JP4298575B2 - Chromate-free surface-treated Al-Zn alloy-plated steel sheet with excellent corrosion resistance and method for producing the same - Google Patents
Chromate-free surface-treated Al-Zn alloy-plated steel sheet with excellent corrosion resistance and method for producing the same Download PDFInfo
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- JP4298575B2 JP4298575B2 JP2004132156A JP2004132156A JP4298575B2 JP 4298575 B2 JP4298575 B2 JP 4298575B2 JP 2004132156 A JP2004132156 A JP 2004132156A JP 2004132156 A JP2004132156 A JP 2004132156A JP 4298575 B2 JP4298575 B2 JP 4298575B2
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- 229910018137 Al-Zn Inorganic materials 0.000 title claims description 58
- 229910018573 Al—Zn Inorganic materials 0.000 title claims description 58
- 229910000831 Steel Inorganic materials 0.000 title claims description 58
- 239000010959 steel Substances 0.000 title claims description 58
- 230000007797 corrosion Effects 0.000 title claims description 55
- 238000005260 corrosion Methods 0.000 title claims description 55
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 239000011347 resin Substances 0.000 claims description 73
- 229920005989 resin Polymers 0.000 claims description 73
- -1 phosphoric acid compound Chemical class 0.000 claims description 70
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 69
- 150000003682 vanadium compounds Chemical class 0.000 claims description 55
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 50
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 41
- 229910000077 silane Inorganic materials 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 239000007788 liquid Substances 0.000 claims description 29
- 238000007747 plating Methods 0.000 claims description 28
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 26
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 22
- 239000000956 alloy Substances 0.000 claims description 22
- 229910045601 alloy Inorganic materials 0.000 claims description 22
- 239000000178 monomer Substances 0.000 claims description 20
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 18
- 229920002554 vinyl polymer Polymers 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- 125000003700 epoxy group Chemical group 0.000 claims description 16
- 125000003277 amino group Chemical group 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 229920006026 co-polymeric resin Polymers 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 12
- 125000005396 acrylic acid ester group Chemical group 0.000 claims description 10
- 125000005397 methacrylic acid ester group Chemical group 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- VLOPEOIIELCUML-UHFFFAOYSA-L vanadium(2+);sulfate Chemical compound [V+2].[O-]S([O-])(=O)=O VLOPEOIIELCUML-UHFFFAOYSA-L 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 claims description 5
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical compound O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 0.000 claims description 3
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 claims 2
- 239000010408 film Substances 0.000 description 66
- 235000011007 phosphoric acid Nutrition 0.000 description 37
- 230000000694 effects Effects 0.000 description 30
- 150000004756 silanes Chemical class 0.000 description 23
- 238000004381 surface treatment Methods 0.000 description 23
- 238000012360 testing method Methods 0.000 description 22
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 20
- 239000000463 material Substances 0.000 description 19
- 150000001875 compounds Chemical class 0.000 description 18
- 238000000034 method Methods 0.000 description 16
- 239000004925 Acrylic resin Substances 0.000 description 9
- 229920000178 Acrylic resin Polymers 0.000 description 9
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 8
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 8
- 239000011651 chromium Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 8
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 7
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 7
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 7
- 239000011324 bead Substances 0.000 description 6
- 150000002736 metal compounds Chemical class 0.000 description 6
- 229910052720 vanadium Inorganic materials 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 4
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 4
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 239000008199 coating composition Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 230000000737 periodic effect Effects 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 230000005856 abnormality Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001845 chromium compounds Chemical class 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 150000003016 phosphoric acids Chemical class 0.000 description 2
- QVLTXCYWHPZMCA-UHFFFAOYSA-N po4-po4 Chemical compound OP(O)(O)=O.OP(O)(O)=O QVLTXCYWHPZMCA-UHFFFAOYSA-N 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000007586 pull-out test Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 125000002813 thiocarbonyl group Chemical group *C(*)=S 0.000 description 2
- 150000003609 titanium compounds Chemical class 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 150000003755 zirconium compounds Chemical class 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical class [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-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
- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-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
- 230000002411 adverse Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 239000002335 surface treatment layer Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-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
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Laminated Bodies (AREA)
- Chemical Treatment Of Metals (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Description
本発明は、建材や家電分野の用途において主として無塗装で用いられるＡｌ−Ｚｎ系合金めっき鋼板の表面処理材、特に、所謂５５％Ａｌ−Ｚｎ系合金めつき鋼板に代表される高Ａｌ−Ｚｎ系合金めっき鋼板に好適な、皮膜中にＣｒを含まないクロメートフリー表面処理材に関する。 The present invention is a surface treatment material for an Al—Zn alloy-plated steel sheet that is mainly used unpainted in applications in the field of building materials and home appliances, in particular, a high Al—Zn represented by a so-called 55% Al—Zn alloy-plated steel sheet. The present invention relates to a chromate-free surface treatment material suitable for an alloy-plated steel sheet and containing no Cr in the film.
所謂５５％Ａｌ−Ｚｎ系合金めっき鋼板に代表される高Ａｌ−Ｚｎ系合金めっき鋼板は、めっき外観が美麗で且つ耐食性にも優れていることから、建材用途として屋根材や外壁材等に、また家電用途として例えば冷蔵庫の裏板等に、いずれも無塗装のままで用いられている。これらの用途では、めっき鋼板に長期にわたる防食性が必要となり、湿潤環境に曝されても優れた密着性、耐食性を有することが求められる。また、建材用途の場合には、めっき鋼板がロールフォーミングにより成形されるため、めっきがロールにピックアップしないこと（すなわち、ロールフォーミング性が良好であること）が求められ、また家電用途の場合には、プレス成形後の外観が金型との摺動により黒化しない特性が必要である。 The high Al-Zn alloy-plated steel sheet represented by the so-called 55% Al-Zn alloy-plated steel sheet has a beautiful plating appearance and is excellent in corrosion resistance. Also, as home appliances, for example, they are used without coating on the back plate of a refrigerator. In these uses, the plated steel sheet needs long-term corrosion resistance, and is required to have excellent adhesion and corrosion resistance even when exposed to a humid environment. In addition, in the case of building materials, the plated steel sheet is formed by roll forming, so it is required that the plating is not picked up by the roll (that is, the roll forming property is good). The appearance after press molding must be such that it does not blacken by sliding with the mold.
従来、このような用途に対しては、有機樹脂とＣｒ６＋を含むクロム化合物を含有する表面処理層をめっき表面に形成することにより対応してきた（例えば、特許文献１〜３）。しかしその一方で、最近では環境に対する影響度の観点からＣｒの規制が進みつつあり、これに伴い表面処理のクロメートフリー化が指向されている。また、Ｃｒ３＋は無害であるが実際に市場で使用された場合、皮膜中のＣｒ６＋とＣｒ３＋を見分けることは困難である。このような背景から、Ｃｒ化合物を含まず、しかもクロメート処理に匹敵する優れた耐食性等の性能を有するクロメートフリー皮膜が強く望まれている。
そのなかで、クロムに代わる成分としてバナジウム化合物を含有した処理液を用い、浸漬、塗布、電解処理等の方法によってめっき表面に薄膜を形成させる技術が数多く開示されている。具体的には、（ａ）主にリン酸イオンとバナジン酸イオンを含有する塗料で処理を行う方法（例えば、特許文献４，５）、（ｂ）有機樹脂とチオカルボニル基含有化合物、バナジウム化合物を含む塗膜を形成する方法（特許文献６）、（ｃ）特殊変性フェノール樹脂とバナジウム化合物とジルコニウム、チタニウム等の金属化合物を含む表面処理剤により処理を行う方法（特許文献７）、（ｄ）バナジウム化合物とジルコニウム化合物、チタニウム化合物等を含む表面処理液で処理を行う方法（特許文献８）などが挙げられる。 Among them, many techniques for forming a thin film on a plating surface by a method such as dipping, coating, electrolytic treatment using a treatment liquid containing a vanadium compound as a component replacing chromium are disclosed. Specifically, (a) a method of treating with a paint mainly containing phosphate ions and vanadate ions (for example, Patent Documents 4 and 5), (b) an organic resin, a thiocarbonyl group-containing compound, and a vanadium compound (Patent Document 6), (c) A method of treating with a surface treatment agent containing a specially modified phenolic resin, a vanadium compound, and a metal compound such as zirconium or titanium (Patent Document 7), (d ) A method of performing treatment with a surface treatment solution containing a vanadium compound, a zirconium compound, a titanium compound and the like (Patent Document 8).
しかしながら、特許文献４、特許文献５の方法は、主に５価のバナジウム化合物による防錆効果を狙ったものであるため、大きな防食効果は得られない。また、特許文献６の場合、耐食性向上効果を発揮しているのはチオカルボニル基を含む化合物であり、バナジウム化合物は主に５価のバナジウム化合物であるため、これも大きな防食効果は得られない。特許文献７の場合も、最も耐食性に効果のあるのは特殊変性フェノール樹脂であって、バナジウム、ジルコニウム等の金属塩の効果は小さく、クロメート処理皮膜に比べ耐食性が十分とは言えない。さらに、特許文献８の場合は、２〜５価のバナジウム化合物とジルコニウム化合物やチタニウム化合物との複合皮膜を形成したものであり、２〜４価のバナジウム化合物を用いることにより皮膜の溶解性はある程度まで向上するが、特に高耐食性を要求される高Ａｌ−Ｚｎ系合金めっき鋼板に適用するまでの耐食性レベルには至っていない。 However, since the methods of Patent Document 4 and Patent Document 5 are mainly aimed at the rust prevention effect by the pentavalent vanadium compound, a large anticorrosion effect cannot be obtained. In the case of Patent Document 6, the corrosion resistance improving effect is exhibited by a compound containing a thiocarbonyl group, and the vanadium compound is mainly a pentavalent vanadium compound. . Also in Patent Document 7, the specially modified phenol resin is most effective in corrosion resistance, and the effect of metal salts such as vanadium and zirconium is small, and it cannot be said that the corrosion resistance is sufficient as compared with the chromate-treated film. Further, in the case of Patent Document 8, a composite film of a 2-5 pentavalent vanadium compound and a zirconium compound or a titanium compound is formed. By using a 2-4 tetravalent vanadium compound, the solubility of the film is to some extent. However, it has not reached the level of corrosion resistance until it is applied to a high Al—Zn alloy-plated steel sheet that requires particularly high corrosion resistance.
