JP5611128B2 - Surface-treated aluminized steel sheet and its manufacturing method - Google Patents
Surface-treated aluminized steel sheet and its manufacturing method Download PDFInfo
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- JP5611128B2 JP5611128B2 JP2011141645A JP2011141645A JP5611128B2 JP 5611128 B2 JP5611128 B2 JP 5611128B2 JP 2011141645 A JP2011141645 A JP 2011141645A JP 2011141645 A JP2011141645 A JP 2011141645A JP 5611128 B2 JP5611128 B2 JP 5611128B2
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- 229910000680 Aluminized steel Inorganic materials 0.000 title claims description 17
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 229910000831 Steel Inorganic materials 0.000 claims description 72
- 239000010959 steel Substances 0.000 claims description 72
- 230000001681 protective effect Effects 0.000 claims description 42
- 238000007747 plating Methods 0.000 claims description 31
- 229910052726 zirconium Inorganic materials 0.000 claims description 28
- 239000011248 coating agent Substances 0.000 claims description 27
- 238000000576 coating method Methods 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 25
- 239000012756 surface treatment agent Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 229910052731 fluorine Inorganic materials 0.000 claims description 21
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 20
- 238000004381 surface treatment Methods 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 229910052698 phosphorus Inorganic materials 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 12
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 11
- 239000000470 constituent Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 7
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 150000003863 ammonium salts Chemical class 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- JZDMNWBZPLJKBT-UHFFFAOYSA-N F.[Zr] Chemical compound F.[Zr] JZDMNWBZPLJKBT-UHFFFAOYSA-N 0.000 claims description 4
- 229910007746 Zr—O Inorganic materials 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 4
- 150000007522 mineralic acids Chemical class 0.000 claims description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical group [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 3
- 230000036961 partial effect Effects 0.000 claims description 3
- 239000011253 protective coating Substances 0.000 claims description 3
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims description 3
- 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 claims description 3
- 239000005416 organic matter Substances 0.000 claims description 2
- 239000004615 ingredient Substances 0.000 claims 1
- 230000007797 corrosion Effects 0.000 description 33
- 238000005260 corrosion Methods 0.000 description 33
- 229910052782 aluminium Inorganic materials 0.000 description 27
- 229920005989 resin Polymers 0.000 description 27
- 239000011347 resin Substances 0.000 description 27
- -1 silica compound Chemical class 0.000 description 25
- 229910052751 metal Inorganic materials 0.000 description 21
- 239000002184 metal Substances 0.000 description 21
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 20
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 19
- 238000011282 treatment Methods 0.000 description 17
- 239000011651 chromium Substances 0.000 description 16
- 229910052804 chromium Inorganic materials 0.000 description 15
- 239000010410 layer Substances 0.000 description 15
- 238000012360 testing method Methods 0.000 description 15
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 14
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 12
- 239000007788 liquid Substances 0.000 description 12
- 238000012545 processing Methods 0.000 description 12
- 150000003609 titanium compounds Chemical class 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 238000001035 drying Methods 0.000 description 9
- 230000007613 environmental effect Effects 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 239000010936 titanium Substances 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 229910052719 titanium Inorganic materials 0.000 description 8
- 229910052725 zinc Inorganic materials 0.000 description 8
- 239000011701 zinc Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000002585 base Substances 0.000 description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 238000005530 etching Methods 0.000 description 6
- 239000000383 hazardous chemical Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 229910052720 vanadium Inorganic materials 0.000 description 6
- WRAGBEWQGHCDDU-UHFFFAOYSA-M C([O-])([O-])=O.[NH4+].[Zr+] Chemical compound C([O-])([O-])=O.[NH4+].[Zr+] WRAGBEWQGHCDDU-UHFFFAOYSA-M 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 239000000314 lubricant Substances 0.000 description 5
- 230000002829 reductive effect Effects 0.000 description 5
- 150000003755 zirconium compounds Chemical class 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000002828 fuel tank Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000001050 lubricating effect Effects 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- 230000003449 preventive effect Effects 0.000 description 4
- 150000003682 vanadium compounds Chemical class 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229910001335 Galvanized steel Inorganic materials 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000010411 cooking Methods 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000010828 elution Methods 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000008397 galvanized steel Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 150000002816 nickel compounds Chemical class 0.000 description 3
- 239000004584 polyacrylic acid Substances 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- 229910018125 Al-Si Inorganic materials 0.000 description 2
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 2
- 229910018520 Al—Si Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229910021364 Al-Si alloy Inorganic materials 0.000 description 1
- 229910017111 AlOF Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229910001122 Mischmetal Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 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 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 125000005586 carbonic acid group Chemical group 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 239000013527 degreasing agent Substances 0.000 description 1
- 238000005237 degreasing agent Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 125000002636 imidazolinyl group Chemical group 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000007603 infrared drying Methods 0.000 description 1
- CDAISMWEOUEBRE-GPIVLXJGSA-N inositol Chemical compound O[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@H](O)[C@@H]1O CDAISMWEOUEBRE-GPIVLXJGSA-N 0.000 description 1
- 229960000367 inositol Drugs 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000005461 organic phosphorous group Chemical group 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- CDAISMWEOUEBRE-UHFFFAOYSA-N scyllo-inosotol Natural products OC1C(O)C(O)C(O)C(O)C1O CDAISMWEOUEBRE-UHFFFAOYSA-N 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 150000003754 zirconium Chemical class 0.000 description 1
- XJUNLJFOHNHSAR-UHFFFAOYSA-J zirconium(4+);dicarbonate Chemical class [Zr+4].[O-]C([O-])=O.[O-]C([O-])=O XJUNLJFOHNHSAR-UHFFFAOYSA-J 0.000 description 1
Landscapes
- Other Surface Treatments For Metallic Materials (AREA)
- Chemical Treatment Of Metals (AREA)
- Coating With Molten Metal (AREA)
Description
本発明は、クロムを含まない保護皮膜を形成した耐熱用途（特に調理器用）アルミめっき鋼板とその製造方法に関する。さらに詳しくは、クロムを含まないことで環境に対する負荷を著しく軽減し、その上で張り出し加工や深絞り加工後の耐食性に極めて優れ、同時に塗装性、耐熱性および耐水性に優れた保護皮膜を有する耐熱用途（特に調理器用）アルミめっき鋼板とその製造方法に関する。 The present invention relates to a heat-resistant use (particularly for a cooker) aluminum-plated steel sheet in which a chromium-free protective film is formed and a method for producing the same. More specifically, it does not contain chromium, significantly reduces the burden on the environment, and has excellent corrosion resistance after overhanging and deep drawing, and at the same time has a protective coating with excellent paintability, heat resistance and water resistance. The present invention relates to a heat-resistant use (particularly for a cooker) aluminized steel sheet and a method for producing the same.
特許文献１には、アルコール燃料と塩害環境に対する耐食性とプレス加工性に優れた自動車用タンク材料として、アルミめっき鋼板表面にクロメート皮膜を形成させ、さらにエポキシ系樹脂を０．１〜３μｇ付与する技術が開示されている。また、特許文献２には、アルミめっき鋼板に特定の熱処理を加えた後、クロメート処理、有機樹脂塗装する事を特徴とする加工後の耐食性に優れた塗装溶融アルミめっき鋼板の製造方法が開示されている。また、特許文献３には、特定のめっき浴で鋼板にめっきを行い、めっき後クロメート処理と続いて有機樹脂被覆処理をする塗装アルミめっき鋼板の製造法が開示されている。また、特許文献４には特定のめっき浴で鋼板にめっきを行い、めっき後クロメート処理を行うアルミめっき鋼板が開示されている。特許文献５には、重量％でＳｉ：２〜１３％を含有し、付着量が片面当り５０ｇ／ｍ２以下である溶融アルミめっき鋼板の片面または両面に、膜厚が０．１〜２μｍであるような樹脂クロメート皮膜を有することを特徴とする溶接性、耐食性に優れた燃料タンク用防錆鋼板が開示されている。 Patent Document 1 discloses a technology for forming a chromate film on the surface of an aluminum-plated steel sheet as an automotive tank material excellent in corrosion resistance and press workability against alcohol fuel and salt damage environment, and further applying 0.1 to 3 μg of epoxy resin. Is disclosed. Patent Document 2 discloses a method for producing a coated hot-dip aluminized steel sheet having excellent post-processing corrosion resistance, characterized by applying a specific heat treatment to an aluminized steel sheet, followed by chromate treatment and organic resin coating. ing. Patent Document 3 discloses a method for producing a coated aluminum-plated steel sheet, in which a steel sheet is plated with a specific plating bath, followed by a chromate treatment after plating and an organic resin coating treatment. Patent Document 4 discloses an aluminum-plated steel sheet in which a steel sheet is plated with a specific plating bath and subjected to chromate treatment after plating. Patent Document 5 contains Si: 2 to 13% by weight, and the film thickness is 0.1 to 2 μm on one side or both sides of a hot-dip aluminized steel sheet having an adhesion amount of 50 g / m 2 or less per side. A rustproof steel sheet for fuel tanks having excellent weldability and corrosion resistance, characterized by having a certain resin chromate film, is disclosed.
