JP6092591B2 - Spray-coated surface treatment composition, method for producing surface-treated galvanized steel sheet, and surface-treated galvanized steel sheet - Google Patents
Spray-coated surface treatment composition, method for producing surface-treated galvanized steel sheet, and surface-treated galvanized steel sheet Download PDFInfo
- Publication number
- JP6092591B2 JP6092591B2 JP2012255599A JP2012255599A JP6092591B2 JP 6092591 B2 JP6092591 B2 JP 6092591B2 JP 2012255599 A JP2012255599 A JP 2012255599A JP 2012255599 A JP2012255599 A JP 2012255599A JP 6092591 B2 JP6092591 B2 JP 6092591B2
- Authority
- JP
- Japan
- Prior art keywords
- titanium
- steel sheet
- galvanized steel
- compound
- mass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000203 mixture Substances 0.000 title claims description 89
- 229910001335 Galvanized steel Inorganic materials 0.000 title claims description 85
- 239000008397 galvanized steel Substances 0.000 title claims description 85
- 238000004381 surface treatment Methods 0.000 title claims description 51
- 238000004519 manufacturing process Methods 0.000 title claims description 29
- 239000007921 spray Substances 0.000 title claims description 8
- 239000010936 titanium Substances 0.000 claims description 70
- 229910052719 titanium Inorganic materials 0.000 claims description 69
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 68
- 150000003609 titanium compounds Chemical class 0.000 claims description 47
- 229910000831 Steel Inorganic materials 0.000 claims description 46
- 238000005507 spraying Methods 0.000 claims description 46
- 239000010959 steel Substances 0.000 claims description 46
- -1 phosphoric acid compound Chemical class 0.000 claims description 29
- 150000001875 compounds Chemical class 0.000 claims description 25
- 239000007787 solid Substances 0.000 claims description 24
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 claims description 23
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 22
- 229910052845 zircon Inorganic materials 0.000 claims description 19
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims description 19
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 18
- 229910052731 fluorine Inorganic materials 0.000 claims description 18
- 239000011737 fluorine Substances 0.000 claims description 18
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 16
- 229920005989 resin Polymers 0.000 claims description 13
- 239000011347 resin Substances 0.000 claims description 13
- 239000003960 organic solvent Substances 0.000 claims description 12
- 150000002816 nickel compounds Chemical class 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 5
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 claims description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 239000007788 liquid Substances 0.000 description 79
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 54
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 44
- 230000007797 corrosion Effects 0.000 description 44
- 238000005260 corrosion Methods 0.000 description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 37
- 238000000576 coating method Methods 0.000 description 32
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 30
- 239000011248 coating agent Substances 0.000 description 23
- 238000000034 method Methods 0.000 description 12
- 125000004432 carbon atom Chemical group C* 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 8
- 229920005749 polyurethane resin Polymers 0.000 description 8
- 238000003860 storage Methods 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 7
- 230000009257 reactivity Effects 0.000 description 7
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 6
- 238000013329 compounding Methods 0.000 description 6
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229910000348 titanium sulfate Inorganic materials 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000005530 etching Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000007747 plating Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 5
- 239000011882 ultra-fine particle Substances 0.000 description 5
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 3
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 238000005246 galvanizing Methods 0.000 description 3
- 230000003301 hydrolyzing effect Effects 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 229960004592 isopropanol Drugs 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 229940078494 nickel acetate Drugs 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 229910007570 Zn-Al Inorganic materials 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 230000003750 conditioning effect Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 2
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 125000005461 organic phosphorous group Chemical group 0.000 description 2
- HJZKOAYDRQLPME-UHFFFAOYSA-N oxidronic acid Chemical compound OP(=O)(O)C(O)P(O)(O)=O HJZKOAYDRQLPME-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 235000003270 potassium fluoride Nutrition 0.000 description 2
- 239000011698 potassium fluoride Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000001846 repelling effect Effects 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XHAZMZWXAOBLQG-UHFFFAOYSA-N (1-hydroxy-1-phosphonopropyl)phosphonic acid Chemical compound CCC(O)(P(O)(O)=O)P(O)(O)=O XHAZMZWXAOBLQG-UHFFFAOYSA-N 0.000 description 1
- LMHAGAHDHRQIMB-UHFFFAOYSA-N 1,2-dichloro-1,2,3,3,4,4-hexafluorocyclobutane Chemical compound FC1(F)C(F)(F)C(F)(Cl)C1(F)Cl LMHAGAHDHRQIMB-UHFFFAOYSA-N 0.000 description 1
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 1