このように従来技術によるクロメートフリーの表面処理皮膜では、従来から高Ａｌ−Ｚｎ合金めっき鋼板に用いられてきたクロメート処理皮膜に匹敵するような耐食性は得られない。
したがって本発明の目的は、クロメート処理皮膜による表面処理材に匹敵する優れた耐食性を有するとともに、外観品質、加工性及び耐水性等の性能にも優れたＡｌ−Ｚｎ合金めっき鋼板のクロメートフリー表面処理材及びその製造方法を提供することにある。Thus, the conventional chromate-free surface-treated film cannot provide corrosion resistance comparable to the chromate-treated film conventionally used for high Al—Zn alloy-plated steel sheets.
Accordingly, an object of the present invention is to provide a chromate-free surface treatment of an Al-Zn alloy-plated steel sheet having excellent corrosion resistance comparable to that of a surface-treated material by a chromate-treated film, and excellent performance such as appearance quality, workability and water resistance. It is in providing a material and its manufacturing method.
上記課題を解決するための本発明の特徴は以下のとおりである。
［1］Ａｌを２５〜７５質量％含有するＡｌ−Ｚｎ系合金めっき皮膜を有するＡｌ−Ｚｎ系合金めっき鋼板の前記めっき皮膜表面に、４価の価数を有するバナジウム化合物（Ａ）と、リン酸又は／及びリン酸系化合物（Ｂ）と、水溶性有機樹脂又は／及び水分散性有機樹脂からなる有機樹脂（Ｃ）とを主成分とし、前記バナジウム化合物（Ａ）が硫酸酸化バナジウム又はバナジン酸還元生成物からなり、前記有機樹脂（Ｃ）が、エポキシ基又は／及びアミノ基を有するシラン化合物（i）と、アクリル酸又は／及びメタクリル酸（ii）と、炭素数１〜６のアルキル鎖を持つアクリル酸エステル又は／及びメタクリル酸エステル（iii）と、前記成分（ｉ）〜（iii）と共重合可能なビニルモノマー（iｖ）とから得られる共重合樹脂であって、該共重合樹脂の固形分１００質量部に対して、前記シラン化合物（i）の割合が０．１〜３０質量部、前記アクリル酸又は／及びメタクリル酸（ii）の割合が０．５〜１０質量部、前記炭素数１〜６のアルキル鎖を持つアクリル酸エステル又は／及びメタクリル酸エステル（iii）の割合が２０〜９５質量部であり、前記バナジウム化合物（Ａ）の金属Ｖ換算での付着量が１〜１００ｍｇ／ｍ２、前記有機樹脂（Ｃ）の付着量が０．５〜５ｇ／ｍ２である表面処理皮膜を有することを特徴とする耐食性に優れたクロメートフリー表面処理Ａｌ−Ｚｎ系合金めっき鋼板。
The features of the present invention for solving the above-described problems are as follows.
[1] A vanadium compound (A) having a tetravalent valence on the surface of the plated film of an Al-Zn based alloy plated steel sheet having an Al-Zn based alloy plated film containing 25 to 75% by mass of Al, phosphorus The main component is an acid or / and phosphoric acid compound (B) and an organic resin (C) composed of a water-soluble organic resin or / and a water-dispersible organic resin, and the vanadium compound (A) is vanadium sulfate oxide or vanadium. It consists of an acid reduction product, and the organic resin (C) is an silane compound (i) having an epoxy group or / and an amino group, acrylic acid or / and methacrylic acid (ii), or an alkyl having 1 to 6 carbon atoms. A copolymer resin obtained from an acrylic ester or / and methacrylic ester (iii) having a chain and a vinyl monomer (iv) copolymerizable with the components (i) to (iii), The proportion of the silane compound (i) is 0.1 to 30 parts by mass, the proportion of the acrylic acid or / and methacrylic acid (ii) is 0.5 to 10 parts by mass with respect to 100 parts by mass of the solid content of the resin. The ratio of the acrylic acid ester or / and methacrylic acid ester (iii) having an alkyl chain having 1 to 6 carbon atoms is 20 to 95 parts by mass, and the amount of adhesion of the vanadium compound (A) in terms of metal V is 1 Chromate-free surface-treated Al—Zn-based alloy plating excellent in corrosion resistance characterized by having a surface-treated film having a surface treatment film of ˜100 mg / m 2 and the organic resin (C) adhesion amount of 0.5 to 5 g / m 2 steel sheet.
［2］Ａｌを２５〜７５質量％含有するＡｌ−Ｚｎ系合金めっき皮膜を有するＡｌ−Ｚｎ系合金めっき鋼板の前記めっき皮膜表面に、４価の価数を有するバナジウム化合物（Ａ）と、リン酸又は／及びリン酸系化合物（Ｂ）と、水溶性有機樹脂又は／及び水分散性有機樹脂からなる有機樹脂（Ｃ）とを主成分とし、前記バナジウム化合物（Ａ）が硫酸酸化バナジウム又はバナジン酸還元生成物からなり、前記有機樹脂（Ｃ）が、エポキシ基又は／及びアミノ基を有するシラン化合物（i）と、アクリル酸又は／及びメタクリル酸（ii）と、炭素数１〜６のアルキル鎖を持つアクリル酸エステル又は／及びメタクリル酸エステル（iii）と、前記成分（ｉ）〜（iii）と共重合可能なビニルモノマー（iｖ）とから得られる共重合樹脂であって、該共重合樹脂の固形分１００質量部に対して、前記シラン化合物（i）の割合が０．１〜３０質量部、前記アクリル酸又は／及びメタクリル酸（ii）の割合が０．５〜１０質量部、前記炭素数１〜６のアルキル鎖を持つアクリル酸エステル又は／及びメタクリル酸エステル（iii）の割合が２０〜９５質量部である処理液を塗布した後、水洗することなく乾燥することを特徴とする、耐食性に優れたクロメートフリー表面処理Ａｌ−Ｚｎ系合金めっき鋼板の製造方法。 [2] A vanadium compound (A) having a tetravalent valence on the surface of the plated film of the Al-Zn based alloy plated steel sheet having an Al-Zn based alloy plated film containing 25 to 75% by mass of Al, phosphorus The main component is an acid or / and phosphoric acid compound (B) and an organic resin (C) composed of a water-soluble organic resin or / and a water-dispersible organic resin, and the vanadium compound (A) is vanadium sulfate oxide or vanadium. It consists of an acid reduction product, and the organic resin (C) is an silane compound (i) having an epoxy group or / and an amino group, acrylic acid or / and methacrylic acid (ii), or an alkyl having 1 to 6 carbon atoms. A copolymer resin obtained from an acrylic ester or / and methacrylic ester (iii) having a chain and a vinyl monomer (iv) copolymerizable with the components (i) to (iii), The proportion of the silane compound (i) is 0.1 to 30 parts by mass, the proportion of the acrylic acid or / and methacrylic acid (ii) is 0.5 to 10 parts by mass with respect to 100 parts by mass of the solid content of the resin. It is characterized by drying without washing with water after applying the treatment liquid in which the ratio of acrylic acid ester or / and methacrylic acid ester (iii) having an alkyl chain having 1 to 6 carbon atoms is 20 to 95 parts by mass. A method for producing a chromate-free surface-treated Al—Zn alloy-plated steel sheet having excellent corrosion resistance.
［3］Ａｌを２５〜７５質量％含有するＡｌ−Ｚｎ系合金めっき皮膜を有するＡｌ−Ｚｎ系合金めっき鋼板の前記めっき皮膜表面に、４価の価数を有するバナジウム化合物（Ａ）とリン酸又は／及びリン酸系化合物（Ｂ）とを主成分とし、前記バナジウム化合物（Ａ）が硫酸酸化バナジウム又はバナジン酸還元生成物からなる処理液を塗布した後、水洗することなく乾燥し、さらにその上部に、水溶性有機樹脂又は／及び水分散性有機樹脂からなる有機樹脂（Ｃ）を主成分とし、該有機樹脂（Ｃ）が、エポキシ基又は／及びアミノ基を有するシラン化合物（i）と、アクリル酸又は／及びメタクリル酸（ii）と、炭素数１〜６のアルキル鎖を持つアクリル酸エステル又は／及びメタクリル酸エステル（iii）と、前記成分（ｉ）〜（iii）と共重合可能なビニルモノマー（iｖ）とから得られる共重合樹脂であって、該共重合樹脂の固形分１００質量部に対して、前記シラン化合物（i）の割合が０．１〜３０質量部、前記アクリル酸又は／及びメタクリル酸（ii）の割合が０．５〜１０質量部、前記炭素数１〜６のアルキル鎖を持つアクリル酸エステル又は／及びメタクリル酸エステル（iii）の割合が２０〜９５質量部である処理液を塗布した後、水洗することなく乾燥することを特徴とする、耐食性に優れたクロメートフリー表面処理Ａｌ−Ｚｎ系合金めっき鋼板の製造方法。 [3] A vanadium compound (A) having a valence of 4 and phosphoric acid on the surface of the plated film of an Al-Zn based alloy plated steel sheet having an Al-Zn based alloy plated film containing 25 to 75% by mass of Al. Or / and a phosphoric acid compound (B) as a main component , the vanadium compound (A) is coated with a treatment solution comprising vanadium sulfate oxide or a vanadic acid reduction product , and then dried without washing with water. In the upper part, an organic resin (C) composed of a water-soluble organic resin and / or a water-dispersible organic resin is a main component, and the organic resin (C) is a silane compound (i) having an epoxy group or / and an amino group. , Acrylic acid or / and methacrylic acid (ii), acrylic acid ester or / and methacrylic acid ester (iii) having an alkyl chain having 1 to 6 carbon atoms, and the above components (i) to (iii) can be copolymerized. Functional vinyl monomer (iv) and a copolymer resin obtained from a solid content of 100 parts by mass of the copolymer resin, wherein the proportion of the silane compound (i) is 0.1 to 30 parts by mass, The ratio of acrylic acid or / and methacrylic acid (ii) is 0.5 to 10 parts by mass, and the ratio of acrylic acid ester or / and methacrylic acid ester (iii) having the alkyl chain having 1 to 6 carbon atoms is 20 to 95. A method for producing a chromate-free surface-treated Al—Zn-based alloy-plated steel sheet having excellent corrosion resistance, wherein the treatment liquid is applied in parts by mass and then dried without being washed with water.