特許文献６には、フランジを有する一対の椀型成型体のフランジ部を連続的にシーム溶接して一体とされた燃料容器であって、その構成部材が内面または／および外面の最表面に樹脂皮膜、好ましくは樹脂クロメート皮膜を有する溶融アルミめっき鋼板であることを特徴とする耐食性に優れた自動車燃料容器が開示されている。特許文献７には、少なくとも片面がＡｌまたはＡｌ−（３〜１５％）Ｓｉ系合金で被覆された鋼板の被覆層表面に、皮膜量がクロム換算で１０ｍｇ／ｍ２以上３５ｍｇ／ｍ２未満であるクロメート皮膜を形成したアルミ系めっき鋼板で、燃料タンク素材として望ましくは皮膜量がクロム換算で２０ｍｇ／ｍ２以上３０ｍｇ／ｍ２以下であるクロメート皮膜を形成したアルミ系めっき鋼板が開示されている。特許文献８には、重量％でＳｉ：２〜１３％をめっき層中に含有する両面溶融アルミめっき鋼板の片方の面に、膜厚が０．１〜２μｍであるような有機樹脂クロメート皮膜を有し、かつ他方の面には、無機系クロメート皮膜もしくは有機リン酸あるいは／更に微量の有機樹脂を含有したクロメート皮膜を金属クロム換算で２００ｍｇ／ｍ２以下被覆したこと、あるいは、樹脂クロメート皮膜とアルミめっき層の間に無機系クロメート皮膜もしくは有機リン酸あるいは／更に微量の有機樹脂を含有したクロメート皮膜を金属クロム換算で１００ｍｇ／ｍ２以下被覆したことを特徴とする、溶接性および耐食性に優れた燃料タンク用防錆鋼板が開示されている。特許文献９には、重量％でＳｉ２〜１３％を含有する溶融アルミめっき鋼板の片面又は両面に、潤滑剤を０．５〜２０重量％含有する膜厚が０．１〜２μｍであるような有機樹脂クロメート皮膜を有し、そのアルミめっき付着量が、片面当たり６０ｇ／ｍ２以下であることを特徴とする、燃料タンク用防錆鋼板が開示されている。これらの技術はクロメートもしくはクロムを含有する技術であり、環境負荷が大きく、現代では使用できない、もしくは推奨されない技術である。 Patent Document 6 discloses a fuel container in which a flange portion of a pair of saddle-shaped molded bodies having a flange is continuously seam welded to be integrated, and its constituent members are resin on the innermost surface and / or outermost surface. An automotive fuel container excellent in corrosion resistance, characterized by being a hot-dip aluminized steel sheet having a coating, preferably a resin chromate coating, is disclosed. Patent Document 7, at least one surface of Al or Al- (3 to 15%) the coating layer surface of the coated steel sheet Si alloy, coating amount of chromium in terms of 10 mg / m 2 or more 35 mg / m 2 less than in An aluminum-plated steel sheet having a chromate film formed thereon, and an aluminum-plated steel sheet having a chromate film that is preferably 20 mg / m 2 or more and 30 mg / m 2 or less in terms of chromium as a fuel tank material is disclosed. . Patent Document 8 discloses an organic resin chromate film having a film thickness of 0.1 to 2 μm on one surface of a double-sided hot-dip aluminum-plated steel sheet containing Si: 2 to 13% by weight in the plating layer. And the other surface is coated with an inorganic chromate film or an organic phosphoric acid or a chromate film containing a trace amount of an organic resin in an amount of 200 mg / m 2 or less in terms of metal chromium, or a resin chromate film Excellent in weldability and corrosion resistance, characterized by coating an inorganic chromate film or organic phosphoric acid or a chromate film containing a small amount of organic resin between the aluminum plating layers in an amount of 100 mg / m 2 or less in terms of metallic chromium A rust-proof steel plate for a fuel tank is disclosed. Patent Document 9 discloses that a film thickness containing 0.5 to 20% by weight of a lubricant is 0.1 to 2 μm on one or both sides of a hot-dip aluminized steel sheet containing 2 to 13% by weight of Si. A rust-proof steel sheet for fuel tanks is disclosed, which has an organic resin chromate film and has an aluminum plating adhesion amount of 60 g / m 2 or less per side. These technologies contain chromate or chromium, have a large environmental impact, and cannot be used or recommended in modern times.
一方、特許文献１０には、プレス油なしに成形加工が可能で、加工後の耐熱性に優れた無塗油型有機被覆金属板として、金属板の片面には、膜厚が５μｍ以上５０μｍ未満、伸び率が１００％以上の有機物塗膜（Ａ）を有し、他方の面には、膜厚が０．２μｍ以上５μｍ以下の有機物塗膜（Ｂ）を有する金属板が開示されている。また、特許文献１１には、片面に導電性を有する金属を含有する塗膜（Ａ）を厚さ０．５μｍ未満形成させ、他方の面には、膜厚が０．２μｍ以上５μｍ以下の有機物塗膜（Ｂ）を有することを特徴とするプレス加工性と導電性に優れた無塗油型有機被覆金属板が開示されている。特許文献１２には、アルミめっき鋼板表面を、潤滑剤を０．５〜２０重量％含有し残部がエチレン系不飽和カルボン酸成分または／及び水酸基含有単量体成分を含有する有機重合体および不可避的不純物から成る、乾燥膜厚０．５〜４．５μｍの樹脂層で被覆したことを特徴とする加工性に優れた樹脂被覆アルミめっき鋼板が開示されている。特許文献１３には、２価の金属で中和されたアイオノマー樹脂（Ａ）の水性分散体を含む金属表面用防錆処理剤、ならびにその防錆処理剤を用いる防錆処理方法および防錆処理金属製品が開示されている。特許文献１４には、電気めっき或いは溶融めっき法で製造されたアルミめっき鋼板表面に、クロメート処理皮膜を施した後、或いはクロメート処理皮膜を施さないで、重量比で潤滑剤を０．５〜２０重量％およびシリカを０．５〜３０重量％含有する樹脂Ｔｇが３０℃以下であるエチレン系不飽和カルボン酸成分または／および水酸基含有単量体成分を含有し、残部が不可避的不純物から成る有機重合体が水性媒体中に安定に分散した有機重合体エマルジョンである樹脂をアルミめっき鋼板表面に塗布した後、乾燥温度１００℃以下で乾燥し、乾燥後の塗膜厚み０．５〜４．５μｍの有機皮膜を処理する技術が開示されている。しかしながら、これらの技術は樹脂を含有しているため１５０℃〜２００℃が上限温度となるような耐熱性を有しているに過ぎず、十分な耐熱性を有しているとは言いがたい。 On the other hand, in Patent Document 10, as an oil-free organic coated metal plate that can be molded without press oil and has excellent heat resistance after processing, the thickness of the metal plate is 5 μm or more and less than 50 μm on one side of the metal plate. A metal plate having an organic coating film (A) with an elongation of 100% or more and an organic coating film (B) with a film thickness of 0.2 μm or more and 5 μm or less is disclosed on the other surface. Further, in Patent Document 11, a coating film (A) containing a conductive metal is formed on one side with a thickness of less than 0.5 μm, and an organic substance having a thickness of 0.2 μm or more and 5 μm or less is formed on the other side. An oil-free organic coated metal plate excellent in press workability and conductivity, characterized by having a coating film (B), is disclosed. In Patent Document 12, an aluminum polymer steel plate surface containing an organic polymer containing 0.5 to 20% by weight of a lubricant and the balance containing an ethylenically unsaturated carboxylic acid component or / and a hydroxyl group-containing monomer component is inevitable. Disclosed is a resin-coated aluminized steel sheet excellent in workability, characterized by being coated with a resin layer having a dry film thickness of 0.5 to 4.5 μm, which is composed of mechanical impurities. Patent Document 13 discloses a rust preventive agent for metal surfaces containing an aqueous dispersion of an ionomer resin (A) neutralized with a divalent metal, and a rust preventive treatment method and a rust preventive treatment using the rust preventive agent. A metal product is disclosed. In Patent Document 14, a lubricant is added in a weight ratio of 0.5 to 20 after a chromate treatment film is applied to the surface of an aluminum-plated steel sheet produced by electroplating or hot dipping, or without a chromate treatment film. An organic unsaturated carboxylic acid component or / and a hydroxyl group-containing monomer component in which the resin Tg containing 30% by weight and silica of 0.5 to 30% by weight is 30 ° C. or lower, and the balance is composed of inevitable impurities A resin, which is an organic polymer emulsion in which a polymer is stably dispersed in an aqueous medium, is applied to the surface of an aluminum-plated steel sheet, and then dried at a drying temperature of 100 ° C. or less, and the coating thickness after drying is 0.5 to 4.5 μm. A technique for treating the organic film is disclosed. However, since these technologies contain a resin, they have only heat resistance such that 150 ° C. to 200 ° C. is the upper limit temperature, and it cannot be said that they have sufficient heat resistance. .
特許文献１５には、溶融アルミめっき系鋼板を大気開放下での５％ＮａＣｌ溶液に７２時間浸漬したあと、めっき表面において少なくともアルカリ土類金属と酸素を含む皮膜を形成し、その皮膜の厚さが１００〜３０００Åであることを特徴とする耐食性に優れた溶融アルミめっき系鋼板が開示されている。また、特許文献１６には、溶融アルミ系めっき鋼板の最表面に、乾燥後塗膜質量比でワックス成分を０．１〜２０％、金属Ａｌ粉を０．３〜２０％含有し、かつワックス質量／金属Ａｌ粉質量＝０．１以上の関係を満たし、残部が透明樹脂よりなる有機樹脂皮膜層を０．５〜１０μｍ有することを特徴とする耐候性に優れた溶融アルミめっき鋼板が開示されている。特許文献１７には、カルボキシル基を有するエチレン性不飽和単量体およびグリシジル基を有するエチレン性不飽和単量体を含有し、さらに重合性不飽和基を有する反応性乳化剤を、全単量体に対し０．１〜３０質量％含有するアクリル系共重合物の水性分散物に、前記分散物の固形分に対する質量比で潤滑剤を０．５〜２０質量％およびクロムを０．５〜３質量％含有させた樹脂組成物を、乾燥膜厚で０．１〜４．５μｍの厚みの皮膜を塗布した加工性と耐食性に優れたアルミめっき鋼板が開示されている。これらの技術は、主に樹脂を用いる技術であって、耐食性は優れるケースもあるが、一様に耐熱性は十分でなく、耐熱用途（特に調理器用）には使用できない。 In Patent Document 15, a hot-dip aluminum-plated steel sheet is immersed in a 5% NaCl solution for 72 hours in the open atmosphere, and then a film containing at least an alkaline earth metal and oxygen is formed on the plating surface. Discloses a hot-dip aluminum-plated steel sheet having excellent corrosion resistance, characterized in that it is 100 to 3000 mm. Patent Document 16 contains 0.1 to 20% of a wax component and 0.3 to 20% of metal Al powder in a coating film mass ratio after drying on the outermost surface of a molten aluminum-based plated steel sheet, and a wax. Disclosed is a hot-dip galvanized steel sheet satisfying the relationship of mass / metal Al powder mass = 0.1 or more and having an organic resin film layer of 0.5 to 10 μm made of a transparent resin as the balance, ing. Patent Document 17 includes an ethylenically unsaturated monomer having a carboxyl group and an ethylenically unsaturated monomer having a glycidyl group, and further a reactive emulsifier having a polymerizable unsaturated group, To an aqueous dispersion of an acrylic copolymer containing 0.1 to 30% by mass with respect to the solid content of the dispersion, 0.5 to 20% by mass of lubricant and 0.5 to 3% of chromium. An aluminum-plated steel sheet excellent in workability and corrosion resistance in which a resin composition containing mass% is coated with a film having a dry film thickness of 0.1 to 4.5 μm is disclosed. These techniques are mainly techniques using a resin, and there are cases where the corrosion resistance is excellent, but the heat resistance is uniformly insufficient, and cannot be used for heat-resistant applications (especially for cookers).