- HHAPGMVKBLELOE-UHFFFAOYSA-N 2-(2-methylpropoxy)ethanol Chemical compound CC(C)COCCO HHAPGMVKBLELOE-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- BDLXTDLGTWNUFM-UHFFFAOYSA-N 2-[(2-methylpropan-2-yl)oxy]ethanol Chemical compound CC(C)(C)OCCO BDLXTDLGTWNUFM-UHFFFAOYSA-N 0.000 description 1
- PAJMKGZZBBTTOY-UHFFFAOYSA-N 2-[[2-hydroxy-1-(3-hydroxyoctyl)-2,3,3a,4,9,9a-hexahydro-1h-cyclopenta[g]naphthalen-5-yl]oxy]acetic acid Chemical compound C1=CC=C(OCC(O)=O)C2=C1CC1C(CCC(O)CCCCC)C(O)CC1C2 PAJMKGZZBBTTOY-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- WRAGBEWQGHCDDU-UHFFFAOYSA-M C([O-])([O-])=O.[NH4+].[Zr+] Chemical compound C([O-])([O-])=O.[NH4+].[Zr+] WRAGBEWQGHCDDU-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- 229910003088 Ti−O−Ti Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- CMMUKUYEPRGBFB-UHFFFAOYSA-L dichromic acid Chemical compound O[Cr](=O)(=O)O[Cr](O)(=O)=O CMMUKUYEPRGBFB-UHFFFAOYSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- DJGLQWCKPYQFJG-UHFFFAOYSA-N hydrogen peroxide;titanium Chemical compound [Ti].OO DJGLQWCKPYQFJG-UHFFFAOYSA-N 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 229910052816 inorganic phosphate Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- ALTWGIIQPLQAAM-UHFFFAOYSA-N metavanadate Chemical compound [O-][V](=O)=O ALTWGIIQPLQAAM-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- GQJPVGNFTLBCIQ-UHFFFAOYSA-L sodium;zirconium(4+);carbonate Chemical compound [Na+].[Zr+4].[O-]C([O-])=O GQJPVGNFTLBCIQ-UHFFFAOYSA-L 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000002436 steel type Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 1
- XROWMBWRMNHXMF-UHFFFAOYSA-J titanium tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[Ti+4] XROWMBWRMNHXMF-UHFFFAOYSA-J 0.000 description 1
- AKMXMQQXGXKHAN-UHFFFAOYSA-N titanium;hydrate Chemical compound O.[Ti] AKMXMQQXGXKHAN-UHFFFAOYSA-N 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical class O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 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
- Chemical Treatment Of Metals (AREA)
Description
本発明は、スプレー塗布表面処理用組成物、表面処理亜鉛めっき鋼板の製造方法、および表面処理亜鉛めっき鋼板に関する。本発明は特に、溶融亜鉛めっき鋼板または合金化溶融亜鉛めっき鋼板である亜鉛めっき鋼板の表面にスプレー塗布法で塗布するのに適した、６価クロムを含まない環境適用型の表面処理用組成物に関する。 The present invention relates to a spray-coated surface treatment composition, a method for producing a surface-treated galvanized steel sheet, and a surface-treated galvanized steel sheet. In particular, the present invention is an environmentally-applicable surface treatment composition that does not contain hexavalent chromium, and is suitable for being applied to the surface of a galvanized steel sheet that is a galvanized steel sheet or an alloyed galvanized steel sheet by a spray coating method. About.
家電用鋼板、建材用鋼板、自動車用鋼板には、従来から溶融亜鉛めっき鋼板または合金化溶融亜鉛めっき鋼板の表面に、耐食性（耐白錆性、耐赤錆性）を向上させる目的で、クロム酸、重クロム酸またはその塩類を主要成分とした処理液によるクロメート処理が施された鋼板が幅広く用いられている。このクロメート処理は、溶融亜鉛めっき鋼板または合金化溶融亜鉛めっき鋼板の生産ラインでは、スプレー塗布法により行われることが多く、経済的である。スプレー塗布法は、クロメート処理液をスプレーで塗布またはシャワーで流しかける比較的簡便な方法であり、その後ロールやエアー絞りで塗布（液膜）量を調整し、オーブンなどで乾燥させる。 For the purpose of improving corrosion resistance (white rust resistance, red rust resistance) on the surface of hot-dip galvanized steel sheets or alloyed hot-dip galvanized steel sheets, steel plates for home appliances, building steels, and automobiles are conventionally used. Steel plates that have been subjected to chromate treatment with a treatment liquid mainly composed of dichromic acid or salts thereof are widely used. This chromate treatment is often performed by a spray coating method in a production line of a hot dip galvanized steel sheet or an alloyed hot dip galvanized steel sheet, and is economical. The spray coating method is a relatively simple method in which a chromate treatment solution is applied by spraying or is poured by a shower. Thereafter, the amount of coating (liquid film) is adjusted with a roll or an air squeezer and dried in an oven or the like.
しかし、クロメート処理は公害規制物質である６価クロムを使用しており、環境に対する配慮から、またクロメート処理液の廃液処理に多大な労力と費用とを要することから、処理液にクロムを含まないクロメートフリー技術が検討されている。 However, the chromate treatment uses hexavalent chromium, which is a pollution-controlling substance, and because of the environmental considerations and the waste liquid treatment of the chromate treatment liquid requires a great deal of labor and expense, the treatment liquid does not contain chromium. Chromate-free technology is being studied.
ここで、６価クロムを含まない処理液を溶融亜鉛めっき鋼板または合金化溶融亜鉛めっき鋼板に塗布する場合、クロメートと同等以上の耐食性を発現させるためには乾燥後の皮膜付着量が１ｇ／ｍ２程度必要となるが、スプレー塗布法ではこれだけの皮膜付着量を得ることが困難である。つまり、スプレーした後にロールやエアーで液膜を強く絞りとるスプレー塗布法では、耐食性を発現させるために必要な皮膜付着量を得ることが困難である。そのため、この場合ロールコート法を用いて鋼板表面に処理液を塗布、乾燥させ、表面処理皮膜を形成することが一般的であった。これは、ロールコート法は、アプリケータロールの回転速度や各ロール間の押付け圧などの調整により、皮膜付着量の調整が比較的に容易なためである。 Here, when a treatment liquid not containing hexavalent chromium is applied to a hot dip galvanized steel sheet or an alloyed hot dip galvanized steel sheet, the coating amount after drying is 1 g / m in order to develop corrosion resistance equivalent to or better than chromate. Although about 2 is required, it is difficult to obtain such a coating amount by the spray coating method. That is, in the spray coating method in which the liquid film is strongly squeezed with a roll or air after spraying, it is difficult to obtain a coating amount necessary for developing corrosion resistance. For this reason, in this case, it has been common to apply a treatment liquid to the surface of the steel sheet using a roll coating method and dry it to form a surface treatment film. This is because the roll coating method makes it relatively easy to adjust the coating amount by adjusting the rotational speed of the applicator roll and the pressing pressure between the rolls.