本発明によれば、耐食性に優れ、且つ外観品質、加工性及び耐水性にも優れたクロメートフリーの表面処理Ａｌ−Ｚｎ系合金めっき鋼板を安定して得ることができる。 According to the present invention, it is possible to stably obtain a chromate-free surface-treated Al—Zn alloy-plated steel sheet having excellent corrosion resistance and excellent appearance quality, workability and water resistance.
本発明のクロメートフリー表面処理Ａｌ−Ｚｎ系合金めっき鋼板のベースとなるめっき鋼板は、めっき皮膜中にＡｌが２５〜７５ｍａｓｓ％含まれるＡｌ−Ｚｎ系合金めっき鋼板であり、所謂５５％Ａｌ−Ｚｎ系合金めっき鋼板が最も代表的なものとして知られている。通常、この種のめっき皮膜中には、ＳｉがＡｌ量の０．５ｍａｓｓ％以上含まれている。また、所謂５５％Ａｌ−Ｚｎ系合金めっき鋼板とは、通常、Ａｌ−Ｚｎ系合金めっき皮膜中にＡｌが５０〜６０ｍａｓｓ％程度含まれるＡｌ−Ｚｎ系合金めっき鋼板（以下の説明において、「高Ａｌ−Ｚｎ系合金めっき鋼板」という場合、上記Ａｌ含有量のＡｌ−Ｚｎ合金めっき鋼板を指すものとする）を指し、そのめっき皮膜中には通常Ｓｉが１〜３ｍａｓｓ％程度含まれている。 The plated steel sheet used as the base of the chromate-free surface-treated Al—Zn alloy-plated steel sheet of the present invention is an Al—Zn-based alloy plated steel sheet containing 25 to 75 mass% of Al in the plating film, so-called 55% Al—Zn. An alloy-plated steel sheet is known as the most typical one. Usually, this type of plating film contains Si in an amount of 0.5 mass% or more of the Al amount. In addition, the so-called 55% Al—Zn alloy-plated steel sheet is usually an Al—Zn-based alloy plated steel sheet in which Al is contained in an Al—Zn alloy plating film in an amount of about 50 to 60 mass% (in the following description, “high The term “Al—Zn alloy-plated steel sheet” refers to an Al—Zn alloy-plated steel sheet having the above-mentioned Al content), and the plating film usually contains about 1 to 3 mass% of Si.
本発明において、めっき皮膜中のＡｌ含有量が２５〜７５ｍａｓｓ％のＡｌ−Ｚｎ系合金めっき鋼板を対象とするのは、このＡｌ含有量の範囲において、特に優れた耐食性（耐赤錆性）が得られるためである。但し、このめっき鋼板には、めっき皮膜中にＡｌを多く含むことに由来する問題として、Ａｌに腐食が生じると黒錆が発生し、赤錆に対しては防錆性を保つものの外観品質が著しく損なわれるという難点がある。また、このめっき鋼板を無塗装で用いる場合、めっきままの外観であることが好まれるためにスキンパスによる表面の著しい平滑化が行われず、このためめっき表面は微細な凹凸が形成されたままの状態になっている。この状態で例えばロールフォーミング加工を受けると、ロールとの接触によってめっき表面にかじりが生じ、ロール損傷の原因となるほか、成形後の外観が劣るという品質面での問題がある。したがって、これらを解消するために、めっき表面にさらに皮膜を形成することが必要となる。
以下に述べるように、本発明による特性改善効果は、めっき皮膜中のＡｌ含有量が２５〜７５ｍａｓｓ％のＡｌ−Ｚｎ系合金めっき鋼板において顕著に得られるものであるが、そのなかでも上記高Ａｌ−Ｚｎ系合金めっき鋼板において特に顕著な特性改善効果が得られる。In the present invention, an Al-Zn alloy-plated steel sheet having an Al content in the plating film of 25 to 75 mass% is targeted, and in this range of Al content, particularly excellent corrosion resistance (red rust resistance) is obtained. Because it is. However, in this plated steel sheet, as a problem derived from the fact that the plating film contains a lot of Al, black rust is generated when corrosion occurs in Al, and the appearance quality of the rust-proofing material is remarkably high against red rust. There is a difficulty that it is damaged. In addition, when this plated steel sheet is used without coating, it is preferred that the appearance is as plated, so that the surface is not significantly smoothed by the skin pass, so that the plated surface remains finely uneven. It has become. In this state, for example, when subjected to roll forming, there is a problem in terms of quality that the plating surface is galling due to contact with the roll and causes damage to the roll, and the appearance after molding is inferior. Therefore, in order to eliminate these, it is necessary to form a film further on the plating surface.
As will be described below, the characteristic improvement effect according to the present invention is remarkably obtained in an Al—Zn alloy-plated steel sheet having an Al content of 25 to 75 mass% in the plating film. -A particularly remarkable characteristic improvement effect is obtained in a Zn-based alloy-plated steel sheet.
次に、Ａｌ−Ｚｎ系合金めっき皮膜の表面に形成する表面処理皮膜について説明する。
本発明において、Ａｌ−Ｚｎ系合金めっき皮膜の表面に形成する表面処理皮膜は、クロム化合物を含まず、４価の価数を有するバナジウム化合物（Ａ）と、リン酸又は／及びリン酸系化合物（Ｂ）と、水溶性有機樹脂又は／及び水分散性有機樹脂からなる有機樹脂（Ｃ）とを主成分とするものである。なお、この表面処理皮膜には、上記成分（Ａ）〜（Ｃ）を主成分とする処理液を塗布して乾燥させて得られる皮膜のほか、上記成分（Ａ）及び（Ｂ）を主成分とする処理液を塗布して乾燥させた後、その上に上記成分（Ｃ）を主成分とする処理液を塗布して乾燥させて得られる皮膜も含まれる。Next, the surface treatment film formed on the surface of the Al—Zn alloy plating film will be described.
In the present invention, the surface treatment film formed on the surface of the Al—Zn alloy plating film does not contain a chromium compound, and has a tetravalent valence vanadium compound (A) and phosphoric acid or / and a phosphoric acid compound. The main component is (B) and an organic resin (C) made of a water-soluble organic resin and / or a water-dispersible organic resin. In addition to the film obtained by applying and drying a treatment liquid containing the above components (A) to (C) as main components, the surface treatment film contains the components (A) and (B) as main components. A coating obtained by applying and drying the treatment liquid and then applying and drying the treatment liquid containing the component (C) as a main component thereon is also included.
本発明が対象とするＡｌ−Ｚｎ系合金めっき鋼板（特に、高Ａｌ−Ｚｎ系合金めっき鋼板）の耐食性を向上させるためには、Ｚｎめっき鋼板、低Ａｌ−Ｚｎ系合金めっき鋼板（例えば、５％Ａｌ−Ｚｎ系合金めっき鋼板）、Ａｌ系めっき鋼板とは異なり、めっき皮膜中のＡｌ、Ｚｎ双方の耐食性を向上させることが必要となる。無機化合物の防食効果について検討を行った結果、本発明が対象となるするようなＡｌ−Ｚｎ系合金めっき、とりわけ高Ａｌ−Ｚｎ系合金めっきに対しては、周期表５Ａに属する元素（Ｖ，Ｎｂ，Ｔａ）の化合物に顕著な防食効果があることを見出した。これら特定元素の化合物による顕著な防食効果は、本発明が対象とするＡｌ−Ｚｎ系合金めっき（特に、高Ａｌ−Ｚｎ系合金めっき）に特有のものであり、Ｚｎめっき等の他めっき種においては認められない効果である。すなわち、Ｚｎめっき等の他めっき種においては、上記化合物と周期表５Ａに属さない他の元素の化合物の効果の違いは認められない。 In order to improve the corrosion resistance of an Al—Zn alloy-plated steel sheet (particularly, a high Al—Zn alloy-plated steel sheet) targeted by the present invention, a Zn-plated steel sheet, a low Al—Zn-based alloy plated steel sheet (for example, 5 % Al—Zn alloy-plated steel sheet) and Al-based plated steel sheet, it is necessary to improve the corrosion resistance of both Al and Zn in the plating film. As a result of examining the anticorrosive effect of the inorganic compound, the elements belonging to the periodic table 5A (V, V, etc.) for Al—Zn alloy plating, particularly high Al—Zn alloy plating, to which the present invention is applied. It has been found that Nb, Ta) compounds have a significant anticorrosive effect. The remarkable anticorrosion effect by the compounds of these specific elements is peculiar to Al—Zn alloy plating (particularly, high Al—Zn alloy plating) targeted by the present invention. Is an unacceptable effect. That is, in other plating species such as Zn plating, there is no difference in the effect between the above compounds and compounds of other elements not belonging to the periodic table 5A.