クロムを含有しない他の技術としては、以下のものが挙げられる。特許文献１８には、めっき層組成がＡｌ：７０質量％以上のアルミめっき鋼板上に、ジルコニウム化合物と、バナジウム化合物と、シリカ化合物と、りん酸化合物と、水酸基、カルボニル基、及びカルボキシル基のうちの少なくとも１つの官能基をもつ有機化合物からなる複合皮膜を有し、かつ複合皮膜中に片面当り、ジルコニウムとして２〜１２００ｍｇ／ｍ２、バナジウムとして０．１〜３００ｍｇ／ｍ２、ＰＯ４換算として０．３〜４５０ｍｇ／ｍ２含有し、クロム、クロム化合物が０．１ｍｇ／ｍ２以下、（クロムとして）フッ素、フッ素化合物が０．１ｍｇ／ｍ２以下（フッ素として）である耐食性、塗装性、溶接性及び加工性に優れるアルミめっき鋼板が開示されている。特許文献１９には、特定の化学式で示されるバナジウム化合物（ａ）の少なくとも１種を添加することにより得られる、クロムを含有しない水系金属表面処理剤が開示されている。特許文献２０には、鋼板と、この鋼板の少なくとも片面に形成された潤滑皮膜とで構成される潤滑鋼板であって、前記鋼板は、ステンレス鋼板、ステンレス−アルミめっき鋼板、又はアルミめっき鋼板であり、前記潤滑皮膜は、水性塗布剤を塗布、乾燥することにより形成され、前記水性塗布剤は、樹脂、ポリオレフィンワックス、及びフルオロジルコニウム酸塩を含有し、且つｐＨが４．５以上８以下であり、前記樹脂はポリエステル樹脂を含み、前記水性塗布剤の固形分中における前記ポリエステル樹脂の含有量が７０質量％以上である潤滑鋼板が開示されている。特許文献２１には、金属成形物、特にアルミニウムおよび錫飲料缶の表面の静摩擦係数を低下させ、かつ当該表面をより低い温度で乾燥することを可能にする潤滑表面調整剤であって、この調整剤は（ｉ）アミンオキサイドおよび第４級アンモニウム塩、エトキシル化ひまし油誘導体、イミダゾリン基含有ホスホン酸塩、および好ましくは（ｉｉ）フルオジルコニウム酸塩、フルオハフニウム酸塩、フルオチタン酸の１種以上、および（ｉｉｉ）りん酸および／又は硝酸イオンを含み、処理された容器は、過熱されたときに摩擦低下効果が損われること、および、殺菌処理による缶底部の黒変に対して良好な抵抗性を有する技術が開示されている。特許文献２２には、（Ａ）炭酸ジルコニウムアンモニウム、（Ｂ）４価のバナジウム化合物、（Ｃ）式（Ｉ）で示される有機ホスホン酸もしくはそのアンモニウム塩、（Ｄ）数式（１）で計算されるガラス転移温度Ｔｇ（Ｋ）を（℃）に換算したものが０〜６０℃であるアニオン性水分散性アクリル樹脂、及び水を含有し、（Ｄ）の全固形分中の割合が１〜６０質量％であり、（Ｂ）をＶに換算したときの割合が全固形分中の０．５〜８質量％であり、Ｖ／（Ｃ）の質量比が０．０５〜１．０であり、（Ａ）をＺｒに換算したときのＺｒ／（Ｖ＋（Ｃ））の質量％が０．１〜６．０であり、ｐＨが７〜１０である亜鉛系めっき鋼板用水系処理液、及び該処理液に由来する皮膜を表面に有する亜鉛系めっき鋼板が開示されている。 Other techniques that do not contain chromium include the following. Patent Document 18 discloses that, on an aluminum plated steel sheet having a plating layer composition of Al: 70% by mass or more, among a zirconium compound, a vanadium compound, a silica compound, a phosphoric acid compound, a hydroxyl group, a carbonyl group, and a carboxyl group. of a composite film comprising an organic compound having at least one functional group, and per side in the composite film, 2~1200mg / m 2 on a zirconium, as 0.1~300mg / m 2, PO 4 calculated as vanadium 0.3~450mg / m 2 and containing chromium, chromium compound 0.1 mg / m 2 or less, the corrosion resistance is (chromium as) fluorine, fluorine compounds 0.1 mg / m 2 or less (as fluorine), paintability An aluminized steel sheet having excellent weldability and workability is disclosed. Patent Document 19 discloses a chromium-free aqueous metal surface treatment agent obtained by adding at least one vanadium compound (a) represented by a specific chemical formula. Patent Document 20 discloses a lubricated steel sheet composed of a steel sheet and a lubricating film formed on at least one surface of the steel sheet, and the steel sheet is a stainless steel sheet, a stainless-aluminum plated steel sheet, or an aluminized steel sheet. The lubricating coating is formed by applying and drying an aqueous coating agent, and the aqueous coating agent contains a resin, a polyolefin wax, and a fluorozirconate salt, and has a pH of 4.5 or more and 8 or less. In addition, there is disclosed a lubricating steel sheet in which the resin contains a polyester resin, and the content of the polyester resin in the solid content of the aqueous coating agent is 70% by mass or more. Patent Document 21 discloses a lubricating surface conditioner that reduces the coefficient of static friction of the surface of a metal molded product, particularly aluminum and tin beverage cans, and enables the surface to be dried at a lower temperature. The agent is (i) an amine oxide and a quaternary ammonium salt, an ethoxylated castor oil derivative, an imidazoline group-containing phosphonate, and preferably (ii) one or more of fluorzirconate, fluorhafnate, fluotitanate, and (Iii) Containers containing phosphoric acid and / or nitrate ions have a reduced resistance to friction when heated and have good resistance to blackening of the bottom of the can due to sterilization. The technology which has is disclosed. In Patent Document 22, (A) ammonium zirconium carbonate, (B) a tetravalent vanadium compound, (C) an organic phosphonic acid represented by formula (I) or an ammonium salt thereof, (D) calculated by formula (1) The glass transition temperature Tg (K) converted to (° C.) contains 0 to 60 ° C. anionic water-dispersible acrylic resin and water, and the ratio of (D) in the total solid content is 1 to 60% by mass, the ratio when (B) is converted to V is 0.5 to 8% by mass in the total solid content, and the mass ratio of V / (C) is 0.05 to 1.0. Yes, an aqueous treatment solution for galvanized steel sheet, wherein the mass% of Zr / (V + (C)), when (A) is converted to Zr, is 0.1 to 6.0 and the pH is 7 to 10, And a zinc-based plated steel sheet having a coating derived from the treatment liquid on its surface.
特許文献２３には、（Ａ）加水分解性チタン化合物、加水分解性チタン化合物の低縮合物、水酸化チタン及び水酸化チタンの低縮合物よりなる群から選ばれる少なくとも１種のチタン化合物を過酸化水素水と混合して得られるチタン含有水性液の固形分１００重量部に基いて、（Ｂ）有機リン酸化合物１〜４００重量部、（Ｃ）水溶性又は水分散性有機樹脂を固形分で１０〜２，０００重量部、（Ｄ）バナジン酸化合物１〜４００重量部、（Ｅ）弗化ジルコニウム化合物１〜４００重量部及び（Ｆ）炭酸ジルコニウム化合物１〜４００重量部を含有してなることを特徴とする金属表面処理組成物が開示されている。特許文献２４には、アルミニウム基材と、その表面に形成した非クロム塗布型下地皮膜と、その上に形成した樹脂被覆膜とを備え、基材表面と下地皮膜との界面に存在するアルミニウム水和酸化物の量が５０ｍｇ／ｍ２以下で、下地皮膜がフッ化ジルコニウム酸及び炭酸ジルコニウムアンモニウムの少なくともいすれかと、ジルコニウム架橋されたポリアクリル酸とを含み、ジルコニウム化合物濃度が、基材側の面から下地皮膜表面に向けて連続的に減少し、かつ、ポリアクリル酸濃度が、基材側の面から下地皮膜表面に向けて連続的に増加しており、ジルコニウム化合物濃度及びポリアクリル酸濃度が１〜２０ｍｇ／ｍ２である樹脂被覆アルミニウム板が開示されている。特許文献２５には、亜鉛系めっき鋼板又はアルミニウム系めっき鋼板の表面に、加水分解性チタン化合物やその低縮合物などのチタン化合物を過酸化水素水と混合して得られるチタン含有水性液（Ａ）の固形分１００質量部に対して、ニッケル化合物（Ｂ）を０．０１〜１０質量部、アルミニウム化合物（Ｃ）を１〜１００質量部、弗素含有化合物（Ｄ）を１〜８００質量部含有し、必要に応じて、有機リン酸化合物、バナジン酸化合物、炭酸ジルコニウム化合物、水溶性又は水分散性有機樹脂の１種以上を適量含有する表面処理組成物（Ｉ）を塗布し、乾燥させることにより形成された皮膜付着量が０．１〜２．０ｇ／ｍ２の表面処理皮膜を有する技術が開示されている。特許文献２６には、（Ａ）有機亜リン酸 １〜１０重量％、（Ｂ）オキシカルボン酸 １〜１０重量％、（Ｃ）ジルコニウム化合物 １〜１０重量％、及び（Ｄ）バナジウム化合物 ０．１〜５重量％を含有することを特徴とする無機系クロムフリー金属表面処理剤が開示されている。 Patent Document 23 contains at least one titanium compound selected from the group consisting of (A) a hydrolyzable titanium compound, a low condensate of a hydrolyzable titanium compound, titanium hydroxide and a low condensate of titanium hydroxide. Based on 100 parts by weight of a solid content of a titanium-containing aqueous liquid obtained by mixing with hydrogen oxide water, (B) 1 to 400 parts by weight of an organic phosphate compound, (C) a water-soluble or water-dispersible organic resin 10 to 2,000 parts by weight, (D) 1 to 400 parts by weight of a vanadic acid compound, (E) 1 to 400 parts by weight of a zirconium fluoride compound, and (F) 1 to 400 parts by weight of a zirconium carbonate compound. A metal surface treatment composition is disclosed. Patent Document 24 includes an aluminum base, a non-chromium coating type base film formed on the surface thereof, and a resin coating film formed thereon, and aluminum present at the interface between the base material surface and the base film. The amount of hydrated oxide is 50 mg / m 2 or less, the undercoat contains at least one of fluorinated zirconium acid and ammonium zirconium carbonate, and zirconium-crosslinked polyacrylic acid, and the zirconium compound concentration is on the substrate side The concentration of polyacrylic acid continuously decreases from the surface of the substrate toward the surface of the undercoating film, and the polyacrylic acid concentration continuously increases from the surface of the base material toward the surface of the undercoating film. A resin-coated aluminum plate having a concentration of 1 to 20 mg / m 2 is disclosed. Patent Document 25 discloses a titanium-containing aqueous liquid (A) obtained by mixing a titanium compound such as a hydrolyzable titanium compound or a low condensate thereof with a hydrogen peroxide solution on the surface of a zinc-based plated steel sheet or an aluminum-based plated steel sheet. ) Containing 0.01 to 10 parts by mass of the nickel compound (B), 1 to 100 parts by mass of the aluminum compound (C), and 1 to 800 parts by mass of the fluorine-containing compound (D). Then, if necessary, a surface treatment composition (I) containing an appropriate amount of one or more of an organic phosphate compound, a vanadic acid compound, a zirconium carbonate compound, a water-soluble or water-dispersible organic resin is applied and dried. The technique which has the surface treatment film | membrane with the film | membrane adhesion amount formed by 0.1-2.0 g / m < 2 > is disclosed. Patent Document 26 includes (A) 1 to 10% by weight of organic phosphorous acid, (B) 1 to 10% by weight of oxycarboxylic acid, (C) 1 to 10% by weight of zirconium compound, and (D) a vanadium compound. An inorganic chromium-free metal surface treatment agent containing 1 to 5% by weight is disclosed.