特許文献１には、６価クロムを含まない処理液として、特定のチタン含有水性液と、ニッケル化合物または／およびコバルト化合物と、弗素含有化合物とを所定の割合で配合した表面処理用組成物を用いて、これをロールコート法により溶融Ｚｎ−Ａｌ系合金めっき鋼板に塗布、乾燥させて表面処理皮膜を形成することで、優れた耐食性と耐黒変性を有し、めっき外観性にも優れたクロムフリー表面処理溶融Ｚｎ−Ａｌ系合金めっき鋼板を得る技術が記載されている。 Patent Document 1 discloses a surface treatment composition in which a specific titanium-containing aqueous liquid, a nickel compound or / and a cobalt compound, and a fluorine-containing compound are blended in a predetermined ratio as a treatment liquid that does not contain hexavalent chromium. Using this, it is applied to a molten Zn-Al alloy-plated steel sheet by a roll coating method and dried to form a surface treatment film, thereby having excellent corrosion resistance and blackening resistance, and excellent plating appearance. A technique for obtaining a chromium-free surface-treated molten Zn-Al alloy-plated steel sheet is described.
ロールコート法は塗布直後の液膜厚を数ミクロン程度に精度よく制御するのに適した方法であるが、２段または３段のバックアップロールなどの大規模な設備を要するため、設備投資が必要となる。そこで本発明者らは、従来設備であり、かつ、より簡易な設備で塗布可能なスプレー塗布法を用いて、特許文献１と同様の組成物を溶融亜鉛めっき鋼板表面および合金化溶融亜鉛めっき鋼板表面のそれぞれに塗布、乾燥させて表面処理皮膜を形成し、特許文献１と同様の特性を得ることを試みた。しかしながら、特許文献１と同様の種々の組成物についてスプレー塗布法で表面処理皮膜を形成したところ、一部の組成物を塗布した場合に塗布直後の液膜に発泡が見られ、その後乾燥させて形成した表面処理皮膜の外観（仕上がり状態）が大きく損なわれるという問題があった。また、上記種々の組成物のいずれを塗布した場合にも、スプレー塗布法では鋼板に十分な耐食性が付与されないという問題もあった。 The roll coating method is suitable for accurately controlling the film thickness immediately after coating to several microns, but requires large-scale equipment such as a two-stage or three-stage backup roll, and requires capital investment. It becomes. Therefore, the inventors of the present invention used a spray coating method that is a conventional facility and that can be applied with a simpler facility, and applied the same composition as that of Patent Document 1 to the surface of the galvanized steel sheet and the galvannealed steel sheet. Each surface was coated and dried to form a surface treatment film, and an attempt was made to obtain the same characteristics as in Patent Document 1. However, when a surface treatment film was formed by spray coating for various compositions similar to Patent Document 1, foaming was observed in the liquid film immediately after coating when a part of the composition was coated, and then the film was dried. There was a problem that the appearance (finished state) of the formed surface treatment film was greatly impaired. Moreover, even when any of the above various compositions is applied, there is a problem that the spray coating method does not provide sufficient corrosion resistance to the steel sheet.
そこで本発明の目的は、上記課題に鑑み、溶融亜鉛めっき鋼板または合金化溶融亜鉛めっき鋼板の表面にスプレー塗布法で塗布して表面処理皮膜を形成する場合にも十分な耐食性および良好な皮膜外観（仕上がり状態）を呈することが可能な、６価クロムを全く含まない環境適用型の表面処理用組成物を提供すること、この組成物を用いた表面処理溶融亜鉛めっき鋼板または合金化溶融亜鉛めっき鋼板である表面処理亜鉛めっき鋼板の製造方法を提供すること、およびこの方法により得られる表面処理亜鉛めっき鋼板を提供することにある。 Therefore, in view of the above problems, the object of the present invention is to provide sufficient corrosion resistance and good coating appearance even when a surface-treated coating is formed by spray coating on the surface of a hot dip galvanized steel plate or an alloyed hot dip galvanized steel plate. The present invention provides an environmentally-applicable surface treatment composition that does not contain hexavalent chromium and can exhibit a (finished state), surface-treated galvanized steel sheet or alloyed galvanized steel using this composition It is providing the manufacturing method of the surface treatment galvanization steel plate which is a steel plate, and providing the surface treatment galvanization steel plate obtained by this method.
この目的を達成すべく本発明者らがさらに検討したところ、特許文献１に記載の組成物のうち樹脂成分を含むものをスプレー塗布法で溶融亜鉛めっき鋼板または合金化溶融亜鉛めっき鋼板の表面に塗布した場合に、いずれも塗布直後の液膜に発泡が見られることが判明した。これは、分子中に親水性部分と疎水性部分とを有する樹脂成分が液気界面に配向し、界面張力を低くして泡を安定化するためと考えられる。 As a result of further investigation by the present inventors to achieve this object, the composition described in Patent Document 1 containing a resin component is applied to the surface of a hot-dip galvanized steel sheet or an alloyed hot-dip galvanized steel sheet by spray coating. In all cases, it was found that foaming was observed in the liquid film immediately after application. This is presumably because the resin component having a hydrophilic part and a hydrophobic part in the molecule is oriented at the liquid-gas interface, and the interfacial tension is lowered to stabilize the foam.