以上の理由から、表面処理皮膜中には周期表５Ａに属する元素の化合物を用いることが好ましいが、そのなかでもＴａ系化合物とＮｂ系化合物は、Ｖ系化合物と較べて非常に高価であるため、Ｖ系化合物が実用性（防食効果及びコスト）の面から最も有望である。そこで、このバナジウム化合物に着目した検討を行った結果、バナジウム化合物の中でも、バナジウムの価数によって得られる耐食性に著しい違いがあることが判明した。具体的には、５価のバナジウム化合物（例えば、バナジン酸アンモン、バナジン酸ナトリウム等）では大きな耐食性向上効果は認められないのに対して、４価のバナジウム化合物（例えば、硫酸酸化バナジウム、水溶液中で５価のバナジウム化合物を還元したもの）では耐食性が顕著に向上することが判明した。また、４価のバナジウム化合物は、５価のバナジウム化合物に較べて溶解性が低く、このため耐水性に優れた皮膜を形成できる特徴を有している。このため、５価のバナジウム化合物を含む表面処理皮膜は水に濡れることによりＶが溶解し、外観品質が著しく低下するが、４価のバナジウム化合物を含む表面処理皮膜は耐水性が向上し、外観品質の向上効果が認められる。以上の理由から本発明では、表面処理皮膜中に４価の価数を有するバナジウム化合物（Ａ）を添加する。 For the above reasons, it is preferable to use a compound of an element belonging to the periodic table 5A in the surface treatment film, but among them, the Ta-based compound and the Nb-based compound are very expensive compared to the V-based compound. V-based compounds are most promising in terms of practicality (anticorrosive effect and cost). Thus, as a result of investigations focusing on this vanadium compound, it was found that among the vanadium compounds, there is a significant difference in the corrosion resistance obtained by the valence of vanadium. Specifically, pentavalent vanadium compounds (for example, ammonium vanadate, sodium vanadate, etc.) do not have a significant effect of improving corrosion resistance, whereas tetravalent vanadium compounds (for example, vanadium sulfate, in aqueous solution) It was found that the corrosion resistance of the pentavalent vanadium compound was significantly improved. Further, the tetravalent vanadium compound has a characteristic that it has a lower solubility than the pentavalent vanadium compound, and can form a film having excellent water resistance. For this reason, the surface-treated film containing the pentavalent vanadium compound dissolves V when wetted with water and the appearance quality is remarkably deteriorated. However, the surface-treated film containing the tetravalent vanadium compound has improved water resistance and appearance. A quality improvement effect is recognized. For the above reasons, in the present invention, the vanadium compound (A) having a tetravalent valence is added to the surface treatment film.
４価の価数を有するバナジウム化合物としては、バナジウムの酸化物、水酸化物、硫化物、硫酸物、炭酸物、ハロゲン化物、窒化物、フッ化物、炭化物、シアン化物（チオシアン化物）及びこれらの塩などが挙げられ、これらの１種又は２種以上を用いることができる。具体的には、硫酸酸化バナジウム水溶液中で５価のバナジウム化合物を還元したバナジン酸還元生成物等が挙げられる。 Examples of vanadium compounds having a tetravalent valence include vanadium oxide, hydroxide, sulfide, sulfate, carbonate, halide, nitride, fluoride, carbide, cyanide (thiocyanide), and these A salt etc. are mentioned, These 1 type (s) or 2 or more types can be used. Specific examples include vanadic acid reduction products obtained by reducing pentavalent vanadium compounds in a vanadium sulfate oxide aqueous solution.
表面処理皮膜中にリン酸又は／及びリン酸系化合物（Ｂ）を添加する理由は、リン酸又は／及びリン酸系化合物の添加により、４価のバナジウム化合物による防食効果をさらに飛躍的に高めることができるからである。
リン酸及びリン酸系化合物としては、例えば、オルトリン酸、ピロリン酸、ポリリン酸、メタリン酸などのほか、リン酸とＭｇ、Ｚｎ、Ｎｉ、Ｃｏ等の１種以上の金属との金属塩、その他のリン酸化合物（いずれも処理液中に溶解可能なもの）の１種又は２種以上を用いることができる。The reason for adding phosphoric acid or / and a phosphoric acid compound (B) in the surface treatment film is that the anticorrosion effect of the tetravalent vanadium compound is further enhanced by adding phosphoric acid or / and the phosphoric acid compound. Because it can.
Examples of phosphoric acid and phosphoric acid compounds include orthophosphoric acid, pyrophosphoric acid, polyphosphoric acid, metaphosphoric acid, etc., metal salts of phosphoric acid and one or more metals such as Mg, Zn, Ni, Co, etc. 1 type (s) or 2 or more types of these can be used.
４価のバナジウム化合物（Ａ）とともにリン酸又は／及びリン酸系化合物（Ｂ）を添加することによって耐食性が飛躍的に向上する理由は必ずしも明らかではないが、リン酸又は／及びリン酸系化合物が４価のバナジウム化合物とめっき皮膜との反応性を高める作用をすること、４価のバナジウム化合物とリン酸又は／及びリン酸系化合物の複合皮膜が形成されること、等の理由が考えられる。また、４価のバナジウム化合物とリン酸又は／及びリン酸系化合物を複合添加した皮膜では、上記のような耐食性の向上効果が得られるだけでなく、皮膜の耐溶解性が向上する結果、皮膜の外観品質（着色防止）及び耐黒変性も向上し、さらにペフ密着性も向上する。 The reason why the corrosion resistance is drastically improved by adding phosphoric acid or / and the phosphoric acid compound (B) together with the tetravalent vanadium compound (A) is not necessarily clear, but phosphoric acid or / and phosphoric acid compound The reason for this is that it acts to increase the reactivity between the tetravalent vanadium compound and the plating film, and that a composite film of the tetravalent vanadium compound and phosphoric acid or / and a phosphoric acid compound is formed. . In addition, in a film in which a tetravalent vanadium compound and phosphoric acid or / and a phosphoric acid compound are added in combination, not only the above-described effect of improving the corrosion resistance is obtained, but also the dissolution resistance of the film is improved. Appearance quality (anti-coloring) and blackening resistance are improved, and Pef adhesion is also improved.
表面処理皮膜中に水溶性有機樹脂又は／及び水分散性有機樹脂からなる有機樹脂（Ｃ）を添加する理由は、主に加工性と耐食性を向上させる点にある。
皮膜中に有機樹脂を含むことによりロールフォーミングやプレス加工におけるロール、金型とのかじりや摺動傷を防止することが可能となる。また、本表面処理材は屋外で使用されることが多いため、有機樹脂には優れた耐候性を必要とされる。このような観点から、有機樹脂としては脂肪族ポリエステル又は脂肪族ポリカーボネートを主骨格とするウレタン系樹脂或いはアクリル系樹脂が有望である。特にウレタン系樹脂は、アクリル系樹脂よりも優れた耐食性等の特性を有しているが、高価な樹脂であるため汎用的に用いるには支障がある。したがって、アクリル系樹脂の耐食性等の特性をウレタン系樹脂同等のレベルまで高め、そのようなアクリル系樹脂を用いることが好ましい。そこで、アクリル系樹脂の特性を高めることを目的としてモノマー組成の検討を行った結果、エポキシ基又は／及びアミノ基を有するシラン化合物（ｉ）と、アクリル酸又は／及びメタクリル酸（ｉｉ）と、炭素数１〜６のアルキル鎖を持つアクリル酸エステル又は／及びメタクリル酸エステル（ｉｉｉ）と、前記成分（ｉ）〜（ｉｉｉ）と共重合可能なビニルモノマー（ｉｖ）とから得られる、すなわち、これら成分を共重合して得られる共重合アクリル系樹脂を用いることにより、ウレタン系樹脂同等以上の優れた特性が得られることを見出した。The reason for adding the organic resin (C) made of a water-soluble organic resin and / or a water-dispersible organic resin to the surface treatment film is mainly to improve workability and corrosion resistance.
By including an organic resin in the film, it becomes possible to prevent galling and sliding scratches with rolls and dies in roll forming and pressing. In addition, since the surface treatment material is often used outdoors, the organic resin is required to have excellent weather resistance. From such a viewpoint, as the organic resin, a urethane resin or an acrylic resin having an aliphatic polyester or an aliphatic polycarbonate as a main skeleton is promising. In particular, urethane resins have characteristics such as corrosion resistance superior to acrylic resins, but are expensive and have a problem in general use. Therefore, it is preferable to increase the characteristics such as the corrosion resistance of the acrylic resin to a level equivalent to that of the urethane resin and use such an acrylic resin. Then, as a result of examining the monomer composition for the purpose of enhancing the properties of the acrylic resin, a silane compound (i) having an epoxy group or / and an amino group, acrylic acid or / and methacrylic acid (ii), It is obtained from an acrylic acid ester or / and methacrylic acid ester (iii) having an alkyl chain having 1 to 6 carbon atoms, and a vinyl monomer (iv) copolymerizable with the components (i) to (iii). It has been found that by using a copolymerized acrylic resin obtained by copolymerizing these components, excellent characteristics equivalent to or higher than those of a urethane resin can be obtained.