特許文献２７には、亜鉛系めっき鋼板又はアルミニウム系めっき鋼板の表面に、加水分解性チタン化合物やその低縮合物などのチタン化合物を過酸化水素水と混合して得られるチタン含有水性液（Ａ）の固形分１００質量部に対して、ニッケル化合物（Ｂ）を０．０１〜１０質量部、アルミニウム化合物（Ｃ）を１〜１００質量部、弗素含有化合物（Ｄ）を１〜８００質量部含有し、さらに、酸化ケイ素（Ｅ）及び金属リン酸塩（Ｆ）を表面処理組成物の全固形分中での合計の割合で２０〜９０ｍａｓｓ％含有する表面処理組成物（Ｋ）を塗布し、乾燥させることにより形成された皮膜付着量が０．１〜２．０ｇ／ｍ２の表面処理皮膜を有する技術が開示されている。特許文献２８には、亜鉛系めっき鋼板又はアルミニウム系めっき鋼板の表面に、加水分解性チタン化合物やその低縮合物などのチタン化合物を過酸化水素水と混合して得られるチタン含有水性液（Ａ）の固形分１００質量部に対して、ニッケル化合物（Ｂ）を０．０１〜１０質量部、アルミニウム化合物（Ｃ）を１〜１００質量部、弗素含有化合物（Ｄ）を１〜８００質量部含有し、さらに、酸化ケイ素（Ｅ）を表面処理組成物の全固形分中での割合で２０〜９０ｍａｓｓ％含有する表面処理組成物（Ｊ）を塗布し、乾燥させることにより形成された皮膜付着量が０．１〜２．０ｇ／ｍ２の表面処理皮膜を有する技術が開示されている。特許文献２９には、亜鉛系めっき鋼板などの表面に、特定のチタン含有水性液と、有機リン酸化合物と、バナジン酸化合物と、フッ化ジルコニウム化合物と、炭酸ジルコニウム化合物を含有する表面処理組成物による表面処理皮膜を有し、その上層に、樹脂中に一級水酸基を有するエポキシ樹脂に、水酸基と架橋する基を有する硬化剤および固形潤滑剤が配合された塗料組成物による上層皮膜を有する技術が開示されている。特許文献３０には亜鉛系めっき鋼板またはアルミニウム系めっき鋼板の表面に、特定のチタン化合物を過酸化水素水と混合して得られるチタン系水性液に対して、有機リン酸化合物、ノニオン系水性ビスフェノールＡ型エポキシ樹脂、バナジン酸化合物、フッ化ジルコニウム化合物および炭酸ジルコニウム化合物を所定の割合で複合添加した表面処理組成物による表面処理皮膜を形成し、好ましくは、その上層に有機系皮膜を形成する技術が開示されている。 Patent Document 27 discloses a titanium-containing aqueous liquid (A) obtained by mixing a titanium compound such as a hydrolyzable titanium compound or a low condensate thereof with a hydrogen peroxide solution on the surface of a zinc-based plated steel sheet or an aluminum-based plated steel sheet. ) Containing 0.01 to 10 parts by mass of the nickel compound (B), 1 to 100 parts by mass of the aluminum compound (C), and 1 to 800 parts by mass of the fluorine-containing compound (D). Furthermore, a surface treatment composition (K) containing 20 to 90 mass% of silicon oxide (E) and metal phosphate (F) in a total ratio in the total solid content of the surface treatment composition is applied, The technique which has the surface treatment film | membrane whose film adhesion amount formed by making it dry 0.1-2.0 g / m < 2 > is disclosed. Patent Document 28 discloses a titanium-containing aqueous liquid (A) obtained by mixing a titanium compound such as a hydrolyzable titanium compound or a low condensate thereof with a hydrogen peroxide solution on the surface of a zinc-based plated steel sheet or an aluminum-based plated steel sheet. ) Containing 0.01 to 10 parts by mass of the nickel compound (B), 1 to 100 parts by mass of the aluminum compound (C), and 1 to 800 parts by mass of the fluorine-containing compound (D). Furthermore, the coating amount formed by applying and drying a surface treatment composition (J) containing 20 to 90 mass% of silicon oxide (E) in the total solid content of the surface treatment composition Discloses a technique having a surface treatment film of 0.1 to 2.0 g / m 2 . Patent Document 29 discloses a surface treatment composition containing a specific titanium-containing aqueous liquid, an organic phosphoric acid compound, a vanadic acid compound, a zirconium fluoride compound, and a zirconium carbonate compound on the surface of a zinc-based plated steel sheet or the like. The technology has a surface treatment film by a coating composition in which an epoxy resin having a primary hydroxyl group in the resin and a curing agent having a group that crosslinks with a hydroxyl group and a solid lubricant are blended in the upper layer. It is disclosed. Patent Document 30 discloses that an organic phosphate compound and a nonionic aqueous bisphenol are used for a titanium-based aqueous liquid obtained by mixing a specific titanium compound with hydrogen peroxide on the surface of a zinc-based plated steel sheet or an aluminum-based plated steel sheet. A technique for forming a surface treatment film by a surface treatment composition in which an A-type epoxy resin, a vanadate compound, a zirconium fluoride compound and a zirconium carbonate compound are added in a predetermined ratio, and preferably forming an organic film on the upper layer Is disclosed.
これらの技術は、総じて亜鉛めっき鋼板やアルミめっき鋼板に、炭酸ジルコニウム化合物とＮｉやＶ、Ｓｉなどの化合物を配合し、ノンクロメートタイプの表面処理として開示されている技術だが、これらの技術は溶出しうる成分として、ＶやＮｉ、Ｃｏなどの重金属を含有しており、これらの人体や健康に及ぼす影響について十分には考慮されておらず、食品に直接接触する調理器には用いることは出来ないことが多い。 These technologies are generally disclosed as non-chromate type surface treatments by compounding zirconium carbonate compounds and compounds such as Ni, V, and Si into galvanized steel sheets and aluminum plated steel sheets. As a possible component, it contains heavy metals such as V, Ni, Co, etc., and these effects on the human body and health are not fully considered, and can be used for cookers that come into direct contact with food. Often not.
特許文献３１には、（Ａ）チタン化合物およびジルコニウム化合物の中から少なくとも１種以上、（Ｂ）ｍｙｏ−イノシト−ルの２〜６個の結合リン酸エステル、およびそのアルカリ金属塩、アルカリ土類金属塩、およびアンモニウム塩の中から少なくとも１種以上と（Ｃ）シリカを含有し、（Ａ）の金属換算量（Ｚｒ＋Ｔｉ）：（Ｂ）：（Ｃ）の質量比が１：０．２〜１．７：０．２〜５である皮膜を（Ａ）の金属換算量で３０〜１０００ｍｇ／ｍ２付与した加熱時の耐変色性、加熱後耐食性に優れたアルミめっき鋼材およびその水系処理薬剤が開示されている。特許文献３２には、ジルコニウム化合物及びチタン化合物の少なくとも１種（Ａ）、ヒドロキシカルボン酸、有機ホスホン酸、多価アルコールリン酸エステル及びリン酸並びにそれらの塩よりなる群から選ばれる少なくとも１種（Ｂ）、並びに金属がＶ、Ｚｎ、Ｍｇ、Ａｌ、Ｃａ、Ｚｒ、Ｔｉ、Ｎｉ、Ｉｎ、Ｃｏ、Ｃｕ、Ｆｅ、Ｍｎ、Ｙ、Ｃｅ、Ｓｒ、Ｂａ、Ｍｏ、Ｌａ又はＳｎであるβ−ジケトン金属錯体の少なくとも１種（Ｃ）を配合してなる水系金属表面処理剤、表面処理方法及び表面処理金属材料が開示されている。しかし、耐熱用途（特に、調理器用）アルミめっき鋼板として、十分な性能が得られていなかった。 Patent Document 31 includes (A) at least one or more of titanium compounds and zirconium compounds, (B) 2 to 6 linked phosphate esters of myo-inositol, and alkali metal salts and alkaline earths thereof. It contains at least one or more of metal salts and ammonium salts and (C) silica, and the mass ratio of (A) in terms of metal (Zr + Ti) :( B) :( C) is from 1: 0.2 to 1.7: An aluminum-plated steel material having excellent coating discoloration resistance upon heating and 30-1000 mg / m 2 in terms of metal equivalent of (A), which is 0.2 to 5 and excellent in corrosion resistance after heating, and its aqueous treatment chemical Is disclosed. Patent Document 32 discloses at least one selected from the group consisting of at least one (A) of a zirconium compound and a titanium compound, hydroxycarboxylic acid, organic phosphonic acid, polyhydric alcohol phosphate ester and phosphoric acid, and salts thereof ( B), and β-diketones in which the metal is V, Zn, Mg, Al, Ca, Zr, Ti, Ni, In, Co, Cu, Fe, Mn, Y, Ce, Sr, Ba, Mo, La or Sn An aqueous metal surface treatment agent, a surface treatment method, and a surface treatment metal material formed by blending at least one metal complex (C) are disclosed. However, sufficient performance has not been obtained as an aluminum-plated steel sheet for heat resistance (especially for cookers).
本発明は、従来技術の上記問題点を解決して、クロムを含まないことで環境に対する負荷を著しく軽減し、かつＶやＣｏなどの重金属群を含有しないにもかかわらず、張り出し加工や深絞り加工後の耐食性に極めて優れ、同時に塗装性、耐熱性および耐水性に優れた保護皮膜を有する調理器用アルミめっき鋼板とその製造方法を提供することを目的とするものである。 The present invention solves the above-mentioned problems of the prior art, remarkably reduces the burden on the environment by not containing chromium, and does not contain heavy metal groups such as V and Co. An object of the present invention is to provide an aluminum-plated steel sheet for cooking appliances having a very excellent corrosion resistance after processing and at the same time having a protective film excellent in paintability, heat resistance and water resistance, and a method for producing the same.
本発明者らはこれらの問題を解決すべく鋭意検討を重ねてきた結果、表面処理剤を塗布し、水洗することなく焼付けることによって形成された保護皮膜を有する特定の組成のアルミめっき鋼板であって、前記保護皮膜が特定の元素のみから成り、かつ特定の有機物を含有せず、特定の構成元素の割合である保護皮膜を形成するための表面処理剤において、特定のＺｒの供給源、Ｆの供給源、Ｐの供給源からなり、特定のｐＨであることを特徴とするアルミめっき鋼板が、環境に対する負荷を著しく軽減し、その上で張り出し加工や深絞り加工後の耐食性に極めて優れ、同時に塗装性、耐熱性および耐水性に優れた保護皮膜を有する調理器用アルミめっき鋼板であることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve these problems, the present inventors have applied a surface treatment agent, and a specific composition of an aluminum-plated steel sheet having a protective film formed by baking without washing with water. In the surface treatment agent for forming the protective film which is composed of only a specific element and does not contain a specific organic substance and has a specific constituent element ratio, a specific Zr supply source, An aluminum-plated steel sheet that consists of a supply source of F and a supply source of P and is characterized by a specific pH significantly reduces the environmental burden, and has excellent corrosion resistance after overhanging and deep drawing. At the same time, the present inventors have found that it is an aluminum-plated steel sheet for cooking appliances having a protective film excellent in paintability, heat resistance and water resistance, and has completed the present invention.