また、本発明者らは、スプレー塗布法で溶融亜鉛めっきに表面処理皮膜を形成した場合に十分な耐食性が得られない理由は、スプレー塗布法ではスプレーされた後、リンガー等で絞り切られるまでの間、ロールコート法に比べて厚い液膜が形成されるためであるとの着想に至った。すなわち、スプレー塗布法では、厚い液膜が形成されるため、特許文献１に記載の組成物のように反応性の高い処理液を用いると、溶融亜鉛めっき鋼板表面に対するエッチングが過剰に進行し、下地素地に達するようなクラックが多数形成され、十分な耐食性を確保できないのである。 In addition, the reason why the present inventors cannot obtain sufficient corrosion resistance when a surface treatment film is formed on a hot dip galvanizing by a spray coating method is that after spraying by a spray coating method, it is squeezed by a ringer or the like. In the meantime, the inventor came up with the idea that a thicker liquid film is formed compared to the roll coating method. That is, in the spray coating method, a thick liquid film is formed. Therefore, when a highly reactive treatment liquid such as the composition described in Patent Document 1 is used, etching on the surface of the hot dip galvanized steel sheet proceeds excessively. Many cracks that reach the base material are formed, and sufficient corrosion resistance cannot be ensured.
また、特許文献１に記載の組成物を合金化溶融亜鉛めっき鋼板に塗布した場合には、特に外観が得られにくく、耐食性が発現しにくいことが判明した。これは、合金化溶融亜鉛めっき鋼板の表面は溶融亜鉛めっき鋼板と比較して反応性が乏しいためであり、また、合金化により表面に多数の凹凸が形成されており、凸部では化成皮膜の薄膜化が、凹部では厚膜化がそれぞれ生じ、凹部の厚膜部では下地素地に到達するようなクラックが多数形成されるためと考えられる。そこで、組成物の成分を見直した結果、溶融亜鉛めっき鋼板および合金化溶融亜鉛めっき鋼板で発生したクラックは、組成物中の炭酸ジルコニウム化合物に起因することが新たに分かった。また、合金化溶融亜鉛めっき鋼板表面での反応性を確保しつつ、溶融亜鉛めっき鋼板表面での過剰エッチングを低減するためには、弗素含有化合物比率と有機リン酸化合物比率を特定範囲にする必要があることが新たに分かった。 Moreover, when the composition of patent document 1 was apply | coated to the galvannealed steel plate, it turned out that an external appearance is hard to be obtained especially and corrosion resistance is hard to express. This is because the surface of the alloyed hot-dip galvanized steel sheet is less reactive than the hot-dip galvanized steel sheet, and many irregularities are formed on the surface due to alloying. This is thought to be because thinning occurs in the concave portions, and many cracks are formed in the thick film portions of the concave portions so as to reach the base material. Therefore, as a result of reviewing the components of the composition, it was newly found that the cracks generated in the hot dip galvanized steel sheet and the alloyed hot dip galvanized steel sheet are caused by the zirconium carbonate compound in the composition. In addition, in order to reduce the excess etching on the surface of the hot dip galvanized steel sheet while ensuring the reactivity on the surface of the galvannealed steel sheet, it is necessary to set the ratio of the fluorine-containing compound and the ratio of the organophosphate compound within a specific range. Newly found that there is.
その結果、溶融亜鉛めっき鋼板または合金化溶融亜鉛めっき鋼板である亜鉛めっき鋼板の表面に、特定のチタン含有水性液、ニッケル化合物、弗素含有化合物、有機リン酸化合物、バナジン酸化合物および特定のエーテル系有機溶剤を、特に弗素含有化合物比率と有機リン酸化合物比率をある特定範囲で含み、樹脂成分および炭酸ジルコニウム化合物を含まない組成物を用いれば、スプレー塗布法という簡易設備でも製造可能で優れた耐食性および皮膜外観（仕上がり状態）を有する亜鉛めっき鋼板が得られることを見出し、本発明を完成させるに至った。 As a result, a specific titanium-containing aqueous liquid, nickel compound, fluorine-containing compound, organophosphate compound, vanadic acid compound, and a specific ether system are formed on the surface of a galvanized steel sheet that is a galvanized steel sheet or an alloyed galvanized steel sheet. Using an organic solvent, in particular a fluorine-containing compound ratio and an organophosphate compound ratio in a certain range, and using a composition that does not contain a resin component and a zirconium carbonate compound, it can be manufactured with simple equipment such as a spray coating method and has excellent corrosion resistance. And it discovered that the galvanized steel plate which has a film | membrane external appearance (finished state) was obtained, and came to complete this invention.
本発明は、このような知見に基づきなされたものであり、その要旨構成は以下のとおりである。
（１）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、水酸化チタンの低縮合物の中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（Ａ）を固形分の割合で１０〜４５質量％と、ニッケル化合物（Ｂ）を固形分の割合で０．０１〜１質量％と、弗素含有化合物（Ｃ）を固形分の割合で１０〜２０質量％と、有機リン酸化合物（Ｄ）を固形分の割合で４０〜６０質量％と、バナジン酸化合物（Ｅ）を固形分の割合で０．１〜３０質量％と、炭素数４から６のエーテル系有機溶剤（Ｆ）を前記（Ａ）、（Ｂ）、（Ｃ）、（Ｄ）および（Ｅ）の合計１００質量部に対する割合で５〜３０質量部と、を含有し、
樹脂成分および炭酸ジルコニウム化合物を含まない組成物であって、
溶融亜鉛めっき鋼板または合金化溶融亜鉛めっき鋼板である亜鉛めっき鋼板の少なくとも片面にスプレー塗布法にて塗布して表面処理皮膜を形成するために用いることを特徴とするスプレー塗布表面処理用組成物。
This invention is made | formed based on such knowledge, The summary structure is as follows.