前記エポキシ基又は／及びアミノ基を有するシラン化合物（ｉ）のうち、エポキシ基を有するシラン化合物としては、例えば、３−グリシドキシプロピルトリメトキシキラン、３−グリシドキシプロピルトリエトキシキラン、３−グリシドキシプロピルトリメチルジエトキシキラン等が挙げられ、また、アミノ基を有するシラン化合物としては、例えば、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等が挙げられ、これらの１種又は２種以上を用いることができる。このようなシラン化合物をアクリル系樹脂に重合することにより、アクリル系樹脂による防食効果が飛躍的に高められることが判った。これに対して、エポキシ基又はアミノ基を有しないシラン化合物、例えば、メタクリロキシ基やアクリロキシ基を有するシラン化合物をアクリル系樹脂に重合した場合には、逆に皮膜特性が低下する。したがって、エポキシ基又は／及びアミノ基を有するシラン化合物を重合することが必要である。
シラン化合物（ｉ）の配合量が、共重合樹脂の固形分１００質量部に対する固形分の割合で０．１質量部未満では、特性の向上効果が十分に認められず、一方、３０質量部を超えても耐食性、加工性が低下する。したがって、エポキシ基又はアミノ基を有するシラン化合物（ｉ）の配合量は、共重合樹脂の固形分１００質量部に対する固形分の割合で０．１〜３０質量部とする。Among the silane compounds (i) having an epoxy group or / and an amino group, examples of the silane compound having an epoxy group include 3-glycidoxypropyltrimethoxyxylane, 3-glycidoxypropyltriethoxyxylane, 3 -Glycidoxypropyltrimethyldiethoxyxylane and the like, and examples of the silane compound having an amino group include 3-aminopropyltrimethoxysilane and 3-aminopropyltriethoxysilane. Species or two or more can be used. It has been found that by polymerizing such a silane compound into an acrylic resin, the anticorrosion effect of the acrylic resin can be dramatically improved. On the other hand, when a silane compound having no epoxy group or amino group, for example, a silane compound having a methacryloxy group or an acryloxy group is polymerized to an acrylic resin, the film characteristics are adversely affected. Therefore, it is necessary to polymerize a silane compound having an epoxy group or / and an amino group.
When the blending amount of the silane compound (i) is less than 0.1 parts by mass with respect to the solid content of 100 parts by mass of the copolymer resin, the effect of improving the characteristics is not sufficiently observed, while 30 parts by mass is added. Even if it exceeds, corrosion resistance and workability will fall. Therefore, the compounding quantity of the silane compound (i) which has an epoxy group or an amino group shall be 0.1-30 mass parts in the ratio of solid content with respect to 100 mass parts of solid content of copolymer resin.
前記アクリル酸又は／及びメタクリル酸（ｉｉ）の配合量は、共重合樹脂の固形分１００質量部に対する固形分の割合で０．５〜１０質量部、好ましくは０．５〜７質量部、より好ましくは１〜４質量部とする。アクリル酸又は／及びメタクリル酸の固形分の割合が０．５質量部未満ではエマルジョンの安定性及び金属表面との密着性が低下し、一方、１０質量部を超えると、得られる皮膜の親水性が強くなり耐水性が低下し、加工性も劣る。 The blending amount of the acrylic acid or / and methacrylic acid (ii) is 0.5 to 10 parts by mass, preferably 0.5 to 7 parts by mass, based on the solid content of 100 parts by mass of the copolymer resin. Preferably it is 1-4 mass parts. When the ratio of the solid content of acrylic acid and / or methacrylic acid is less than 0.5 parts by mass, the stability of the emulsion and the adhesion to the metal surface are lowered, whereas when it exceeds 10 parts by mass, the hydrophilicity of the resulting film is obtained. Becomes stronger, the water resistance is lowered, and the processability is also poor.
前記炭素数１〜６のアルキル鎖を持つアクリル酸エステル又は／及びメタクリル酸エステル（ｉｉｉ）としては、メチルメタクリレート及びその異性体、（メタ）アクリル酸−ｎ−プロピル及びその異性体、（メタ）アクリル酸−ｎ−ブチル及びその異性体、（メタ）アクリル酸−ｎ−ペンチル及びその異性体、（メタ）アクリル酸−ｎ−ヘキシル及びその異性体等が挙げられ、これらの１種又は２種以上を用いることができる。この（メタ）アクリル酸エステル（ｉｉｉ）は皮膜の加工性向上に寄与する。アルキル鎖が７以上の（メタ）アクリル酸エステルから得られる有機樹脂を含む皮膜は、加工性が劣るために加工時の金型との摺動により皮膜が剥離しやすい。したがって、（メタ）アクリル酸エステルは炭素数１〜６、好ましくは３〜５のアルキル鎖を持つものを用いる必要がある。
前記アクリル酸エステル又は／及びメタクリル酸エステル（ｉｉｉ）の配合量は、共重合樹脂の固形分１００質量部に対する固形分の割合で２０〜９５質量部とする。（メタ）アクリル酸エステルの固形分の割合が２０質量部未満或いは９５質量部を超えると加工性が劣る。Examples of the acrylic acid ester and / or methacrylic acid ester (iii) having an alkyl chain having 1 to 6 carbon atoms include methyl methacrylate and its isomer, (meth) acrylic acid-n-propyl and its isomer, (meth) Acrylic acid-n-butyl and its isomer, (meth) acrylic acid-n-pentyl and its isomer, (meth) acrylic acid-n-hexyl and its isomer, etc., one or two of these The above can be used. This (meth) acrylic acid ester (iii) contributes to the improvement of the workability of the film. Since a film containing an organic resin obtained from a (meth) acrylic acid ester having an alkyl chain of 7 or more has poor processability, the film is easily peeled off by sliding with a mold during processing. Therefore, it is necessary to use (meth) acrylic acid ester having an alkyl chain having 1 to 6, preferably 3 to 5 carbon atoms.
The blending amount of the acrylic ester or / and methacrylic ester (iii) is 20 to 95 parts by mass in terms of the solid content with respect to 100 mass parts of the solid content of the copolymer resin. If the ratio of the solid content of the (meth) acrylic acid ester is less than 20 parts by mass or exceeds 95 parts by mass, the processability is inferior.
前記成分（ｉ）〜（ｉｉｉ）と共重合可能なビニルモノマー（ｉｖ）としては、例えば、−ＯＨ基を有する２−ヒドロキシエチルアクリレート、２−ヒドロキシエチルメタクリレート、ヒドロキシプロピルアクリレート、ヒドロキシプロピルメタクリレート、エポキシ基を有するグリシジルメタクリレート、アミノ基を有するアクリルアミド、ニトリル基を有するアクリルニトリル、或いは高疎水性を示すスチレン等が挙げられ、これらの１種又は２種以上を用いることができる。−ＯＨ基、エポキシ基、アミド基等の官能基を有するビニルモノマーを重合させることにより、皮膜の密着性や耐食性が向上する。その一方で、これらの官能基は親水性が高いため、鋼板表面にペフと称す断熱材を貼り合わせた場合、その耐水密着性を低下させる傾向がある。その場合、樹脂の親水性を調整する目的で疎水性のスチレンを重合させることにより耐水密着性を向上させることが可能となる。本発明においては、これらビニルモノマーの組成を制限するものではないが、通常、−ＯＨ基、エポキシ基を有するビニルモノマーでは０〜２０％、アミド基を有するビニルモノマーでは０〜３０％、スチレンは０〜５０％程度の重合が可能である。 Examples of the vinyl monomer (iv) copolymerizable with the components (i) to (iii) include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, epoxy having an —OH group. Examples thereof include glycidyl methacrylate having a group, acrylamide having an amino group, acrylonitrile having a nitrile group, or styrene having high hydrophobicity, and one or more of these can be used. By polymerizing a vinyl monomer having a functional group such as —OH group, epoxy group, amide group, etc., the adhesion and corrosion resistance of the film are improved. On the other hand, since these functional groups have high hydrophilicity, when a heat insulating material called pef is bonded to the steel plate surface, the water-resistant adhesion tends to be lowered. In that case, water-resistant adhesion can be improved by polymerizing hydrophobic styrene for the purpose of adjusting the hydrophilicity of the resin. In the present invention, the composition of these vinyl monomers is not limited, but usually 0-20% for vinyl monomers having —OH groups and epoxy groups, 0-30% for vinyl monomers having amide groups, and styrene Polymerization of about 0 to 50% is possible.
表面処理皮膜は、４価の価数を有するバナジウム化合物（Ａ）と、リン酸又は／及びリン酸系化合物（Ｂ）と、水溶性有機樹脂又は／及び水分散性有機樹脂からなる有機樹脂（Ｃ）とを主成分とするものであるが、それ以外に、耐食性のさらなる向上等を目的として適宜な添加成分を添加してもよい。例えば、コロイダルシリカ及びその派生化合物、リン酸塩系防錆剤及びその複合化化合物、Ｚｎ，Ｍｇ，Ｃｏ，Ｎｉ，Ｆｅ，Ｓｒ，Ｙ，Ｎｂ，Ｔａ，Ｃａ，Ｂａ系の金属化合物等を添加することが可能である。また、Ｔａ系化合物、Ｎｂ系化合物、４価のバナジウム化合物以外のバナジウム化合物を添加してもよい。 The surface treatment film is an organic resin (A) composed of a vanadium compound (A) having a tetravalent valence, phosphoric acid or / and a phosphoric acid compound (B), a water-soluble organic resin and / or a water-dispersible organic resin. In addition to this, an appropriate additive component may be added for the purpose of further improving the corrosion resistance. For example, colloidal silica and its derivatives, phosphate rust preventives and composite compounds thereof, Zn, Mg, Co, Ni, Fe, Sr, Y, Nb, Ta, Ca, Ba based metal compounds, etc. Is possible. Moreover, you may add vanadium compounds other than Ta type compound, Nb type compound, and a tetravalent vanadium compound.
