維、粒状または塊状の有機骨材、粒状または塊状の無機骨材、つや消し材などを配合してもよい。鱗片状無機質添加材の例には、ガラスフレーク、硫酸バリウムフレーク、グラファイトフレーク、合成マイカフレーク、合成アルミナフレーク、シリカフレーク、雲母状酸化鉄（ＭＩＯ）などが含まれる。無機質繊維の例には、チタン酸カリウム繊維、ウォラスナイト繊維、炭化ケイ素繊維、アルミナ繊維、アルミナシリケート繊維、シリカ繊維、ロックウール、スラグウール、ガラス繊維、炭素繊維などが含まれる。有機骨材の例には、アクリルビーズ、ポリアクリロニトリルビーズなどが含まれる。無機骨材、つや消し剤の例には、ガラスビース、シリカ粉などが含まれる。 Further, from the viewpoint of improving the coating film hardness and abrasion resistance, or from the viewpoint of improving the appearance by imparting irregularities to the coating film surface, the scaly inorganic additive, inorganic fiber, granular or massive organic aggregate In addition, granular or massive inorganic aggregates, matting materials and the like may be blended. Examples of the flaky inorganic additive include glass flake, barium sulfate flake, graphite flake, synthetic mica flake, synthetic alumina flake, silica flake, mica-like iron oxide (MIO) and the like. Examples of the inorganic fiber include potassium titanate fiber, wollastonite fiber, silicon carbide fiber, alumina fiber, alumina silicate fiber, silica fiber, rock wool, slag wool, glass fiber, carbon fiber and the like. Examples of the organic aggregate include acrylic beads and polyacrylonitrile beads. Examples of inorganic aggregates and matting agents include glass beads and silica powder.
本発明の塗装鋼板は、塗膜密着性、耐湿性および耐食性に優れており、かつ六価クロムを含まず環境負荷が小さいため、例えば外装材用のプレコート鋼板として好適である。 The coated steel sheet of the present invention is suitable as, for example, a pre-coated steel sheet for exterior materials because it has excellent coating film adhesion, moisture resistance, and corrosion resistance and does not contain hexavalent chromium and has a small environmental load.
以下、本発明を実施例を参照して詳細に説明するが、本発明はこれらの実施例により限定されない。 EXAMPLES Hereinafter, although this invention is demonstrated in detail with reference to an Example, this invention is not limited by these Examples.
１．塗装鋼板の作製
（１）塗装原板
塗装原板として、以下の６種類のめっき鋼板（板厚０.５ｍｍ）を準備した。
１）めっき鋼板Ａ
・溶融Ｚｎ−０.２質量％Ａｌ合金めっき鋼板
・片面付着量：１２５ｇ／ｍ２
２）めっき鋼板Ｂ
・溶融Ｚｎ−４質量％Ａｌ合金めっき鋼板
・片面付着量：１２５ｇ／ｍ２
３）めっき鋼板Ｃ
・溶融Ｚｎ−６質量％Ａｌ−３質量％Ｍｇ合金めっき鋼板
・片面付着量：９０ｇ／ｍ２
４）めっき鋼板Ｄ
・溶融Ｚｎ−５５質量％Ａｌ合金めっき鋼板
・片面付着量：７５ｇ／ｍ２
５）めっき鋼板Ｅ
・溶融Ａｌ−９質量％Ｓｉ合金めっき鋼板
・片面付着量：５０ｇ／ｍ２
６）めっき鋼板Ｆ（比較材）
・電気Ｚｎめっき鋼板
・片面付着量：２０ｇ／ｍ２
1. Preparation of coated steel plate (1) Painted raw plate The following six types of plated steel plates (plate thickness 0.5 mm) were prepared as coated raw plates.