すなわち本発明は、保護皮膜を有するめっき層組成がＡｌ：７０質量％以上のアルミめっき鋼板であって、前記保護皮膜は、Ｚｒ、Ｆ、Ｐ、Ｃ、Ｏ、ＮおよびＨのみから成り、ＺｒとＯを主成分とし、Ｚｒ−Ｏのネットワークの一部にＦを導入していることに加え、Ｐをリン酸ジルコニウムの形で、三次元のジルコニウム酸化構造中の一部骨格として取り込んでおり、かつ数平均分子量が２００以上の有機物を含有せず、前記保護皮膜の構成元素のうち、ＺｒとＦの質量比Ｚｒ／Ｆが１．０〜１０．０であり、ＺｒとＰの質量比Ｚｒ／Ｐが８．５〜１８．０であり、前記保護皮膜中に含まれるＺｒ含有量が２３．０質量％〜４８．０質量％であることを特徴とする、表面処理アルミめっき鋼板に関する。
That is, the present invention is an aluminum-plated steel sheet having a plating layer composition having a protective film of Al: 70% by mass or more, wherein the protective film is composed only of Zr, F, P, C, O, N, and H. Zr In addition to introducing F into a part of the Zr-O network, P is incorporated in the form of zirconium phosphate as a partial skeleton in the three-dimensional zirconium oxide structure. And the organic compound whose number average molecular weight is 200 or more is not contained, Among the constituent elements of the protective film, the mass ratio Zr / F of Zr and F is 1.0 to 10.0, and the mass ratio of Zr and P Zr / P is 8.5 to 18.0, and the Zr content contained in the protective film is 23.0% by mass to 48.0% by mass. .
また、本発明の表面処理アルミめっき鋼板では、前記保護皮膜の皮膜量が、０．２〜２．０ｇ／ｍ２であることが好ましい。 Moreover, in the surface treatment aluminum plating steel plate of this invention, it is preferable that the film quantity of the said protective film is 0.2-2.0 g / m < 2 >.
また、本発明は、めっき組成がＡｌ：７０質量％以上のアルミめっき鋼板に、表面処理剤を塗布し、水洗することなく焼付けることによって、前記アルミめっき鋼板の表面に保護皮膜を形成する表面処理アルミめっき鋼板の製造方法であって、前記表面処理剤は、前記保護皮膜がＺｒ、Ｆ、Ｐ、Ｃ、Ｏ、ＮおよびＨのみから成り、かつ数平均分子量が２００以上の有機物を含有せず、前記保護皮膜の構成元素のうち、ＺｒとＦの質量比Ｚｒ／Ｆが１．０〜１０．０となり、ＺｒとＰの質量比Ｚｒ／Ｐが８．５〜１８．０となり、前記保護皮膜中に含まれるＺｒ含有量が２３．０質量％〜４８．０質量％となるように成分が調整され、前記表面処理剤の各成分の供給源が、炭酸、りん酸、フッ化水素酸からなる群から選ばれる１種以上の無機酸および／又はそのアンモニウム塩と、ジルコニウムフッ化水素酸を除くジルコニウム含有錯化合物からなり、前記表面処理剤のｐＨが８．０〜１１．０であることを特徴とする、表面処理アルミめっき鋼板の製造方法に関する。 Further, the present invention provides a surface on which a protective film is formed on the surface of the aluminum-plated steel sheet by applying a surface treatment agent to an aluminum-plated steel sheet having a plating composition of Al: 70% by mass or more and baking it without washing with water. A method for producing a treated aluminum-plated steel sheet, wherein the surface treatment agent contains an organic substance in which the protective film is composed only of Zr, F, P, C, O, N, and H, and the number average molecular weight is 200 or more. Of the constituent elements of the protective film, the mass ratio Zr / F between Zr and F is 1.0 to 10.0, the mass ratio Zr / P between Zr and P is 8.5 to 18.0, The components are adjusted so that the Zr content contained in the protective film is 23.0 mass% to 48.0 mass%, and the source of each component of the surface treatment agent is carbonic acid, phosphoric acid, hydrogen fluoride One or more inorganic acids selected from the group consisting of acids And / or an ammonium salt thereof and a zirconium-containing complex compound excluding zirconium hydrofluoric acid, wherein the surface treatment agent has a pH of 8.0 to 11.0. It relates to a manufacturing method.
本発明の耐熱用途用アルミめっき鋼板とその製造方法は、環境に対する負荷を著しく軽減し、その上で張り出し加工や深絞り加工後の耐食性に極めて優れ、同時に塗装性、耐熱性および耐水性に優れる。 The aluminum-plated steel sheet for heat-resistant use and the method for producing the same of the present invention significantly reduce the burden on the environment, and are extremely excellent in corrosion resistance after overhanging and deep drawing, and at the same time, excellent in paintability, heat resistance and water resistance. .
以下に、本発明の好適な実施の形態について詳細に説明する。 Hereinafter, preferred embodiments of the present invention will be described in detail.
本発明において、アルミめっき鋼板のめっき層はＡｌ含有量が７０質量％以上で、好ましくは、Ａｌ含有量が７０〜９７質量％かつＳｉ含有量が３〜１５質量％の２成分系または多成分系のめっきである。本発明の表面処理液は、めっき層のＡｌとＡｌＯＦの化合物を形成することで皮膜の密着性を確保し平面部耐食性を発揮し、保護皮膜中にて生成するめっき層との反応化合物である（ＮＨ４）ＡｌＦ４が溶解性であるため腐食環境下において溶解して加工部等の新規露出面上で沈殿皮膜を形成して加工部耐食性にも効果を発揮する。そのため、Ａｌ含有量が７０質量％未満のＡｌ分の少ないめっきでは、めっきからのＡｌ供給量が不足するために十分な耐食性を発現できない。当初より表面処理剤にＡｌイオンを添加すると液安定性が悪くなるために添加することはできない。また、Ｓｉ添加の目的は、アルミニウム系めっき層と母材鋼との界面に生成するＦｅ−Ａｌ合金層をＦｅ−Ａｌ−Ｓｉ合金層に改質、薄層化して過大な成長を抑制するためであるが、めっきのＳｉ含有量が３質量％未満ではＦｅ−Ａｌ合金層が成長しすぎて加工後の耐食性が低下し、一方、Ｓｉ含有量が１５質量％を超えると、粗大なＳｉ初晶が晶出して加工後の耐食性が低下するおそれがある。 In the present invention, the plating layer of the aluminum-plated steel sheet has an Al content of 70% by mass or more, preferably a two-component system or a multicomponent having an Al content of 70 to 97% by mass and an Si content of 3 to 15% by mass. System plating. The surface treatment liquid of the present invention is a reaction compound with the plating layer formed in the protective film by ensuring the adhesion of the film by forming the compound of Al and AlOF of the plating layer and exhibiting the flat surface corrosion resistance. Since (NH 4 ) AlF 4 is soluble, it dissolves in a corrosive environment and forms a precipitate film on a newly exposed surface such as a processed part, thereby exhibiting an effect on the processed part corrosion resistance. Therefore, plating with a small Al content with an Al content of less than 70% by mass cannot exhibit sufficient corrosion resistance because the Al supply from the plating is insufficient. If Al ions are added to the surface treatment agent from the beginning, the liquid stability deteriorates, so that it cannot be added. The purpose of Si addition is to modify the Fe-Al alloy layer formed at the interface between the aluminum-based plating layer and the base steel to a Fe-Al-Si alloy layer and to reduce the thickness by suppressing the excessive growth. However, if the Si content of the plating is less than 3% by mass, the Fe—Al alloy layer grows too much and the corrosion resistance after processing decreases, whereas if the Si content exceeds 15% by mass, the coarse Si initial Crystals may crystallize and the corrosion resistance after processing may be reduced.
めっき中の不純物元素として、微量のＦｅ、Ｎｉ、Ｃｏ等が介在することがある。また、必要に応じ、Ｍｇ、Ｓｎ、ミッシュメタル、Ｓｂ、Ｚｎ、Ｃｒ、Ｗ、Ｖ、Ｍｏ、等を添加してもよい。アルミめっき鋼板の製造法について特に制限はないが、溶融フラックスめっきや、ゼンジマー法、オールラジアント法等による溶融めっき、電気めっき、蒸着めっきが好ましい。 Trace amounts of Fe, Ni, Co, etc. may be present as impurity elements during plating. Moreover, you may add Mg, Sn, Misch metal, Sb, Zn, Cr, W, V, Mo, etc. as needed. Although there is no restriction | limiting in particular about the manufacturing method of an aluminum plating steel plate, Hot dip plating, electroplating, and vapor deposition plating by the melt flux plating, the Sendzimer method, the all radiant method, etc. are preferable.
本発明において、アルミめっき鋼板に使用する母材鋼の成分については限定しないが、鋼種としては、例えば、Ｔｉ、Ｎｂ、Ｂ等を添加したＩＦ鋼、Ａｌ−ｋ鋼、Ｃｒ添加鋼、ステンレス鋼、ハイテン等が挙げられる。これらのうち、耐熱用途にはＡｌ−ｋ鋼の適用が好ましい。 In this invention, although it does not limit about the component of the base material steel used for an aluminum plating steel plate, As a steel grade, IF steel, Al-k steel, Cr addition steel, stainless steel which added Ti, Nb, B etc., for example And high ten. Of these, application of Al-k steel is preferred for heat resistant applications.