次に、表面処理皮膜の付着量について述べると、まず、表面処理皮膜中の有機樹脂（Ｃ）の付着量は０．５〜５ｇ／ｍ２とする。有機樹脂の付着量が０．５ｇ／ｍ２未満では耐食性、加工性が著しく低下する。一方、有機樹脂を５ｇ／ｍ２を超えて付着させると、ロールフォーミングやプレス加工の際のロールや金型に皮膜が付着しやすくなる。また、以上の観点から有機樹脂（Ｃ）の付着量のより好ましい範囲は１．０〜４．５ｇ／ｍ２、さらに望ましくは１．５〜４．０ｇ／ｍ２である。
また、バナジウム化合物（Ａ）の付着量は、金属Ｖ換算で１〜１００ｍｇ／ｍ２とする。バナジウム化合物の付着量が１ｍｇ／ｍ２未満では耐食性向上効果が認められず、一方、１００ｍｇ／ｍ２を超えて付着させても耐食性向上効果が飽和し、逆に、皮膜の耐水性、加工性が低下する傾向が認められる。また、以上の観点からバナジウム化合物（Ａ）の金属Ｖ換算での付着量のより好ましい範囲は３〜５０ｍｇ／ｍ２、さらに望ましくは５〜４０ｍｇ／ｍ２である。Next, the adhesion amount of the surface treatment film will be described. First, the adhesion amount of the organic resin (C) in the surface treatment film is set to 0.5 to 5 g / m 2 . When the adhesion amount of the organic resin is less than 0.5 g / m 2 , the corrosion resistance and workability are remarkably lowered. On the other hand, when organic resin is made to adhere exceeding 5 g / m < 2 >, a film | membrane will adhere easily to the roll and metal mold | die in the case of roll forming or press work. Moreover, the more preferable range of the adhesion amount of organic resin (C) from the above viewpoint is 1.0-4.5 g / m < 2 >, More desirably, it is 1.5-4.0 g / m < 2 >.
Moreover, the adhesion amount of a vanadium compound (A) shall be 1-100 mg / m < 2 > in conversion of the metal V. FIG. If the amount of vanadium compound deposited is less than 1 mg / m 2 , the effect of improving corrosion resistance is not recognized. On the other hand, even if the amount exceeds 100 mg / m 2 , the effect of improving corrosion resistance is saturated. There is a tendency to decrease. Moreover, the more preferable range of the adhesion amount in conversion of the metal V of a vanadium compound (A) from the above viewpoint is 3-50 mg / m < 2 >, More desirably, it is 5-40 mg / m < 2 >.
また、リン酸又は／及びリン酸系化合物（Ｂ）の付着量は、ＰＯ４換算で５〜２００ｍｇ／ｍ２とすることが好ましい。付着量が５ｍｇ／ｍ２未満では耐食性の向上効果が十分ではなく、一方、過剰に添加すると皮膜の耐水性が低下し、水との接触により皮膜が白化する傾向がある。但し、この白化に関しては樹脂の物性によっても大きく影響されるため、これらの観点から添加量を選択することができる。
さらに、Ｚｎ、Ｎｉ、Ｍｇ等のリン酸塩を用いる場合は、処理液に溶解することが必要であり、また、過剰に多いと処理液安定性が低下するため、適正範囲に収めることが必要である。Further, adhesion of the phosphoric acid or / and phosphoric acid compound (B) is preferably set to 5 to 200 mg / m 2 at PO 4 terms. When the adhesion amount is less than 5 mg / m 2 , the effect of improving the corrosion resistance is not sufficient. On the other hand, when added excessively, the water resistance of the film is lowered and the film tends to be whitened by contact with water. However, since this whitening is greatly influenced by the physical properties of the resin, the addition amount can be selected from these viewpoints.
Furthermore, when using phosphates such as Zn, Ni, Mg, etc., it is necessary to dissolve in the treatment liquid, and if it is excessively large, the stability of the treatment liquid will be lowered, so it is necessary to keep it within an appropriate range. It is.
次に、本発明の表面処理材の製造方法について説明する。
本発明の第１の製造方法では、上述したようなＡｌ−Ｚｎ系合金めっき鋼板のめっき皮膜表面に、４価の価数を有するバナジウム化合物（Ａ）と、リン酸又は／及びリン酸系化合物（Ｂ）と、水溶性有機樹脂又は／及び水分散性有機樹脂からなる有機樹脂（Ｃ）とを主成分とする処理液（上記成分（Ａ）〜（Ｃ）を水に溶解又は／及び分散させた処理液）を塗布した後、水洗することなく乾燥する。
また、本発明の第２の製造方法では、上述したようなＡｌ−Ｚｎ系合金めっき鋼板のめっき皮膜表面に、まず、４価の価数を有するバナジウム化合物（Ａ）とリン酸又は／及びリン酸系化合物（Ｂ）とを主成分とする処理液（上記成分（Ａ）及び（Ｂ）を水に溶解又は／及び分散させた処理液）を塗布した後、水洗することなく乾燥し、さらにその上部に、水溶性有機樹脂又は／及び水分散性有機樹脂からなる有機樹脂（Ｃ）を主成分する処理液（有機樹脂（Ｃ）を水に溶解又は／及び分散させた処理液）を塗布した後、水洗することなく乾燥する。Next, the manufacturing method of the surface treatment material of this invention is demonstrated.
In the first production method of the present invention, a vanadium compound (A) having a tetravalent valence and phosphoric acid or / and a phosphoric acid-based compound on the surface of the plating film of the Al-Zn alloy-plated steel sheet as described above. (B) and a treatment liquid mainly composed of a water-soluble organic resin and / or an organic resin (C) composed of a water-dispersible organic resin (the above components (A) to (C) are dissolved or / and dispersed in water) And then dried without washing with water.
In the second production method of the present invention, the vanadium compound (A) having a tetravalent valence and phosphoric acid or / and phosphorus are first formed on the surface of the plating film of the Al—Zn alloy-plated steel sheet as described above. After applying the treatment liquid containing the acid compound (B) as a main component (the treatment liquid in which the above components (A) and (B) are dissolved or / and dispersed) in water, it is dried without washing, On top of this, a treatment liquid (treatment liquid in which the organic resin (C) is dissolved or dispersed in water) containing an organic resin (C) composed of a water-soluble organic resin and / or a water-dispersible organic resin is applied. Then, it is dried without washing with water.
この２つの製造方法のうち、耐食性の観点からは第２の製造方法の方が優れる傾向を示すが、設備的負荷の観点では第１の製造方法が有利である。但し、いずれにおいても必要レベルの品質が得られる。
また、上記第２の製造方法においては、有機樹脂（Ｃ）を主成分とする処理液中に、バナジウム化合物（Ａ）とリン酸又は／及びリン酸系化合物（Ｂ）のうちの１種以上を添加することも可能である。
処理液は、水に対して各成分（Ａ）〜（Ｃ）を添加することにより調整される。各成分（Ａ）〜（Ｃ）の種類、各成分を添加する際の化合物の形態や添加方法は先に述べたとおりである。また、処理液には、上記成分（Ａ）〜（Ｃ）以外に、必要に応じて先に述べた添加成分を添加することができる。Of these two manufacturing methods, the second manufacturing method tends to be superior from the viewpoint of corrosion resistance, but the first manufacturing method is advantageous from the viewpoint of equipment load. However, in either case, the required level of quality can be obtained.
Moreover, in the said 2nd manufacturing method, 1 or more types of a vanadium compound (A) and phosphoric acid or / and a phosphoric acid type compound (B) in the process liquid which has organic resin (C) as a main component. It is also possible to add.
A processing liquid is adjusted by adding each component (A)-(C) with respect to water. The type of each component (A) to (C), the form of the compound when adding each component, and the method of addition are as described above. Moreover, in addition to the said components (A)-(C), the additive component described previously can be added to a process liquid as needed.
処理液の塗布方法は、例えば、スプレー＋ロール絞り、ロールコーターなど任意であり、また、塗布後の乾燥方式についても、例えば、熱風方式、誘導加熱方式、電気炉方式など任意である。
処理液の乾燥温度は６０〜２５０℃程度とすることが好ましい。乾燥温度が６０℃未満では、皮膜形成が不十分となり耐食性等に劣る皮膜となる。一方、２５０℃を超える板温で乾燥させても耐食性等の品質を高める効果が得られず、逆に低下する場合がある。これは、特に有機樹脂の耐熱限界を超えているために皮膜が熱により損傷されるためであると考えられる。The application method of the treatment liquid is arbitrary, for example, spray + roll squeezing, roll coater, and the drying method after application is arbitrary, for example, a hot air method, an induction heating method, an electric furnace method, and the like.
The drying temperature of the treatment liquid is preferably about 60 to 250 ° C. When the drying temperature is less than 60 ° C., the film formation is insufficient and the film is inferior in corrosion resistance and the like. On the other hand, even if it is dried at a plate temperature exceeding 250 ° C., the effect of improving the quality such as corrosion resistance cannot be obtained, and it may be lowered. This is presumably because the film is damaged by heat because the heat resistance limit of the organic resin is exceeded.
［実施例１］
表１及び表２に示す金属化合物及び有機樹脂とリン酸（オルトリン酸）が添加された処理液を５５％Ａｌ−Ｚｎ系合金めっき鋼板と電気亜鉛めっき鋼板に塗布し、板温１２０℃で乾燥したものを供試材とした。
処理液に配合した有機樹脂（ａ）〜（ｈ）は、以下のような成分で合成した。[Example 1]
The treatment liquid to which the metal compound and organic resin and phosphoric acid (orthophosphoric acid) shown in Tables 1 and 2 are added is applied to 55% Al—Zn alloy-plated steel sheet and electrogalvanized steel sheet, and dried at a plate temperature of 120 ° C. This was used as a test material.