1) Plated steel sheet A
・ Fused Zn-0.2 mass% Al alloy-plated steel sheet ・ Adhesion on one side: 125 g / m 2
2) Plated steel plate B
・ Fused Zn-4 mass% Al alloy-plated steel sheet ・ Adhesion on one side: 125 g / m 2
3) Plated steel sheet C
-Molten Zn-6 mass% Al-3 mass% Mg alloy plated steel sheet-Adhesion on one side: 90 g / m 2
4) Plated steel sheet D
-Molten Zn-55 mass% Al alloy plated steel sheet-Adhesion on one side: 75 g / m 2
5) Plated steel sheet E
-Molten Al-9 mass% Si alloy plated steel sheet-Adhesion on one side: 50 g / m 2
6) Plated steel sheet F (comparative material)
And electrical Zn-plated steel sheet, single-sided coating weight: 20g / m 2
めっき鋼板Ａ、Ｂ、ＣおよびＦについては、表面調整剤（ＮＰコンディショナー７００；日本ペイント株式会社）を用いてＮｉ置換析出型の表面調整（化成処理）を行った。めっき鋼板ＤおよびＥについては、アルカリ脱脂し、水洗した。 About the plated steel plates A, B, C, and F, the surface adjustment (chemical conversion treatment) of Ni substitution precipitation type was performed using a surface conditioner (NP conditioner 700; Nippon Paint Co., Ltd.). The plated steel plates D and E were alkali degreased and washed with water.
各めっき鋼板について、めっき層表面から４ｎｍの厚み領域における全金属元素の原子数とＣを除く半金属元素の原子数との総和に対するＡｌの原子数の割合を、Ｘ線光電子分光分析装置（ＸＰＳ）を用いて測定した。ＸＰＳ分析は、Ｘ線源をＭｇ Ｋα線とし、取り出し角を４５°として行った。表１に測定結果を示す。 For each plated steel sheet, the ratio of the number of Al atoms to the sum of the number of atoms of all metal elements and the number of metalloid elements other than C in a thickness region of 4 nm from the surface of the plated layer was measured using an X-ray photoelectron spectrometer (XPS). ). The XPS analysis was performed with an X-ray source of Mg Kα ray and an extraction angle of 45 °. Table 1 shows the measurement results.
（２）表面処理（塗装前処理）
表２に示すめっき鋼板の表面（片面）に、表２に示す組成の表面処理液をバーコーターで塗布し、１００℃で乾燥させて、表面処理皮膜（塗装前処理皮膜）を形成した。なお、表２の比較例５および９については、調製直後に表面処理液に沈殿が生じてしまったため、表面処理液を塗装原板に塗布することができなかった。
(2) Surface treatment (pre-painting treatment)
A surface treatment liquid having the composition shown in Table 2 was applied to the surface (one side) of the plated steel sheet shown in Table 2 with a bar coater and dried at 100 ° C. to form a surface treatment film (pre-treatment film). In Comparative Examples 5 and 9 in Table 2, precipitation occurred in the surface treatment liquid immediately after preparation, and therefore the surface treatment liquid could not be applied to the coating original plate.
表面処理液は、以下の手順で調製した。まず、０.５Ｌのイオン交換水および所定量のシランカップリング剤をビーカーに入れて攪拌した後、１日放置してシランカップリング剤を加水分解させた。次いで、ビーカー内の水溶液に所定量のレゾール型フェノール樹脂を添加した後、合計量が１Ｌとなるようにイオン交換水を加え、攪拌した。 The surface treatment liquid was prepared by the following procedure. First, 0.5 L of ion exchange water and a predetermined amount of a silane coupling agent were placed in a beaker and stirred, and then left for 1 day to hydrolyze the silane coupling agent. Next, after adding a predetermined amount of resol-type phenol resin to the aqueous solution in the beaker, ion-exchanged water was added and stirred so that the total amount became 1 L.
調製した各表面処理液について、３０℃の恒温槽内で７日間静置した後の様子を観察して、安定性を評価した。調製直後と変化がない場合を「○」、わずかに変色が見られたものを「△」、沈殿が発生したりゲル化したりしたものを「×」と評価した。各表面処理液の安定性の評価結果を表２に示す。 About each prepared surface treatment liquid, the mode after leaving still for 7 days in a 30 degreeC thermostat was observed, and stability was evaluated. The case where there was no change immediately after the preparation was evaluated as “◯”, the case where slight discoloration was observed was evaluated as “Δ”, and the case where precipitation occurred or gelled was evaluated as “×”. Table 2 shows the evaluation results of the stability of each surface treatment liquid.