本発明のアルミめっき鋼板に形成された保護皮膜は、Ｚｒ、Ｆ、Ｐ、Ｃ、Ｏ、ＮおよびＨのみから成る必要がある。また、各成分の供給源は、炭酸、りん酸、フッ化水素酸からなる群から選ばれる１種以上の無機酸および／又はそのアンモニウム塩と、ジルコニウムフッ化水素酸を除くジルコニウム含有錯化合物である必要がある。特に、Ｚｒの供給源は、炭酸ジルコニウムアンモニウムおよび／又は酢酸ジルコニウムが好ましく、Ｆの供給源はフッ化水素酸および／又はフッ化水素酸アンモニウムが好ましく、Ｐの供給源はりん酸および／又はりん酸のアンモニウム中和物であることが好ましい。Ｚｒ供給源については炭酸ジルコニウムアンモニウムがより好ましい。Ｆ供給源およびＰ供給源については、明示した化合物の双方が好適である。本発明のアルミめっき鋼板は調理器用であるため、Ｚｒ、ＰおよびＦの供給源については人体に影響を及ぼす物質ではないことが必要であり、そのため人体への影響が十分に検討されている前記化合物を用いる必要がある。Ｚｒ、ＦおよびＰの供給源が前記化合物で無い場合、人体へ深刻な影響を及ぼす可能性があるため好ましくない。 The protective film formed on the aluminized steel sheet of the present invention needs to be composed only of Zr, F, P, C, O, N and H. The source of each component is one or more inorganic acids selected from the group consisting of carbonic acid, phosphoric acid and hydrofluoric acid and / or ammonium salts thereof, and a zirconium-containing complex compound excluding zirconium hydrofluoric acid. There must be. In particular, the source of Zr is preferably ammonium zirconium carbonate and / or zirconium acetate, the source of F is preferably hydrofluoric acid and / or ammonium hydrofluoride, and the source of P is phosphoric acid and / or phosphorus. It is preferably an acid neutralized ammonium product. As the Zr supply source, ammonium zirconium carbonate is more preferable. For the F and P sources, both the specified compounds are suitable. Since the aluminized steel sheet of the present invention is for a cooker, it is necessary that the supply source of Zr, P and F is not a substance that affects the human body, and therefore the influence on the human body has been sufficiently studied. It is necessary to use a compound. If the source of Zr, F and P is not the above-mentioned compound, it is not preferable because it may seriously affect the human body.
また、本発明のアルミめっき鋼板に形成された保護皮膜は、数平均分子量が２００以上の有機物を含有しないことが必要である。数平均分子量が２００未満であっても、人体への有害性が証明もしくは懸念されている物質は含有してはならない。数平均分子量が２００以上の有機物、特に一般に樹脂と呼ばれる高分子体やオリゴマーを含有すると、耐熱性が低下するだけでなく、使用環境により毒性や蓄積性を有する化合物に分解・縮重合および変態する可能性があるため好ましくない。本発明の保護皮膜に使用できる有機物としては、特に限定するものではないが、酒石酸、酢酸、クエン酸および乳酸などが挙げられる。 Moreover, the protective film formed on the aluminized steel sheet of the present invention needs to contain no organic matter having a number average molecular weight of 200 or more. Even if the number average molecular weight is less than 200, it should not contain substances that are proved to be harmful or harmful to human bodies. When an organic substance having a number average molecular weight of 200 or more, particularly a polymer or oligomer generally called a resin, is contained, not only the heat resistance is lowered, but also decomposed / condensed and transformed into a compound having toxicity and accumulation properties depending on the use environment. This is not preferable because there is a possibility. Examples of organic substances that can be used in the protective film of the present invention include, but are not limited to, tartaric acid, acetic acid, citric acid, and lactic acid.
また、前記保護皮膜の構成元素の含有量に関して、ＺｒとＦの質量比Ｚｒ／Ｆは１．０〜１０．０である必要があり、２〜４であることが好ましく、２．５〜３．０であることがより好ましい。ＺｒとＦの質量比Ｚｒ／Ｆが１．０未満であると、耐水性が得られず、環境負荷物質の溶出を助長するだけでなく、エッチング性が増加し、処理液安定性が得られないため好ましくなく、１０．０を超えると、張り出し加工や深絞り加工後の耐食性が得られないため好ましくない。逆に２．５〜３．０であると、極めて優れた張り出し加工や深絞り加工後の耐食性が得られ、かつ、耐水性も十分となり、環境負荷物質の溶出を抑制できるため、本発明のアルミめっき鋼板に形成された保護皮膜として最も好適である。 Moreover, regarding the content of the constituent elements of the protective film, the mass ratio Zr / F of Zr to F needs to be 1.0 to 10.0, preferably 2 to 4, and preferably 2.5 to 3 0.0 is more preferable. When the mass ratio Zr / F between Zr and F is less than 1.0, water resistance cannot be obtained, and not only does it promote elution of environmentally hazardous substances, but also etching property increases, and processing solution stability is obtained. It is not preferable because it is not, and if it exceeds 10.0, the corrosion resistance after overhanging or deep drawing cannot be obtained, which is not preferable. On the other hand, if it is 2.5 to 3.0, the corrosion resistance after the overhanging process or deep drawing process is obtained, and the water resistance is sufficient, so that the elution of environmentally hazardous substances can be suppressed. It is most suitable as a protective film formed on an aluminum plated steel sheet.
また、前記構成元素の含有量に関して、ＺｒとＰの質量比Ｚｒ／Ｐは８．５〜１８．０である必要があり、１０〜１５であることが好ましく、１２．０〜１３．５であることがより好ましい。ＺｒとＰの質量比Ｚｒ／Ｐが８．５未満であると、塗装性、耐熱性が得られず実用上の問題が生じ、加えて、耐水性が得られないため環境負荷物質の溶出が生じ、処理液安定性も得られないため好ましくなく、１８．０を超えると耐熱性と処理液安定性が得られないため好ましくない。逆に１２．０〜１３．５であると、極めて優れた張り出し加工や深絞り加工後の耐食性が得られ、本発明のアルミめっき鋼板に形成された保護皮膜として最も好適である。 Further, regarding the content of the constituent elements, the mass ratio Zr / P of Zr and P needs to be 8.5 to 18.0, preferably 10 to 15, and preferably 12.0 to 13.5. More preferably. If the mass ratio Zr / P of Zr and P is less than 8.5, paintability and heat resistance cannot be obtained, resulting in practical problems. In addition, water resistance cannot be obtained, so that environmental load substances can be eluted. This is not preferable because the stability of the processing solution is not obtained, and it is not preferable because the heat resistance and the stability of the processing solution cannot be obtained when the value exceeds 18.0. On the other hand, when it is 12.0 to 13.5, extremely excellent corrosion resistance after overhanging or deep drawing is obtained, and it is most suitable as a protective film formed on the aluminum-plated steel sheet of the present invention.
さらに、保護皮膜中に含まれるＺｒ含有量が２３質量％〜４８質量％である必要があり、２８質量％〜４１質量％であることが好ましく、３１質量％〜３７質量％であることがより好ましい。造膜成分であるＺｒの含有量が低下した場合、他の成分を添加しないとすると、前記Ｚｒ／ＦやＺｒ／Ｐが本発明の好適範囲を満たさず、然るに前記の不具合が生じるため好ましくない。 Furthermore, the Zr content contained in the protective film needs to be 23% by mass to 48% by mass, preferably 28% by mass to 41% by mass, and more preferably 31% by mass to 37% by mass. preferable. If the content of Zr, which is a film-forming component, is reduced, if other components are not added, the above Zr / F and Zr / P do not satisfy the preferred range of the present invention, but the above-mentioned problems occur, which is not preferable. .
前記質量比算出に用いる各成分の質量に関しては、蛍光Ｘ線分析装置にて測定することができ、他の方法としては、保護皮膜を水に溶解させ、ＩＣＰ（発光分光分析）やＴＯＣ（全有機炭素分析）などの機器分析にて求めることもできる。 The mass of each component used for the mass ratio calculation can be measured with a fluorescent X-ray analyzer. As another method, a protective film is dissolved in water, ICP (emission spectroscopic analysis) or TOC (total It can also be determined by instrumental analysis such as organic carbon analysis.
本発明のアルミめっき鋼板の保護皮膜を形成する前記表面処理剤のｐＨは８．０〜１１．０である必要があり、８．５〜１０．５であることが好ましく、９〜１０であることがより好ましい。前記表面処理剤のｐＨが８．０未満であると処理液安定性が得られないため好ましくなく、１１．０を超えると、素材であるアルミめっき鋼板のエッチングが過多となり、耐水性も低下するため環境負荷物質の溶出が助長されるため好ましくない。 The pH of the surface treatment agent for forming the protective film of the aluminum-plated steel sheet of the present invention needs to be 8.0 to 11.0, preferably 8.5 to 10.5, and preferably 9 to 10. It is more preferable. When the pH of the surface treatment agent is less than 8.0, it is not preferable because the stability of the treatment solution cannot be obtained. When the pH exceeds 11.0, etching of the aluminum-plated steel sheet, which is a material, becomes excessive, and water resistance is also lowered. Therefore, elution of environmentally hazardous substances is promoted, which is not preferable.
本発明のアルミめっき鋼板の保護皮膜は、前記表面処理剤を塗布し、水洗することなく乾燥させる必要がある。本発明の保護皮膜を形成する表面処理剤は塗布型であり、反応型の表面処理剤のように水洗をする必要がなく、乾燥前に水洗をすると、皮膜の大部分が溶け落ちるため好ましくない。塗布方法に関しては、ロールコート、流しかけ、スプレーおよび浸漬など公知の方法であれば、限定されるものではないが、中でもロールコートが好ましい。乾燥方法に関しては、熱風乾燥、誘導加熱乾燥および近赤外線乾燥など公知の方法であれば限定されるものではない。乾燥温度については、到達温度で７０℃〜１５０℃であることが好ましく、９０℃〜１２０℃であることがより好ましい。到達温度が７０〜１５０℃であると、皮膜の含水率や皮膜成分の造膜状態が好ましい状態になるため、本発明の効果である張り出し加工や深絞り加工後の耐食性が極めて優れる。 The protective film of the aluminum-plated steel sheet of the present invention needs to be applied without applying the surface treatment agent and washing it with water. The surface treatment agent for forming the protective film of the present invention is a coating type, and it is not necessary to wash with water like a reactive surface treatment agent, and washing with water before drying is not preferable because most of the film dissolves away. . The coating method is not limited as long as it is a known method such as roll coating, pouring, spraying, and dipping, but roll coating is particularly preferable. The drying method is not limited as long as it is a known method such as hot air drying, induction heating drying, and near infrared drying. About drying temperature, it is preferable that it is 70 to 150 degreeC by ultimate temperature, and it is more preferable that it is 90 to 120 degreeC. When the ultimate temperature is 70 to 150 ° C., the moisture content of the film and the film forming state of the film components are in a preferable state, and therefore the corrosion resistance after the overhanging process or deep drawing process, which is the effect of the present invention, is extremely excellent.
皮膜質量に関しては、０．２〜２．０ｇ／ｍ２であることが好ましく、０．３〜０．．８ｇ／ｍ２であることがより好ましく、０．３〜０．６ｇ／ｍ２であることが最も好ましい。皮膜質量が０．２〜２．０ｇ／ｍ２の範囲であると全ての性能が満足する理想的な保護皮膜が形成される。 The film mass is preferably 0.2 to 2.0 g / m 2 and preferably 0.3 to 0. . More preferably 8 g / m 2, and most preferably 0.3-0.6 g / m 2. When the film mass is in the range of 0.2 to 2.0 g / m 2 , an ideal protective film satisfying all the performances is formed.
本発明のアルミめっき鋼板は、クロムを含まないことで環境に対する負荷を著しく軽減し、その上で張り出し加工や深絞り加工後の耐食性に極めて優れ、同時に塗装性、耐熱性および耐水性に優れる。この理由は以下のように推測されるが、本発明はかかる推測に縛られるものではない。 The aluminum-plated steel sheet of the present invention is remarkably reduced in environmental load because it does not contain chromium, and has excellent corrosion resistance after overhanging and deep drawing, and at the same time, excellent paintability, heat resistance and water resistance. The reason is presumed as follows, but the present invention is not limited to such presumption.