Organic resin (a)-(h) mix | blended with the process liquid was synthesize | combined with the following components.
・有機樹脂（ａ）：本発明条件を満足する
シラン化合物（ｉ）：３−アミノプロピルトリメトキシシラン（１０部）
（メタ）アクリル酸（ｉｉ）：アクリル酸（５部）
（メタ）アクリル酸エステル（ｉｉｉ）：メチルメタクリレート、ブチルアクリレート（５５部）
ビニルモノマー（ｉｖ）：２−ヒドロキシエチルメタクリレート、スチレン、２−エチルヘキシルアクリレート（３０部）
・有機樹脂（ｂ）：本発明条件を満足しない
（メタ）アクリル酸（ｉｉ）：アクリル酸（５部）
（メタ）アクリル酸エステル（ｉｉｉ）：メチルメタクリレート、ブチルアクリレート（６０部）
ビニルモノマー（ｉｖ）：２−ヒドロキシエチルメタクリレート、スチレン、２−エチルヘキシルアクリレート（３５部）Organic resin (a): satisfies the conditions of the present invention Silane compound (i): 3-aminopropyltrimethoxysilane (10 parts)
(Meth) acrylic acid (ii): acrylic acid (5 parts)
(Meth) acrylic acid ester (iii): methyl methacrylate, butyl acrylate (55 parts)
Vinyl monomer (iv): 2-hydroxyethyl methacrylate, styrene, 2-ethylhexyl acrylate (30 parts)
Organic resin (b): does not satisfy the conditions of the present invention (meth) acrylic acid (ii): acrylic acid (5 parts)
(Meth) acrylic acid ester (iii): methyl methacrylate, butyl acrylate (60 parts)
Vinyl monomer (iv): 2-hydroxyethyl methacrylate, styrene, 2-ethylhexyl acrylate (35 parts)
・有機樹脂（ｃ）：本発明条件を満足しない
シラン化合物（ｉ）：３−アミノプロピルトリメトキシシラン（３５部）
（メタ）アクリル酸（ｉｉ）：アクリル酸（５部）
（メタ）アクリル酸エステル（ｉｉｉ）：メチルメタクリレート、ブチルアクリレート（４０部）
ビニルモノマー（ｉｖ）：２−ヒドロキシエチルメタクリレート、スチレン、２−エチルヘキシルアクリレート（２０部）
・有機樹脂（ｄ）：本発明条件を満足しない
シラン化合物（ｉ）：３−アミノプロピルトリメトキシシラン（１０部）
（メタ）アクリル酸（ｉｉ）：アクリル酸（１部）
（メタ）アクリル酸エステル（ｉｉｉ）：メチルメタクリレート、ブチルアクリレート（５９部）
ビニルモノマー（ｉｖ）：２−ヒドロキシエチルメタクリレート、スチレン、２−エチルヘキシルアクリレート（３０部）Organic resin (c): does not satisfy the conditions of the present invention Silane compound (i): 3-aminopropyltrimethoxysilane (35 parts)
(Meth) acrylic acid (ii): acrylic acid (5 parts)
(Meth) acrylic acid ester (iii): methyl methacrylate, butyl acrylate (40 parts)
Vinyl monomer (iv): 2-hydroxyethyl methacrylate, styrene, 2-ethylhexyl acrylate (20 parts)
Organic resin (d): does not satisfy the conditions of the present invention Silane compound (i): 3-aminopropyltrimethoxysilane (10 parts)
(Meth) acrylic acid (ii): acrylic acid (1 part)
(Meth) acrylic acid ester (iii): methyl methacrylate, butyl acrylate (59 parts)
Vinyl monomer (iv): 2-hydroxyethyl methacrylate, styrene, 2-ethylhexyl acrylate (30 parts)
・有機樹脂（ｅ）：本発明条件を満足しない
シラン化合物（ｉ）：３−アミノプロピルトリメトキシシラン（１０部）
（メタ）アクリル酸（ｉｉ）：アクリル酸（２０部）
（メタ）アクリル酸エステル（ｉｉｉ）：メチルメタクリレート、ブチルアクリレート（４０部）
ビニルモノマー（ｉｖ）：２−ヒドロキシエチルメタクリレート、スチレン、２−エチルヘキシルアクリレート（３０部）
・有機樹脂（ｆ）：本発明条件を満足しない
シラン化合物（ｉ）：３−アミノプロピルトリメトキシシラン（１０部）
（メタ）アクリル酸（ｉｉ）：アクリル酸（５部）
（メタ）アクリル酸エステル（ｉｉｉ）：メチルメタクリレート、ブチルアクリレート（１０部）
ビニルモノマー（ｉｖ）：２−ヒドロキシエチルメタクリレート、スチレン、２−エチルヘキシルアクリレート（７５部）Organic resin (e): does not satisfy the conditions of the present invention Silane compound (i): 3-aminopropyltrimethoxysilane (10 parts)
(Meth) acrylic acid (ii): acrylic acid (20 parts)
(Meth) acrylic acid ester (iii): methyl methacrylate, butyl acrylate (40 parts)
Vinyl monomer (iv): 2-hydroxyethyl methacrylate, styrene, 2-ethylhexyl acrylate (30 parts)
Organic resin (f): does not satisfy the conditions of the present invention Silane compound (i): 3-aminopropyltrimethoxysilane (10 parts)
(Meth) acrylic acid (ii): acrylic acid (5 parts)
(Meth) acrylic acid ester (iii): methyl methacrylate, butyl acrylate (10 parts)
Vinyl monomer (iv): 2-hydroxyethyl methacrylate, styrene, 2-ethylhexyl acrylate (75 parts)
得られた供試材について、以下の試験条件で耐食性、耐水性及び加工性を評価した（但し、電気亜鉛めっき鋼板の供試材は耐食性のみ）。
（１）耐食性
塩水噴霧試験（ＳＳＴ：ＪＩＳ Ｚ ２３７１）を、高Ａｌ−Ｚｎ系合金めっき鋼板の供試材では２４０時間、電気亜鉛めっき鋼板の供試材では４８時間実施し、白錆の発生状況を下記基準にて評価した。
○：白錆（黒錆）発生面積率１０％未満
△：白錆（黒錆）発生面積率１０％以上、５０％未満
×：白錆（黒錆）発生面積率５０％以上About the obtained test material, corrosion resistance, water resistance, and workability were evaluated on the following test conditions (however, the test material of an electrogalvanized steel sheet is only corrosion resistance).
(1) Corrosion resistance A salt spray test (SST: JIS Z 2371) was conducted for 240 hours for the high Al-Zn alloy-plated steel specimen and 48 hours for the electrogalvanized steel specimen, and white rust was generated. The situation was evaluated according to the following criteria.
○: White rust (black rust) generation area rate of less than 10% △: White rust (black rust) generation area rate of 10% or more, less than 50% ×: White rust (black rust) generation area rate of 50% or more
（２）耐水性
上記耐食性試験で“○”又は“△”の評価を示した高Ａｌ−Ｚｎ系合金めっき鋼板の供試材についてのみ、耐水性の評価試験を行った。
耐水性は、幅３０ｍｍのサンプルを２０時間水中に浸漬した後、ビード先端５ｍｍＲ、ビード高さ６ｍｍ、押付け荷重１５０Ｋｇｆで引抜き試験を行い、さらに摺動部をテープ剥離した状態のものについて、下記基準により目視で評価した。
○：異常なし（テープに付着物ごくわずか）
△：剥離あり（サンプル表面に明らかなテープ剥離跡あり）
×：ドロービードを行った時点で明らかな剥離あり(2) Water resistance The water resistance evaluation test was performed only on the specimens of the high Al—Zn alloy-plated steel sheets that showed “◯” or “Δ” in the corrosion resistance test.
For water resistance, a sample with a width of 30 mm is immersed in water for 20 hours, and then subjected to a pull-out test with a bead tip of 5 mmR, a bead height of 6 mm, and a pressing load of 150 kgf, and the sliding part is tape-peeled and the following standards are used: Was evaluated visually.
○: No abnormalities (very little deposit on the tape)
Δ: Peeling (clear tape peeling trace on sample surface)
X: Clear peeling at the time of drawing bead
（３）加工性
上記耐食性試験で“○”及び“△”の評価を示した高Ａｌ−Ｚｎ系合金めっき鋼板の供試材についてのみ、加工性の評価試験を行った。
ドロービード試験機を用い、ビード先端平板（先端周囲は０．５ｍｍＲ）を幅３０ｍｍの供試材表面に１５０ｋｇｆの荷重で押し付けて引抜き試験を行い、目視により下記基準にて評価した。
○：異常なし
△：供試材表面が黒化するか、若しくは供試材の外観は良好であるがビードに著しい付着物あり
×：明らかに皮膜が剥離(3) Workability The workability evaluation test was performed only on the specimens of the high Al—Zn alloy-plated steel sheets that were evaluated as “◯” and “Δ” in the corrosion resistance test.
Using a draw bead tester, a bead tip flat plate (0.5 mmR around the tip) was pressed against the surface of the test material having a width of 30 mm with a load of 150 kgf, and a pull-out test was performed.
○: No abnormality △: The surface of the test material is blackened, or the appearance of the test material is good, but there is a significant deposit on the bead.