(1) Mixing at least one titanium compound selected from hydrolyzable titanium compounds, low-condensates of hydrolyzable titanium compounds, titanium hydroxide, and low-condensates of titanium hydroxide with hydrogen peroxide water The obtained titanium-containing aqueous liquid (A) is 10 to 45% by mass in terms of solid content, the nickel compound (B) is 0.01 to 1% by mass in terms of solid content, and the fluorine-containing compound (C) is solid. 10 to 20% by mass, 40 to 60% by mass of the organic phosphoric acid compound (D) and 0.1 to 30% by mass of the vanadic acid compound (E) in terms of the solid content. And 5 to 30 parts by mass of the ether-based organic solvent (F) having 4 to 6 carbon atoms with respect to the total of 100 parts by mass of (A), (B), (C), (D) and (E). Containing,
A composition containing no resin component and zirconium carbonate compound,
A composition for spray coating surface treatment, which is used for forming a surface treatment film by applying at least one surface of a galvanized steel plate which is a hot dip galvanized steel plate or an alloyed hot dip galvanized steel plate by a spray coating method.
（２）前記弗素含有化合物（Ｃ）が、ジルコン弗化アンモニウム、ジルコン弗化水素酸の中から選ばれる少なくとも１種である上記（１）に記載のスプレー塗布表面処理用組成物。 (2) The composition for surface treatment by spray application according to the above (1), wherein the fluorine-containing compound (C) is at least one selected from zircon ammonium fluoride and zircon hydrofluoric acid.
（３）溶融亜鉛めっき鋼板または合金化溶融亜鉛めっき鋼板である亜鉛めっき鋼板の少なくとも片面に、上記（１）または（２）に記載のスプレー塗布表面処理用組成物をスプレー塗布法にて塗布し、リンガーロールまたはエアーで塗布量を絞り、乾燥させることにより表面処理皮膜を形成することを特徴とする表面処理亜鉛めっき鋼板の製造方法。 (3) The spray coating surface treatment composition described in (1) or (2) above is applied to at least one surface of a galvanized steel sheet which is a hot dip galvanized steel sheet or an alloyed hot dip galvanized steel sheet by a spray coating method. A method for producing a surface-treated galvanized steel sheet, characterized in that a surface-treated film is formed by squeezing the coating amount with a ringer roll or air and drying.
（４）上記（３）に記載の製造方法により製造された表面処理亜鉛めっき鋼板。 (4) A surface-treated galvanized steel sheet produced by the production method described in (3) above.
本発明によれば、表面処理用組成物に樹脂成分を含有させていないため、溶融亜鉛めっき鋼板または合金化溶融亜鉛めっき鋼板の表面にスプレー塗布法で塗布した際に発泡しにくく、その後乾燥させて得た表面処理皮膜の外観（仕上がり状態）が損なわれることがない。また、炭素数４から６のエーテル系有機溶剤を添加することにより、合金化溶融亜鉛めっき鋼板表面でのはじきを防止することができるため、これも表面処理皮膜の良好な外観に寄与する。さらに、炭酸ジルコニウム化合物を含有させていないため、合金化溶融亜鉛めっき鋼板上の凹部での皮膜クラックの発生を抑制し、その結果十分な耐食性を得ることができる。また、反応性に大きく影響する弗素含有化合物を固形分の割合で１０〜２０質量％にすることで、スプレー塗布法を用いる場合の鋼板表面との反応性が適切な組成物となり、スプレー塗布法で塗布して形成した表面処理皮膜であっても十分な耐食性を得ることができる。また、有機リン酸化合物を固形分の割合で４０〜６０質量％にすることで、合金化溶融亜鉛めっき鋼板表面との反応性が適切な組成物となり、特に優れた耐食性が発現可能となる。このようにして、溶融亜鉛めっき鋼板または合金化溶融亜鉛めっき鋼板の表面にスプレー塗布法で塗布して表面処理皮膜を形成する場合に十分な耐食性および良好な皮膜外観（仕上がり状態）を呈することが可能な、６価クロムを全く含まない環境適用型の表面処理用組成物を提供することができた。 According to the present invention, since the resin component is not contained in the surface treatment composition, it is difficult to foam when applied to the surface of a hot dip galvanized steel sheet or an alloyed hot dip galvanized steel sheet by a spray coating method, and then dried. The appearance (finished state) of the surface-treated film thus obtained is not impaired. Further, by adding an ether-based organic solvent having 4 to 6 carbon atoms, it is possible to prevent repelling on the surface of the galvannealed steel sheet, which also contributes to a good appearance of the surface-treated film. Furthermore, since no zirconium carbonate compound is contained, the occurrence of film cracks in the recesses on the galvannealed steel sheet can be suppressed, and as a result, sufficient corrosion resistance can be obtained. Moreover, the reactivity with the steel plate surface in the case of using a spray coating method becomes an appropriate composition by setting the fluorine-containing compound that greatly affects the reactivity to a solid content ratio of 10 to 20% by mass. Even a surface-treated film formed by coating with can provide sufficient corrosion resistance. Moreover, the reactivity with an alloyed hot-dip galvanized steel plate surface becomes a suitable composition by making an organic phosphoric acid compound into 40-60 mass% in the ratio of solid content, and especially outstanding corrosion resistance can be expressed. In this way, sufficient corrosion resistance and good coating appearance (finished state) can be exhibited when a surface-treated film is formed by spray coating on the surface of a hot-dip galvanized steel sheet or an alloyed hot-dip galvanized steel sheet. It was possible to provide an environmentally applicable surface treatment composition that does not contain any hexavalent chromium.
以下、本発明をより詳細に説明する。 Hereinafter, the present invention will be described in more detail.