本発明のアルミめっき鋼板は、保護皮膜の主成分としてＺｒ化合物を有する。Ｚｒ化合物としては、皮膜形成源としてジルコニウムフッ化水素酸を除くジルコニウム含有錯化合物を用いることができ、炭酸ジルコニウムアンモニウムが最も好ましい。これらは、その構造からもわかるように、皮膜形成時に炭酸やアンモニアが揮発し、Ｚｒと酸素を主成分とする皮膜が形成される。この皮膜が所謂ガラスのような皮膜を形成するため、環境遮断能に優れた耐食性の良好な皮膜を形成するものと推察される。しかしながら、前記したようにガラスのような皮膜であるため、皮膜に加工負荷がかかると容易に割れが生じ、特徴であった環境遮断能が発揮されなくなる。また、表面が平滑であるため、塗装などの上塗りが密着しにくい。このようなＺｒ−Ｏ皮膜にＦを添加することで、Ｚｒ−Ｏのネットワークの一部にＦを導入でき、強固なネットワークを部分的に柔軟にすることができる。また、素材表面をエッチングし、密着性の乏しい酸化膜を除去し、加えて表面を反応性の高い状態にすることで、Ｚｒの密着性を改善することができる。これらの効果によりＦを添加することで、張り出し加工や深絞り加工後の耐食性に極めて優れる皮膜とすることができるのである。 The aluminized steel sheet of the present invention has a Zr compound as a main component of the protective film. As the Zr compound, a zirconium-containing complex compound excluding zirconium hydrofluoric acid can be used as a film forming source, and ammonium zirconium carbonate is most preferable. As can be seen from the structure of these, carbonic acid and ammonia are volatilized during film formation, and a film mainly composed of Zr and oxygen is formed. Since this film forms a so-called glass-like film, it is presumed that a film having excellent corrosion resistance and excellent environmental barrier ability is formed. However, as described above, since it is a glass-like film, when the film is subjected to a processing load, it easily breaks, and the characteristic environmental barrier ability cannot be exhibited. Moreover, since the surface is smooth, it is difficult for the top coat such as paint to adhere. By adding F to such a Zr—O film, F can be introduced into a part of the Zr—O network, and the strong network can be partially made flexible. Moreover, the adhesion of Zr can be improved by etching the surface of the material, removing the oxide film with poor adhesion, and making the surface highly reactive. By adding F due to these effects, it is possible to obtain a film having extremely excellent corrosion resistance after the overhanging process or the deep drawing process.
また、Ｐは、リン酸ジルコニウムの形で、三次元のジルコニウム酸化構造中の一部骨格として取り込まれ、ジルコニウム錯体とリン酸が架橋された構造となる。 Further, P is incorporated in the form of zirconium phosphate as a partial skeleton in a three-dimensional zirconium oxide structure, and has a structure in which a zirconium complex and phosphoric acid are crosslinked.
以下に本発明の実施例及び比較例を挙げて本発明を具体的に説明するが、本発明はこれらにより限定されるものではない。試験板の調製、実施例および比較例、および表面処理剤の塗布の方法について下記に説明する。 EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples of the present invention, but the present invention is not limited thereto. Preparation of the test plate, examples and comparative examples, and a method for applying the surface treatment agent will be described below.
（試験板の調製）
（１）試験素材
厚さ０．８ｍｍの冷延鋼板を溶融めっきラインに通板し、Ａｌ−１０ｍａｓｓ％Ｓｉ（９０ｍａｓｓ％Ａｌ）組成のＡｌ−Ｓｉめっきを実施した。めっき付着量を約４０ｇ／ｍ２に調整したＡｌ−Ｓｉめっきを使用した。
（２）脱脂処理
素材を、６０℃のアルカリ脱脂剤（サーフクリーナー１５５、日本ペイント社製）２％水溶液を用いて３０秒間スプレー処理して脱脂し、純水で３０秒間水洗したのちに乾燥したものを試験板とした。
(Preparation of test plate)
(1) Test material A cold rolled steel sheet having a thickness of 0.8 mm was passed through a hot dipping line, and Al-Si plating with an Al-10 mass% Si (90 mass% Al) composition was performed. Al-Si plating with the plating adhesion amount adjusted to about 40 g / m 2 was used.
(2) Degreasing treatment The material was sprayed for 30 seconds using a 2% aqueous solution of a 60 ° C. alkaline degreasing agent (Surf Cleaner 155, manufactured by Nippon Paint Co., Ltd.), washed with pure water for 30 seconds, and then dried. This was used as a test plate.
実施例および比較例に使用した保護皮膜形成用表面処理剤の配合例を表１に示す。試験に供した表面処理剤は、イオン交換水に表１の成分を順次攪拌しながら加え、固形分が１０質量％となるように調整した。 Table 1 shows formulation examples of the surface treatment agent for forming a protective film used in Examples and Comparative Examples. The surface treatment agent used in the test was adjusted so that the solid content was 10% by mass by adding the components in Table 1 to ion-exchanged water while sequentially stirring.
表１に示す実施例用表面処理剤および比較例用表面処理剤を表１に示す処理条件にて保護皮膜を形成させ、試験に供した。保護皮膜中に含まれる元素の比を蛍光Ｘ線分析装置にて確認し、蛍光Ｘ線装置測定で得られた強度と実付着量の検量線により算出した。また、比較例１３〜１７については、表２に記載の特許文献を参考として作製した。 A protective film was formed on the surface treatment agent for Examples and the surface treatment agent for Comparative Examples shown in Table 1 under the treatment conditions shown in Table 1 and used for the test. The ratio of the elements contained in the protective film was confirmed with a fluorescent X-ray analyzer, and the intensity obtained by the fluorescent X-ray apparatus measurement and the calibration curve of the actual adhesion amount were calculated. Moreover, about Comparative Examples 13-17, it produced with reference to the patent document of Table 2.
＜張り出し加工部耐食性＞
試験片の中央をエリクセン試験機にて７ｍｍ押し出し、ＪＩＳ−Ｚ−２３７１による塩水噴霧試験を１２０時間行い、白錆発生状況を観察した。
（評価基準）
◎＝錆発生が全面積の３％未満
○＝錆発生が全面積の３％以上１０％未満
△＝錆発生が全面積の１０％以上３０％未満
×＝錆発生が全面積の３０％以上
<Corrosion resistance of overhang processed part>
The center of the test piece was extruded 7 mm with an Erichsen tester, a salt spray test according to JIS-Z-2371 was performed for 120 hours, and the occurrence of white rust was observed.
(Evaluation criteria)
◎ = Rust generation is less than 3% of the total area ○ = Rust generation is 3% or more and less than 10% of the total area Δ = Rust generation is 10% or more and less than 30% of the total area × = Rust generation is 30% or more of the total area
＜深絞り加工後の耐食性＞
高速深絞り試験機にて、絞り比：２．０、しわ押さえ荷重：２．０ｔｏｎ、ポンチ速度：６０ｍ／ｍｉｍにて深絞り加工を行い、ＪＩＳ−Ｚ−２３７１による塩水噴霧試験を７２時間行い、側面の白錆発生状況を観察した。
（評価基準）
◎＝錆発生が全面積の３％未満
○＝錆発生が全面積の３％以上１０％未満
△＝錆発生が全面積の１０％以上３０％未満
×＝錆発生が全面積の３０％以上
<Corrosion resistance after deep drawing>
Using a high-speed deep drawing tester, deep drawing is performed at a drawing ratio: 2.0, wrinkle holding load: 2.0 ton, punch speed: 60 m / mim, and a salt spray test according to JIS-Z-2371 is conducted for 72 hours. The occurrence of white rust on the side was observed.
(Evaluation criteria)
◎ = Rust generation is less than 3% of the total area ○ = Rust generation is 3% or more and less than 10% of the total area Δ = Rust generation is 10% or more and less than 30% of the total area × = Rust generation is 30% or more of the total area
＜塗装性＞
メラミンアルキッド系塗料をバーコートで塗布し、１２０℃で２０分焼付けた後、１ｍｍ碁盤目にカットし、密着性の評価を残個数割合（残個数／カット数：１００個）にて行った。
（評価基準）
◎＝１００％
○＝９５％以上
△＝９０％以上、９５％未満
×＝９０％未満
<Paintability>
A melamine alkyd paint was applied with a bar coat, baked at 120 ° C. for 20 minutes, and then cut into 1 mm grids, and the adhesion was evaluated by the remaining number ratio (remaining number / number of cuts: 100).
(Evaluation criteria)
◎ = 100%
○ = 95% or more Δ = 90% or more, less than 95% × = less than 90%
＜耐熱性＞
炉内温度が３００℃のオーブンに１０分間投入し、試験前および後の色調をカラーコンピューターにて測定し、色差を求めた。
（評価基準）
◎＝△Ｅが１．０未満
○＝△Ｅが１．０以上２．０未満
△＝△Ｅが２．０以上３．０未満
×＝△Ｅが３．０以上
<Heat resistance>
The oven temperature was 300 ° C. for 10 minutes, and the color tone before and after the test was measured with a color computer to obtain the color difference.
(Evaluation criteria)
◎ = ΔE is less than 1.0 ○ = ΔE is 1.0 or more and less than 2.0 Δ = ΔE is 2.0 or more and less than 3.0 × = ΔE is 3.0 or more
＜耐水性＞
超純水を入れた１Ｌ密閉容器（ステンレス製）に試験片を入れ、オートクレーブにて、溶出成分を測定した。なお使用した試験液（超純水）は９００ｍＬで、使用した試験片は寸法：９０ｍｍ×１００ｍｍを５枚（総面積：０．０９ｍ２（１３９．５ｉｎｃｈ２））とし、温度１２１℃にて１２０分保持した。試験後の試験液をＩＣＰにて含有成分量を測定した。
（評価基準）
◎＝０．０２ｍｇ／ｉｎｃｈ２未満
○＝０．０２ｍｇ／ｉｎｃｈ２以上、０．０５ｍｇ／ｉｎｃｈ２未満
×＝０．０５ｍｇ／ｉｎｃｈ２以上
<Water resistance>
The test piece was put in a 1 L sealed container (made of stainless steel) containing ultrapure water, and the eluted components were measured with an autoclave. In addition, the test liquid (ultra pure water) used was 900 mL, and the test piece used was made into 5 pieces (total area: 0.09 m 2 (139.5 inch 2 )) of dimensions: 90 mm × 100 mm, and 120 ° C. at a temperature of 121 ° C. Held for a minute. The amount of components contained in the test solution after the test was measured by ICP.