各供試材の皮膜構成を表１及び表２に、上記試験の結果を表３及び表４に示す。
Ｎｏ．１〜Ｎｏ．１６は表面処理皮膜中に添加した金属化合物による防食効果を比較したものであり、高Ａｌ−Ｚｎ系合金めっき鋼板の表面処理皮膜中に４価のバナジウム化合物を添加したＮｏ．７（発明例）のみが優れた耐食性を示している。また、このような４価のバナジウム化合物による効果は、亜鉛めつき鋼板では得られておらず、高Ａｌ−Ｚｎ系合金めっき鋼板に特有の効果であることが判る。
Ｎｏ．１７〜Ｎｏ．１９は皮膜付着量の影響を調べたものであり、皮膜付着量が本発明範囲未満であるＮｏ．１７（比較例）は耐食性が劣り、一方、皮膜付着量が本発明範囲を超えるＮｏ．１９（比較例）は耐水性、加工性が劣っている。Tables 1 and 2 show the coating composition of each test material, and Tables 3 and 4 show the results of the above tests.
No. 1-No. No. 16 is a comparison of the anticorrosive effect of the metal compound added to the surface treatment film. No. 16 in which a tetravalent vanadium compound was added to the surface treatment film of the high Al—Zn alloy-plated steel sheet. Only 7 (invention example) shows excellent corrosion resistance. Further, it can be seen that the effect of such a tetravalent vanadium compound is not obtained with a zinc-plated steel sheet, and is an effect specific to a high Al—Zn alloy-plated steel sheet.
No. 17-No. No. 19 is an investigation of the effect of the coating amount. No. 19 having a coating amount less than the range of the present invention. No. 17 (Comparative Example) is inferior in corrosion resistance, while No. 17 in which the coating amount exceeds the range of the present invention. 19 (Comparative Example) is inferior in water resistance and workability.
Ｎｏ．２０（比較例）は有機樹脂中にシラン化合物が含まれていない例であり、耐食性、耐水性が劣っている。
Ｎｏ．２１（比較例）は、有機樹脂に重合したシラン化合物（ｉ）が過剰に多い場合の例であり、いずれも耐食性、耐水性、加工性が劣っている。
Ｎｏ．２２、Ｎｏ．２３（いずれも比較例）は、（メタ）アクリル酸（ｉｉ）が過剰に少ない場合と多い場合の例であり、いずれも耐水性、加工性が劣っている。
Ｎｏ．２４（比較例）は、（メタ）アクリル酸エステル（ｉｉｉ）が過剰に少ない場合の例であり、加工性が劣っている。
Ｎｏ．２５（発明例）は、上記Ｎｏ．１〜Ｎｏ．２４とは製造条件が異なり、４価のバナジウム化合物とリン酸を含む処理液を塗布・乾燥した後、有機樹脂を含む処理液を塗布・乾燥することにより表面処理皮膜を形成したものであり、Ｎｏ．７（発明例）と同様の優れた特性が得られている。No. No. 20 (comparative example) is an example in which no silane compound is contained in the organic resin, and the corrosion resistance and water resistance are poor.
No. 21 (Comparative Example) is an example in which the silane compound (i) polymerized on the organic resin is excessively large, and all of them are inferior in corrosion resistance, water resistance and workability.
No. 22, no. No. 23 (both are comparative examples) is an example where the amount of (meth) acrylic acid (ii) is excessively small and large, and both are inferior in water resistance and workability.
No. 24 (Comparative Example) is an example in which the (meth) acrylic acid ester (iii) is excessively small, and the processability is inferior.
No. No. 25 (invention example) 1-No. 24, the manufacturing conditions are different, and after applying and drying a treatment liquid containing a tetravalent vanadium compound and phosphoric acid, a surface treatment film is formed by applying and drying a treatment liquid containing an organic resin. No. Excellent characteristics similar to those of No. 7 (Invention Example) are obtained.
［実施例２］
表５に示す金属化合物とリン酸又はリン酸系化合物、実施例１の有機樹脂（ａ）が添加された処理液を５５％Ａｌ−Ｚｎ系合金めっき鋼板に塗布し、板温１２０℃で乾燥したものを供試材とした。各供試材の耐食性、耐水性、加工性について、実施例１と同じ方法及び基準で評価した。
各供試材の皮膜構成を表５に、上記試験の結果を表６に示す。
Ｎｏ．１（比較例）は表面処理皮膜中にリン酸が添加されていない例であり、耐食性と耐水性が劣っている。
Ｎｏ．２〜Ｎｏ．５（いずれも発明例）は表面処理皮膜中に添加するリン酸又はリン酸系化合物の種類の影響を調べたものであり、オルトリン酸、リン酸Ｍｇ、リン酸Ｚｎのいずれについても優れた特性が得られている。
Ｎｏ．６（発明例）は４価のバナジウム化合物として、５価のバナジウム化合物の還元生成物を用いた例であり、Ｎｏ．２〜Ｎｏ．５で用いた硫酸酸化バナジウムと同様の優れた特性が得られている。[Example 2]
The treatment liquid to which the metal compound and phosphoric acid or phosphoric acid compound shown in Table 5 and the organic resin (a) of Example 1 were added was applied to a 55% Al—Zn alloy-plated steel sheet and dried at a plate temperature of 120 ° C. This was used as a test material. The corrosion resistance, water resistance, and workability of each test material were evaluated by the same method and standard as in Example 1.
Table 5 shows the coating composition of each test material, and Table 6 shows the results of the above test.
No. No. 1 (Comparative Example) is an example in which phosphoric acid is not added to the surface treatment film, and the corrosion resistance and water resistance are inferior.
No. 2-No. No. 5 (all invention examples) investigated the effect of the type of phosphoric acid or phosphoric acid compound added to the surface treatment film, and was excellent in all of orthophosphoric acid, phosphoric acid Mg and Zn phosphate. Is obtained.
No. No. 6 (invention example) is an example using a reduction product of a pentavalent vanadium compound as a tetravalent vanadium compound. 2-No. The same excellent characteristics as the vanadium sulfate oxide used in No. 5 were obtained.
［実施例３］
表７に示す金属化合物及び有機樹脂とリン酸（オルトリン酸）が添加された処理液を５５％Ａｌ−Ｚｎ系合金めっき鋼板に塗布し、板温１２０℃で乾燥したものを供試材とした。
処理液に配合した有機樹脂は、シラン化合物（ｉ）：１〜１５部、（メタ）アクリル酸（ｉｉ）としてアクリル酸：５部、（メタ）アクリル酸エステル（ｉｉｉ）としてメチルメタクリレート、ブチルアクリレート：５０〜６４部、ビニルモノマー（ｉｖ）として２−ヒドロキシエチルメタクリレート、スチレン、２−エチルヘキシルアクリレート：３０部で合成したが、シラン化合物（ｉ）としては下記Ａ〜Ｆの中から選ばれる１種を用いた。なお、Ｎｏ．１では、シラン化合物（ｉ）を配合しないで合成されたものを用いた。[Example 3]
A test liquid was prepared by applying a treatment liquid to which a metal compound and an organic resin and phosphoric acid (orthophosphoric acid) shown in Table 7 were added to a 55% Al—Zn alloy-plated steel sheet and drying at a plate temperature of 120 ° C. .
The organic resin blended in the treatment liquid is silane compound (i): 1 to 15 parts, (meth) acrylic acid (ii) as acrylic acid: 5 parts, (meth) acrylic acid ester (iii) as methyl methacrylate, butyl acrylate : 50 to 64 parts, 2-hydroxyethyl methacrylate, styrene, 2-ethylhexyl acrylate as vinyl monomer (iv): 30 parts, but silane compound (i) is selected from the following A to F Was used. In addition, No. In No. 1, one synthesized without blending the silane compound (i) was used.
・シラン化合物（ｉ）
Ａ：３−メタクリロキシプロピルトリメトキシシラン
Ｂ：３−アクリロキシプロピルトリメトキシシラン
Ｃ：３−グリシドキシプロピルトリメトキシシラン
Ｄ：３−グリシドキシプロピルトリエトキシシラン
Ｅ：３−アミノプロピルトリメトキシシラン
Ｆ：３−アミノプロピルトリエトキシシランSilane compound (i)
A: 3-methacryloxypropyltrimethoxysilane B: 3-acryloxypropyltrimethoxysilane C: 3-glycidoxypropyltrimethoxysilane D: 3-glycidoxypropyltriethoxysilane E: 3-aminopropyltrimethoxy Silane F: 3-Aminopropyltriethoxysilane
各供試材の耐食性、耐水性、加工性について、実施例１と同じ方法及び基準で評価した。
各供試材の皮膜構成を表７に、上記試験の結果を表８に示す。
Ｎｏ．１（比較例）は有機樹脂にシラン化合物（ｉ）が含まれていない例であり、耐食性、耐水性、加工性が劣っている。
Ｎｏ．２〜Ｎｏ．７は、エポキシ基、あるいはアミノ基を含まないシラン化合物を適用した例であるが、添加により耐食性の低下が認められる。Ｎｏ．８〜１０は、エポキシ基を含むシラン化合物、Ｎｏ．１１〜１７はアミノ基を含むシラン化合物を適用した例であるが、添加量により効果に差があるもののいずれも効果が認められ、また、適正量の添加により著しい効果が認められる。The corrosion resistance, water resistance, and workability of each test material were evaluated by the same method and standard as in Example 1.
Table 7 shows the coating composition of each test material, and Table 8 shows the results of the above test.
No. 1 (Comparative Example) is an example in which the silane compound (i) is not contained in the organic resin, and is inferior in corrosion resistance, water resistance, and workability.
No. 2-No. No. 7 is an example in which a silane compound containing no epoxy group or amino group is applied, but a decrease in corrosion resistance is observed by addition. No. Nos. 8 to 10 are silane compounds containing an epoxy group; Although 11 to 17 are examples in which a silane compound containing an amino group is applied, the effect is recognized although there is a difference in effect depending on the addition amount, and a remarkable effect is recognized when an appropriate amount is added.
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