各表面処理めっき鋼板の表面処理皮膜中のＳｉおよび各種金属含有量を蛍光Ｘ線分析装置を用いて測定し、測定されたＳｉおよび各種金属含有量から表面処理皮膜の付着量を算出した。シランカップリング剤を含有しない表面処理皮膜（比較例１）については、赤外線分光法の吸光度法により付着量を測定した。前述の通り、比較例５および９については、表面処理液を塗装原板に塗布することができなかったため、付着量は測定しなかった。各表面処理めっき鋼板の表面処理皮膜の付着量を表２に示す。 Si and various metal contents in the surface-treated film of each surface-treated plated steel sheet were measured using a fluorescent X-ray analyzer, and the adhesion amount of the surface-treated film was calculated from the measured Si and various metal contents. About the surface treatment film | membrane (comparative example 1) which does not contain a silane coupling agent, the adhesion amount was measured by the absorbance method of infrared spectroscopy. As described above, in Comparative Examples 5 and 9, since the surface treatment liquid could not be applied to the coating original plate, the adhesion amount was not measured. Table 2 shows the adhesion amount of the surface-treated film on each surface-treated plated steel sheet.
また、各表面処理めっき鋼板の表面処理皮膜中のＡｌの含有量をＸ線光電子分光分析装置（ＸＰＳ）を用いて測定した。各表面処理めっき鋼板の表面処理皮膜中のＡｌの含有量を表２に示す。 Moreover, the content of Al in the surface treatment film of each surface-treated plated steel sheet was measured using an X-ray photoelectron spectrometer (XPS). Table 2 shows the Al content in the surface-treated film of each surface-treated plated steel sheet.
表２に示される水溶性レゾール型フェノール樹脂について、樹脂Ａは、スミライトレジンＰＲ−５０７８１（住友ベークライト株式会社）を使用した。樹脂Ｂは、スミライトレジンＰＲ−１４１７０（住友ベークライト株式会社）を使用した。 About the water-soluble resol type phenol resin shown in Table 2, resin A used Sumireite resin PR-50781 (Sumitomo Bakelite Co., Ltd.). Resin B used was Sumitrite Resin PR-14170 (Sumitomo Bakelite Co., Ltd.).
また、シランカップリング剤について、アミノシランＡは、Ｚ−６０１１（３−アミノプロピルトリエトキシシラン；東レ・ダウコーニング株式会社）を使用した。アミノシランＢは、ＫＢＭ−６０２（Ｎ−（２−アミノエチル）３−アミノプロピルメチルジメトキシシラン；信越化学工業株式会社）を使用した。エポキシシランは、ＫＢＥ−４０３（３−グリシドキシプロピルトリエトキシシラン；信越化学工業株式会社）を使用した。メタクリロキシシランは、Ｚ−６０３０（３−メタクリロキシプロピルトリメトキシシラン；東レ・ダウコーニング株式会社）を使用した。メルカプトシランは、ＫＢＭ−８０３（３−メルカプトプロピルトリメトキシシラン；信越化学工業株式会社）を使用した。 Moreover, Z-6011 (3-aminopropyltriethoxysilane; Toray Dow Corning Co., Ltd.) was used for aminosilane A about the silane coupling agent. As aminosilane B, KBM-602 (N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane; Shin-Etsu Chemical Co., Ltd.) was used. As the epoxy silane, KBE-403 (3-glycidoxypropyltriethoxysilane; Shin-Etsu Chemical Co., Ltd.) was used. As the methacryloxysilane, Z-6030 (3-methacryloxypropyltrimethoxysilane; Toray Dow Corning Co., Ltd.) was used. As the mercaptosilane, KBM-803 (3-mercaptopropyltrimethoxysilane; Shin-Etsu Chemical Co., Ltd.) was used.