（溶融亜鉛めっき鋼板および合金化溶融亜鉛めっき鋼板）
本発明の表面処理用組成物を適用する溶融亜鉛めっき鋼板および合金化溶融亜鉛めっき鋼板は、ＪＩＳ Ｇ ３３０２：２０１０に規定される溶融亜鉛めっきおよび合金化溶融亜鉛めっきをそれぞれ行った鋼板である。この溶融亜鉛めっきおよび合金化溶融亜鉛めっきを行った鋼板（それぞれ溶融亜鉛めっき鋼板および合金化溶融亜鉛めっき鋼板）は、その酸化物層の厚さおよび被エッチング性が本発明の表面処理用組成物に適するものであり、本発明の表面処理用組成物をスプレー塗布して表面処理皮膜が形成された表面処理溶融亜鉛めっき鋼板および表面処理合金化溶融亜鉛めっき鋼板はいずれも優れた耐食性を有する。なお、素地鋼板の鋼種は特に限定されず、低炭素鋼、極低炭素鋼、ＩＦ鋼、各種合金元素を添加した高張力鋼板等の種々の鋼板を用いることができる。
(Hot-dip galvanized steel sheet and galvannealed steel sheet)
The hot dip galvanized steel sheet and the alloyed hot dip galvanized steel sheet to which the surface treatment composition of the present invention is applied are steel sheets that have been subjected to hot dip galvanization and galvannealed hot dip galvanization as defined in JIS G 3302: 2010, respectively. The steel sheet subjected to hot dip galvanizing and alloying hot dip galvanizing (hot dip galvanized steel sheet and galvannealed steel sheet, respectively) has the thickness of the oxide layer and the etching property according to the present invention. The surface-treated hot-dip galvanized steel sheet and the surface-treated galvannealed steel sheet on which the surface-treated film is formed by spray-coating the surface-treating composition of the present invention have excellent corrosion resistance. The steel type of the base steel plate is not particularly limited, and various steel plates such as low carbon steel, extremely low carbon steel, IF steel, and high tensile steel plates to which various alloy elements are added can be used.
表面処理皮膜をめっき皮膜表面に形成した際に皮膜欠陥やムラが生じないようにするため、必要に応じて、予めめっき皮膜表面にアルカリ脱脂、溶剤脱脂、表面調整処理（アルカリ性の表面調整処理または酸性の表面調整処理）などの処理を施しておくことができる。 In order to prevent film defects and unevenness when the surface treatment film is formed on the surface of the plating film, alkali degreasing, solvent degreasing, surface adjustment treatment (alkaline surface adjustment treatment or Treatment such as acidic surface conditioning treatment can be performed.
また、使用環境下での黒変（めっき表面の酸化現象の一種）を防止する目的で、必要に応じて予めめっき表面に鉄族金属イオン（Ｎｉイオン，Ｃｏイオン，Ｆｅイオンの１種以上）を含む酸性またはアルカリ性水溶液による表面調整処理を施しておくこともできる。 In addition, for the purpose of preventing blackening in the usage environment (a kind of oxidation phenomenon on the plating surface), an iron group metal ion (one or more kinds of Ni ion, Co ion, Fe ion) is previously applied to the plating surface as necessary. Surface conditioning treatment with an acidic or alkaline aqueous solution containing can also be performed.
（表面処理皮膜の形成方法）
本発明において、溶融亜鉛めっき鋼板または合金化溶融亜鉛めっき鋼板の表面に表面処理用組成物を塗布する方法は、スプレー塗布法である。ここで、本明細書において「スプレー塗布法」とは、表面処理用組成物（処理液）を鋼板表面に対してスプレーで塗布する方法、またはシャワーで流しかける方法を意味する。その後、リンガーロールまたはエアーで塗布量を絞り、乾燥させることにより鋼板表面に皮膜を形成する。塗布の詳細な条件については後述する。
(Method for forming surface treatment film)
In the present invention, the method of applying the surface treatment composition to the surface of the hot dip galvanized steel sheet or alloyed hot dip galvanized steel sheet is a spray coating method. Here, the “spray coating method” in the present specification means a method of spraying the surface treatment composition (treatment liquid) on the steel plate surface or a method of pouring it with a shower. Thereafter, the coating amount is squeezed with a ringer roll or air and dried to form a film on the surface of the steel sheet. Detailed conditions for coating will be described later.
（スプレー塗布表面処理用組成物）
本発明のスプレー塗布表面処理用組成物は、特定のチタン含有水性液（Ａ）を固形分の割合で１０〜４５質量％と、ニッケル化合物（Ｂ）を固形分の割合で０．０１〜１質量％と、弗素含有化合物（Ｃ）を固形分の割合で１０〜２０質量％と、有機リン酸化合物（Ｄ）を固形分の割合で４０〜６０質量％と、バナジン酸化合物（Ｅ）を固形分の割合で０．１〜３０質量％と、炭素数４から６のエーテル系有機溶剤（Ｆ）を（Ａ）、（Ｂ）、（Ｃ）、（Ｄ）および（Ｅ）の合計１００質量部に対する割合で５〜３０質量部と、を含有し、樹脂成分および炭酸ジルコニウム化合物を含まない組成物であり、この組成物は６価クロムを含有しない。このような組成物を採用することによって、これを溶融亜鉛めっき鋼板または合金化溶融亜鉛めっき鋼板の表面にスプレー塗布法で塗布しても、十分な耐食性および良好な皮膜外観（仕上がり状態）を呈する表面処理皮膜を得ることができる。以下、より詳細に説明する。
(Composition for spray coating surface treatment)
In the composition for spray coating surface treatment of the present invention, the specific titanium-containing aqueous liquid (A) is 10 to 45% by mass in terms of the solid content, and the nickel compound (B) is 0.01 to 1 in terms of the solid content. 10% to 20% by mass of the fluorine-containing compound (C) in a proportion of the solid content, 40 to 60% by mass of the organophosphate compound (D) in the proportion of the solid content, and the vanadic acid compound (E). 0.1 to 30% by mass in terms of the solid content, and the ether organic solvent (F) having 4 to 6 carbon atoms is a total of 100 of (A), (B), (C), (D) and (E) The composition contains 5 to 30 parts by mass with respect to parts by mass and does not contain a resin component and a zirconium carbonate compound, and this composition does not contain hexavalent chromium. By adopting such a composition, even if it is applied to the surface of a hot-dip galvanized steel sheet or an alloyed hot-dip galvanized steel sheet by a spray coating method, sufficient corrosion resistance and good film appearance (finished state) are exhibited. A surface-treated film can be obtained. This will be described in more detail below.