(Evaluation criteria)
◎ = 0.02mg / inch 2 less than ○ = 0.02mg / inch 2 or more, 0.05mg / inch 2 less than × = 0.05mg / inch 2 or more
＜エッチング性＞
温度２５℃の処理液が３００ｍＬ入った容器に試験片（寸法：７５ｍｍ×５０ｍｍ ２０枚 面積：０．１５ｍ２）を１０分浸漬させ、ＩＣＰにて溶出したアルミニウムの量を測定した。
（評価基準）
◎＝０．１ｍｇ／ｍ２・ｓｅｃ未満
○＝０．１ｍｇ／ｍ２・ｓｅｃ以上、０．３ｍｇ／ｍ２・ｓｅｃ未満
×＝０．０３ｍｇ／ｍ２・ｓｅｃ以上
<Etching property>
A test piece (size: 75 mm × 50 mm, 20 areas: 0.15 m 2 ) was immersed for 10 minutes in a container containing 300 mL of a treatment liquid at a temperature of 25 ° C., and the amount of aluminum eluted with ICP was measured.
(Evaluation criteria)
◎ = less than 0.1 mg / m 2 · sec ○ = 0.1 mg / m 2 · sec or more, less than 0.3 mg / m 2 · sec × = 0.03 mg / m 2 · sec or more
＜環境負荷性＞
表面処理に係わる工程における環境負荷を、直接的および間接的に評価した。
（評価基準）
○＝環境負荷が無い
△＝処理工程における排水に環境負荷物質が含有される
×＝皮膜から環境負荷物質が溶出する
<Environmental impact>
The environmental load in the process related to the surface treatment was evaluated directly and indirectly.
(Evaluation criteria)
○ = No environmental impact △ = Environmentally hazardous substances are contained in wastewater in the treatment process × = Environmentally hazardous substances are eluted from the film
＜処理液安定性＞
処理液を４０℃の恒温保管庫に静置し、保管安定性を評価した。
（評価基準）
○＝３ヶ月経時にて変化なし
△＝１ヶ月経時にて変化は無いものの、３ヶ月経時までの間で沈殿が生じる
×＝１ヶ月経時にて沈殿が生じる
<Processing solution stability>
The treatment liquid was left in a constant temperature storage at 40 ° C., and storage stability was evaluated.
(Evaluation criteria)
○ = No change after 3 months; Δ = No change after 1 month, but precipitation occurs until 3 months; x = Precipitation occurs after 1 month
評価結果を表３および表４に示す。実施例１〜２は比較例１〜３と比較して、皮膜性能に優れるだけでなく、比較例１〜３のように、本発明のＺｒ、ＦおよびＰ源を別の物質に置き換えたることで、環境負荷物質が排出されやすくなる。また、Ｚｒを使用しない場合、皮膜の全性能が著しく低下するだけでなく、皮膜成分が溶出する。実施例１および３〜１２を比較例４〜６と比較すると、Ｚｒ／Ｆが本発明の好適範囲にあることで耐食性などの皮膜性能に優れることがわかる。実施例３〜７よりＺｒ／Ｆが小さくなると、耐水性やエッチング性が低下する傾向にあり、逆に、実施例８〜１２より、Ｚｒ／Ｆが大きくなると、加工部耐食性が低下する傾向があるが、好適範囲であれば十分に実使用可能な状態である。実施例１および１３〜２５を比較例７〜９と比較すると、Ｚｒ／Ｐが本発明の好適範囲にあることで耐食性などの皮膜性能に優れることがわかる。実施例１３〜１９より、Ｚｒ／Ｐが小さくなると、塗装性、耐水性およびエッチング性が低下する傾向にあり、逆に、実施例２０〜２５より、Ｚｒ／Ｐが大きくなると、加工性がやや低下する他、耐熱性および処理液安定性が低下するが、好適範囲であれば十分に実使用可能な状態である。実施例１および２６〜３１は比較例１０〜１１と比較すると、ｐＨが本発明の好適範囲にあることで耐食性などの皮膜性能に優れることがわかる。また、実施例１および３２〜３６より、本発明の好適範囲を満たすことで、皮膜量０．２ｇ／ｍ２〜０．８ｇ／ｍ２で実用に十分である性能が得られることがわかる。一方、比較例１３〜１７より、類似した開示技術のいずれにおいても、本発明の優れた効果を十分に得ることは出来ず、本発明の保護皮膜を形成したアルミめっき鋼板がこれまでに無い技術的に優れたものであることがわかる。以上より、本発明の好適成分を好適な範囲にて保護皮膜を形成すると、クロムを含まないことで環境に対する負荷を著しく軽減し、その上で張り出し加工や深絞り加工後の耐食性に極めて優れ、同時に塗装性、耐熱性および耐水性に優れた保護皮膜を有する調理器用アルミめっき鋼板を得ることができる。 The evaluation results are shown in Table 3 and Table 4. Examples 1-2 are not only excellent in film performance as compared with Comparative Examples 1-3, but also replaced the Zr, F and P sources of the present invention with other substances as in Comparative Examples 1-3. This makes it easier to discharge environmentally hazardous substances. Further, when Zr is not used, not only the overall performance of the film is remarkably lowered but also the film components are eluted. When Example 1 and 3-12 are compared with Comparative Examples 4-6, it turns out that it is excellent in film | membrane performances, such as corrosion resistance, because Zr / F exists in the suitable range of this invention. When Zr / F is smaller than in Examples 3 to 7, water resistance and etching properties tend to decrease. Conversely, from Examples 8 to 12, when Zr / F is increased, the corrosion resistance of processed parts tends to decrease. However, if it is within a suitable range, it is sufficiently practically usable. When Examples 1 and 13 to 25 are compared with Comparative Examples 7 to 9, it can be seen that Zr / P is excellent in film performance such as corrosion resistance when it is in the preferred range of the present invention. From Examples 13 to 19, when Zr / P decreases, the paintability, water resistance and etching properties tend to decrease. Conversely, from Examples 20 to 25, when Zr / P increases, the workability is slightly increased. In addition to lowering, the heat resistance and the stability of the processing solution are lowered, but if it is in a suitable range, it is sufficiently usable. When Examples 1 and 26 to 31 are compared with Comparative Examples 10 to 11, it can be seen that the pH is in the preferred range of the present invention and the coating performance such as corrosion resistance is excellent. In Examples from 1 and 32 - 36, by satisfying the preferable range of the present invention, it can be seen that performance in coating amount 0.2g / m 2 ~0.8g / m 2 is sufficient for practical use can be obtained. On the other hand, from Comparative Examples 13 to 17, in any of the similar disclosed technologies, the excellent effect of the present invention cannot be sufficiently obtained, and there is no technology with an aluminum-plated steel sheet on which the protective film of the present invention is formed so far. It can be seen that this is excellent. From the above, when a protective film is formed in a suitable range of the preferred component of the present invention, the load on the environment is remarkably reduced by not containing chromium, and on top of that, it is extremely excellent in corrosion resistance after overhang processing and deep drawing processing, At the same time, an aluminized steel sheet for cooking appliances having a protective coating excellent in paintability, heat resistance and water resistance can be obtained.
以上、本発明の好適な実施形態について説明したが、本発明はかかる例に限定されないことは言うまでもない。当業者であれば、特許請求の範囲に記載された範疇内において、各種の変更例または修正例に想到し得ることは明らかであり、それらについても当然に本発明の技術的範囲に属するものと了解される。
As mentioned above, although preferred embodiment of this invention was described, it cannot be overemphasized that this invention is not limited to this example. It will be apparent to those skilled in the art that various changes and modifications can be made within the scope of the claims, and these are naturally within the technical scope of the present invention. Understood.
Claims (3)
前記保護皮膜は、Ｚｒ、Ｆ、Ｐ、Ｃ、Ｏ、ＮおよびＨのみから成り、ＺｒとＯを主成分とし、Ｚｒ−Ｏのネットワークの一部にＦを導入していることに加え、Ｐをリン酸ジルコニウムの形で、三次元のジルコニウム酸化構造中の一部骨格として取り込んでおり、かつ数平均分子量が２００以上の有機物を含有せず、
前記保護皮膜の構成元素のうち、ＺｒとＦの質量比Ｚｒ／Ｆが１．０〜１０．０であり、ＺｒとＰの質量比Ｚｒ／Ｐが８．５〜１８．０であり、
前記保護皮膜中に含まれるＺｒ含有量が２３．０質量％〜４８．０質量％であることを特徴とする、表面処理アルミめっき鋼板。 A plating layer composition having a protective film is an aluminum-plated steel sheet of Al: 70% by mass or more,
The protective film is composed of only Zr, F, P, C, O, N, and H. The protective film is mainly composed of Zr and O, and F is introduced into a part of the Zr—O network. In the form of zirconium phosphate, as a partial skeleton in the three-dimensional zirconium oxide structure, and containing no organic matter having a number average molecular weight of 200 or more,
Among the constituent elements of the protective film, the mass ratio Zr / F of Zr and F is 1.0 to 10.0, the mass ratio Zr / P of Zr and P is 8.5 to 18.0,
The surface-treated aluminized steel sheet, wherein the Zr content contained in the protective film is 23.0 mass% to 48.0 mass%.
前記表面処理剤は、前記保護皮膜がＺｒ、Ｆ、Ｐ、Ｃ、Ｏ、ＮおよびＨのみから成り、かつ数平均分子量が２００以上の有機物を含有せず、前記保護皮膜の構成元素のうち、ＺｒとＦの質量比Ｚｒ／Ｆが１．０〜１０．０となり、ＺｒとＰの質量比Ｚｒ／Ｐが８．５〜１８．０となり、前記保護皮膜中に含まれるＺｒ含有量が２３．０質量％〜４８．０質量％となるように成分が調整され、
前記表面処理剤の各成分の供給源が、炭酸、りん酸、フッ化水素酸からなる群から選ばれる１種以上の無機酸および／又はそのアンモニウム塩と、ジルコニウムフッ化水素酸を除くジルコニウム含有錯化合物からなり、
前記表面処理剤のｐＨが８．０〜１１．０であることを特徴とする、表面処理アルミめっき鋼板の製造方法。
Manufacture of a surface-treated aluminum-plated steel sheet that forms a protective film on the surface of the aluminum-plated steel sheet by applying a surface treatment agent to an aluminum-plated steel sheet having a plating composition of Al: 70% by mass or more and baking it without washing with water. A method,
In the surface treatment agent, the protective film is composed only of Zr, F, P, C, O, N and H, and does not contain an organic substance having a number average molecular weight of 200 or more. Among the constituent elements of the protective film, The mass ratio Zr / F between Zr and F is 1.0 to 10.0, the mass ratio Zr / P between Zr and P is 8.5 to 18.0, and the Zr content contained in the protective film is 23. The ingredients are adjusted to be 0.0 mass% to 48.0 mass%,
The source of each component of the surface treatment agent is one or more inorganic acids selected from the group consisting of carbonic acid, phosphoric acid and hydrofluoric acid and / or ammonium salts thereof, and zirconium containing except for zirconium hydrofluoric acid Consisting of complex compounds,
The method for producing a surface-treated aluminized steel sheet, wherein the surface treatment agent has a pH of 8.0 to 11.0.
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