（３）下塗り塗装および上塗り塗装
各表面処理めっき鋼板（表面処理できなかった比較例５および９を除く）の表面に、溶剤系下塗り塗料を塗布し、２００℃で焼き付けて、膜厚５μｍの下塗り塗膜を形成した。
(3) Undercoating and overcoating Applying a solvent-based undercoating paint to the surface of each surface-treated plated steel sheet (excluding Comparative Examples 5 and 9 where surface treatment was not possible), baking at 200 ° C., and undercoating the film thickness of 5 μm A coating film was formed.
溶剤系下塗り塗料としては、イソシアネート架橋型エポキシ樹脂をベースとし、防錆顔料として、リン酸水素マグネシウム（塗料固形分中５質量％）、リン酸亜鉛（１０質量％）およびトリポリリン酸アルミニウム（１０質量％）を配合し、体質顔料として、酸化チタン（１５質量％）および硫酸バリウム（１０質量％）を配合したものを使用した。 Solvent-based undercoats are based on isocyanate-crosslinked epoxy resins, and as antirust pigments, magnesium hydrogen phosphate (5% by mass in the solid content of paint), zinc phosphate (10% by mass) and aluminum tripolyphosphate (10% by mass). %) And titanium pigment (15% by mass) and barium sulfate (10% by mass) were used as extender pigments.
次いで、下塗り塗膜を形成した各めっき鋼板の表面に、ポリエステル樹脂をベースとする上塗り塗料（フレキコート１０６０；日本ペイント株式会社）を塗布し、２１５℃で焼き付けて、膜厚１５μｍの上塗り塗膜を形成した。 Next, a top coat paint based on a polyester resin (Flexcoat 1060; Nippon Paint Co., Ltd.) is applied to the surface of each plated steel sheet on which an undercoat coat has been formed, and baked at 215 ° C. Formed.
２．評価試験
（１）塗膜密着性試験
各塗装鋼板（実施例１〜１４、比較例１〜４、６〜８および１０）から試験片を切り出し、塗膜密着性試験を実施した。各試験片を沸騰水に２時間浸漬した後、沸騰水から取り出した。次いで、各試験片に２Ｔの折り曲げ加工を施した。各試験片の折り曲げ加工部に粘着テープを貼り付けた後、瞬時にテープを引き剥がした。テープ剥離後、各試験片について塗膜の剥離状態を観察した。塗膜が剥離しなかった場合は「◎」、１０面積％未満の微小な剥離が発生した場合は「○」、１０面積％以上３０面積％未満の剥離が発生した場合は「△」、３０面積％以上の剥離が発生した場合は「×」と評価した。
2. Evaluation test (1) Coating film adhesion test A test piece was cut out from each coated steel sheet (Examples 1 to 14, Comparative Examples 1 to 4, 6 to 8 and 10), and a coating film adhesion test was performed. Each test piece was immersed in boiling water for 2 hours and then removed from the boiling water. Next, each test piece was subjected to 2T bending. After affixing the adhesive tape to the bent part of each test piece, the tape was instantly peeled off. After the tape peeling, the peeled state of the coating film was observed for each test piece. “◎” if the coating did not peel, “◯” if a fine peeling of less than 10 area% occurred, “△” if a peeling of 10 area% or more but less than 30 area% occurred, “30” When peeling of area% or more occurred, it was evaluated as “x”.