前記チタン含有水性液（Ａ）は、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、水酸化チタンの低縮合物の中から選ばれる少なくとも１種のチタン化合物と過酸化水素水とを混合して得られるチタンを含む水性液である。 The titanium-containing aqueous liquid (A) contains at least one titanium compound selected from hydrolyzable titanium compounds, hydrolyzable titanium compound low condensates, titanium hydroxide and titanium hydroxide low condensates. It is an aqueous liquid containing titanium obtained by mixing with hydrogen oxide water.
前記加水分解性チタン化合物は、チタンに直接結合する加水分解性基を有するチタン化合物であって、水、水蒸気などの水分と反応することにより水酸化チタンを生成するものである。また、加水分解性チタン化合物は、チタンに結合する基の全てが加水分解性基であるものでもよいし、チタンに結合する基の一部が加水分解性基であるものでもよい。前記加水分解性基としては、上記したように水分と反応することにより水酸化チタンを生成させるものであれば特に制限はないが、例えば、低級アルコキシル基やチタンと塩を形成する基（例えば、塩素などのハロゲン原子、水素原子、硫酸イオンなど）などが挙げられる。 The hydrolyzable titanium compound is a titanium compound having a hydrolyzable group directly bonded to titanium, and generates titanium hydroxide by reacting with water such as water or water vapor. The hydrolyzable titanium compound may be one in which all of the groups bonded to titanium are hydrolyzable groups, or a part of the groups bonded to titanium may be hydrolyzable groups. The hydrolyzable group is not particularly limited as long as it generates titanium hydroxide by reacting with moisture as described above. For example, a lower alkoxyl group or a group that forms a salt with titanium (for example, Halogen atoms such as chlorine, hydrogen atoms, sulfate ions, etc.).
加水分解性基として低級アルコキシル基を含有する加水分解性チタン化合物としては、特に、一般式Ｔｉ（ＯＲ）４（式中、Ｒは同一または異なる炭素数１〜５のアルキル基を示す）で示されるテトラアルコキシチタンが好ましい。炭素数１〜５のアルキル基としては、例えば、メチル基、エチル基、ｎ−プロピル基、ｉｓｏ−プロピル基、ｎ−ブチル基、ｉｓｏ−ブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基などが挙げられる。加水分解性基として、チタンと塩を形成する基を有する加水分解性チタン化合物としては、塩化チタン、硫酸チタンなどが代表的なものとして挙げられる。 As the hydrolyzable titanium compound containing a lower alkoxyl group as a hydrolyzable group, in particular, represented by the general formula Ti (OR) 4 (wherein R represents the same or different alkyl group having 1 to 5 carbon atoms) Tetraalkoxy titanium is preferred. Examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, and a tert-butyl group. Can be mentioned. Typical examples of the hydrolyzable titanium compound having a group capable of forming a salt with titanium as a hydrolyzable group include titanium chloride and titanium sulfate.
加水分解性チタン化合物の低縮合物は、上記した加水分解性チタン化合物同士の低縮合物である。この低縮合物は、チタンに結合する基の全てが加水分解性基であるものでもよいし、チタンに結合する基の一部が加水分解性であるものでもよい。加水分解性基がチタンと塩を形成する基である加水分解性チタン化合物（例えば、塩化チタン、硫酸チタンなど）については、その加水分解性チタン化合物の水溶液とアンモニアや苛性ソーダなどのアルカリ溶液との反応により得られるオルトチタン酸（水酸化チタンゲル）も低縮合物として使用できる。 The low condensate of the hydrolyzable titanium compound is a low condensate of the above hydrolyzable titanium compounds. The low condensate may be one in which all of the groups bonded to titanium are hydrolyzable groups, or a part of the groups bonded to titanium may be hydrolyzable. For hydrolyzable titanium compounds whose hydrolyzable group forms a salt with titanium (for example, titanium chloride, titanium sulfate, etc.), an aqueous solution of the hydrolyzable titanium compound and an alkaline solution such as ammonia or caustic soda are used. Orthotitanic acid (titanium hydroxide gel) obtained by the reaction can also be used as a low condensate.
加水分解性チタン化合物の低縮合物および水酸化チタンの低縮合物としては、縮合度が２〜３０の化合物が使用可能であり、特に縮合度が２〜１０の化合物を使用することが好ましい。縮合度が３０以下であれば、過酸化水素と混合した際に白色沈殿を生じることなく、安定なチタン含有水性液が得られるからである。 As the low condensate of the hydrolyzable titanium compound and the low condensate of titanium hydroxide, a compound having a condensation degree of 2 to 30 can be used, and a compound having a condensation degree of 2 to 10 is particularly preferable. This is because if the degree of condensation is 30 or less, a stable titanium-containing aqueous liquid can be obtained without causing white precipitation when mixed with hydrogen peroxide.