（２）耐食性試験
各塗装鋼板（実施例１〜１４、比較例１〜４、６〜８および１０）から試験片を切り出し、耐食性試験を実施した。塗膜の表面からめっき層に達するＸ字型の切り込み（クロスカット部）を各試験片にカッターナイフを用いて形成した。クロスカット部を形成した各試験片について、「ＪＩＳ Ｋ ５６００−７−９：２００６、塗料一般試験方法、第７部：塗膜の長期耐久性、第９節：サイクル腐食試験方法 サイクルＡ」に準拠して、１０００時間（１２５サイクル）サイクル腐食試験を行った。試験後、各試験片について、クロスカット部からの最大フクレ幅を計測した。フクレ幅が１ｍｍ以下の場合は「◎」、１ｍｍ超２ｍｍ以下の場合は「○」、２ｍｍ超４ｍｍ以下の場合は「△」、４ｍｍ超の場合は「×」と評価した。
(2) Corrosion resistance test A test piece was cut out from each coated steel sheet (Examples 1 to 14, Comparative Examples 1 to 4, 6 to 8 and 10), and a corrosion resistance test was performed. An X-shaped cut (cross cut portion) reaching the plating layer from the surface of the coating film was formed on each test piece using a cutter knife. For each test piece in which the cross cut portion is formed, “JIS K 5600-7-9: 2006, paint general test method, Part 7: Long-term durability of coating film, Section 9: Cyclic corrosion test method Cycle A” In conformity with this, a 1000 hour (125 cycles) cycle corrosion test was conducted. After the test, the maximum swelling width from the cross cut portion was measured for each test piece. When the blister width was 1 mm or less, the evaluation was “」 ”, when it was more than 1 mm and 2 mm or less,“ ◯ ”, when it was 2 mm or more and 4 mm or less,“ Δ ”, and when it was more than 4 mm, it was evaluated as“ x ”.
（３）評価結果
各表面処理めっき鋼板（実施例１〜１４、比較例１〜４、６〜８および１０）の塗膜密着性試験および耐食性試験の結果を表３に示す。
(3) Evaluation results Table 3 shows the results of the coating film adhesion test and the corrosion resistance test of each surface-treated plated steel sheet (Examples 1 to 14, Comparative Examples 1 to 4, 6 to 8 and 10).
めっき層がＡｌを含有しない塗装原板Ｆを用いた比較例３の塗装鋼板では、表面処理皮膜中にＡｌが取り込まれず、安定した強固かつ緻密な皮膜を形成できないため、塗膜密着性および耐食性のいずれについても良好な結果を得られなかった。同様に、水溶性レゾール型フェノール樹脂を配合していない表面処理液を用いた比較例７の塗装鋼板、および水溶性レゾール型フェノール樹脂の配合比率が小さい表面処理液を用いた比較例２の塗装鋼板でも、安定した強固かつ緻密な皮膜を形成できないため、塗膜密着性および耐食性のいずれについても良好な結果を得られなかった。 In the coated steel sheet of Comparative Example 3 using the coating original plate F in which the plating layer does not contain Al, Al is not taken into the surface treatment film, and a stable strong and dense film cannot be formed. In either case, good results were not obtained. Similarly, the coated steel sheet of Comparative Example 7 using a surface treatment liquid that does not contain a water-soluble resol type phenolic resin, and the coating of Comparative Example 2 using a surface treatment liquid that contains a small proportion of water-soluble resol type phenolic resin. Even with a steel plate, a stable, strong and dense film could not be formed, and therefore good results were not obtained for both coating film adhesion and corrosion resistance.
シランカップリング剤を配合していない表面処理液を用いた比較例１の塗装鋼板、ならびにアミノ基およびエポキシ基のいずれも有しないシランカップリング剤を配合した表面処理液を用いた比較例１０の塗装鋼板では、表面処理皮膜の下塗り塗膜に対する密着性が不十分なため、塗膜密着性および耐食性のいずれについても良好な結果を得られなかった。 The coated steel plate of Comparative Example 1 using a surface treatment liquid that does not contain a silane coupling agent, and the Comparative Example 10 using a surface treatment liquid that contains a silane coupling agent that has neither an amino group nor an epoxy group. In the coated steel sheet, since the adhesion to the undercoat film of the surface treatment film was insufficient, good results were not obtained with respect to both the film adhesion and the corrosion resistance.
酸性〜中性の表面処理液を用いた比較例４、６、８および１０の塗装鋼板では、めっき層と表面処理層との界面に形成される反応層が厚くなってしまったため、塗膜密着性および耐食性のいずれについても良好な結果を得られなかった。また、表面処理液に金属化合物を配合した比較例６、８では、表面処理液の安定性が悪かった。 In the coated steel sheets of Comparative Examples 4, 6, 8 and 10 using an acidic to neutral surface treatment solution, the reaction layer formed at the interface between the plating layer and the surface treatment layer was thickened, so that the coating film adheres Good results were not obtained with respect to both corrosion resistance and corrosion resistance. Moreover, in Comparative Examples 6 and 8 in which a metal compound was blended in the surface treatment liquid, the stability of the surface treatment liquid was poor.
一方、水溶性レゾール型フェノール樹脂と、アミノ基またはエポキシ基を有するシランカップリング剤とを含有し、かつ金属化合物を含有しない、アルカリ性の表面処理液水溶液を用いた実施例１〜１４の塗装鋼板では、塗膜密着性および耐食性のいずれについても良好な結果を得られた。 On the other hand, the coated steel sheets of Examples 1 to 14 using an aqueous solution of an alkaline surface treatment liquid containing a water-soluble resol type phenol resin and a silane coupling agent having an amino group or an epoxy group and containing no metal compound. Then, good results were obtained for both coating film adhesion and corrosion resistance.
以上の結果から、実施例１〜１４の塗装鋼板は、塗膜密着性および耐食性に優れていることがわかる。 From the above results, it can be seen that the coated steel sheets of Examples 1 to 14 are excellent in coating film adhesion and corrosion resistance.
本発明の表面処理液は、塗膜密着性および耐水性が高い表面処理鋼板を容易に製造することができるため、塗装前処理用の処理液として有用である。また、本発明の製造方法により得られた表面処理鋼板は、塗膜密着性および耐水性に優れているため、例えば外装建材用のプレコート鋼板の塗装原板として有用である。
The surface treatment liquid of the present invention is useful as a treatment liquid for pre-coating treatment because a surface-treated steel sheet having high coating film adhesion and high water resistance can be easily produced. Moreover, since the surface-treated steel plate obtained by the production method of the present invention is excellent in coating film adhesion and water resistance, it is useful, for example, as a coating raw plate for pre-coated steel plates for exterior building materials.
Claims (10)
水溶性レゾール型フェノール樹脂と、アミノ基またはエポキシ基を有するシランカップリング剤とを含有し、かつ金属成分を含有しない、ｐＨが８〜１３の水溶液である表面処理液を準備するステップと、
前記Ａｌ含有めっき鋼板に前記表面処理液を塗布し、乾燥させて、表面処理皮膜を形成するステップと、
を有する、表面処理鋼板の製造方法。 The number of Al atoms with respect to the sum of the number of atoms of all metal elements and the number of metalloid elements excluding C in the thickness region of 4 nm from the surface of the plating layer when Al is 0.17% by mass or more in the plating layer Preparing an Al-containing plated steel sheet having a ratio of 0.25 or more;
Preparing a surface treatment liquid which is an aqueous solution having a pH of 8 to 13 and containing a water-soluble resol type phenolic resin and a silane coupling agent having an amino group or an epoxy group and not containing a metal component;
Applying the surface treatment liquid to the Al-containing plated steel sheet and drying to form a surface treatment film;
A method for producing a surface-treated steel sheet, comprising:
前記Ａｌ含有めっき鋼板は、めっき層中にＡｌを０.１７質量％以上含有し、かつめっき層表面から４ｎｍの厚み領域における全金属元素の原子数とＣを除く半金属元素の原子数との総和に対するＡｌの原子数の割合が０.２５以上であり、
前記表面処理液は、水溶性レゾール型フェノール樹脂と、アミノ基またはエポキシ基を有するシランカップリング剤とを含有し、かつ金属成分を含有しない、ｐＨが８〜１３の水溶液である、表面処理鋼板。 A surface-treated steel sheet obtained by applying a surface treatment liquid to an Al-containing plated steel sheet and drying to form a surface-treated film,
The Al-containing plated steel sheet contains 0.17% by mass or more of Al in the plating layer, and includes the number of atoms of all metal elements and the number of metalloid elements excluding C in a thickness region of 4 nm from the surface of the plating layer. The ratio of the number of Al atoms to the sum is 0.25 or more,
The surface treatment liquid is a surface-treated steel sheet containing a water-soluble resol-type phenol resin, a silane coupling agent having an amino group or an epoxy group, and not containing a metal component, and an aqueous solution having a pH of 8 to 13. .
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