以上挙げた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、水酸化チタンの低縮合物は、１種または２種以上を使用できるが、そのなかでも、上述した一般式で示される加水分解性チタン化合物であるテトラアルコキシチタンが、過酸化水素と混合した際に沈殿が生じにくいので、より好ましい。 The hydrolyzable titanium compounds listed above, low-condensates of hydrolyzable titanium compounds, titanium hydroxide, and low-condensates of titanium hydroxide can be used alone or in combination of two or more thereof. Tetraalkoxytitanium, which is a hydrolyzable titanium compound represented by the formula, is more preferred because precipitation hardly occurs when mixed with hydrogen peroxide.
チタン含有水性液（Ａ）としては、上記したチタン化合物と過酸化水素水とを混合することにより得られるチタンを含む水性液であれば、従来公知のものを特に制限なしに使用することができる。具体的には、下記のものを挙げることができる。 As the titanium-containing aqueous liquid (A), any conventionally known liquid can be used without particular limitation as long as it is an aqueous liquid containing titanium obtained by mixing the above-described titanium compound and hydrogen peroxide solution. . Specifically, the following can be mentioned.
（ｉ）含水酸化チタンのゲルまたはゾルに過酸化水素水を添加して得られるチタニルイオン過酸化水素錯体またはチタン酸（ペルオキソチタン水和物）水溶液（特開昭６３−３５４１９号公報、特開平１−２２４２２０号公報参照）。 (I) A titanyl ion hydrogen peroxide complex or an aqueous solution of titanic acid (peroxotitanium hydrate) obtained by adding hydrogen peroxide to a hydrous titanium oxide gel or sol (JP-A 63-35419, JP 1-2224220 gazette).
（ｉｉ）塩化チタンや硫酸チタンの水溶液と塩基性溶液から製造した水酸化チタンゲルに過酸化水素水を作用させ、合成することで得られるチタニア膜形成用液体（特開平９−７１４１８号公報、特開平１０−６７５１６号公報参照）。 (Ii) A liquid for forming a titania film obtained by synthesizing a titanium hydroxide gel produced from an aqueous solution of titanium chloride or titanium sulfate and a basic solution with a hydrogen peroxide solution (Japanese Patent Laid-Open No. 9-71418, (See Kaihei 10-67516).
このチタニア膜形成用液体を得る場合、チタンと塩を形成する基を有する塩化チタンや硫酸チタンの水溶液とアンモニアや苛性ソーダなどのアルカリ溶液とを反応させることによりオルトチタン酸と呼ばれる水酸化チタンゲルを沈殿させる。次いで、水を用いたデカンテーションによって水酸化チタンゲルを分離し、良く水洗し、さらに過酸化水素水を加え、余分な過酸化水素を分解除去することにより、黄色透明粘性液体を得ることができる。 When obtaining this titania film-forming liquid, titanium hydroxide gel called orthotitanic acid is precipitated by reacting an aqueous solution of titanium chloride or titanium sulfate having a salt-forming group with titanium and an alkaline solution such as ammonia or caustic soda. Let Next, the titanium hydroxide gel is separated by decantation with water, washed thoroughly with water, further added with hydrogen peroxide water, and excess hydrogen peroxide is decomposed and removed, whereby a yellow transparent viscous liquid can be obtained.
沈殿した上記オルトチタン酸は、ＯＨ同士の重合や水素結合によって高分子化したゲル状態にあり、そのままではチタンを含む水性液としては使用できない。このゲルに過酸化水素水を添加するとＯＨの一部が過酸化状態になり、ペルオキソチタン酸イオンとして溶解あるいは高分子鎖が低分子に分断された一種のゾル状態になり、余分な過酸化水素は水と酸素になって分解し、無機膜形成用のチタンを含む水性液として使用できるようになる。このゾルはチタン原子以外に酸素原子と水素原子しか含まないので、乾燥や焼成によって酸化チタンに変化する場合、水と酸素しか発生しないため、ゾルゲル法や硫酸塩などの熱分解に必要な炭素成分やハロゲン成分の除去が必要でなく、低温でも比較的密度の高い酸化チタン膜を形成することができる。 The ortho-titanic acid thus precipitated is in a gel state polymerized by polymerization of OH or hydrogen bonds, and as such cannot be used as an aqueous liquid containing titanium. When hydrogen peroxide solution is added to this gel, a part of OH is in a peroxidized state, dissolved as a peroxotitanate ion or in a kind of sol state in which the polymer chain is divided into low molecules, and excess hydrogen peroxide Is decomposed into water and oxygen, and can be used as an aqueous liquid containing titanium for forming an inorganic film. Since this sol contains only oxygen and hydrogen atoms in addition to titanium atoms, when it is changed to titanium oxide by drying or firing, only water and oxygen are generated, so carbon components necessary for thermal decomposition such as sol-gel method and sulfate Further, it is not necessary to remove the halogen component, and a titanium oxide film having a relatively high density can be formed even at a low temperature.
（ｉｉｉ）塩化チタンや硫酸チタンの無機チタン化合物水溶液に過酸化水素を加えてペルオキソチタン水和物を生成させた後に、塩基性物質を添加して得られた溶液を放置または加熱することによってペルオキソチタン水和物重合体の沈殿物を生成させ、次いで、少なくともチタン含有原料溶液に由来する水以外の溶解成分を除去した後に過酸化水素を作用させて得られるチタン酸化物形成用溶液（特開２０００−２４７６３８号公報、特開２０００−２４７６３９号公報参照）。 (Iii) Hydrogen peroxide is added to an aqueous solution of an inorganic titanium compound such as titanium chloride or titanium sulfate to form a peroxotitanium hydrate, and then the solution obtained by adding a basic substance is allowed to stand or be heated. A titanium oxide forming solution obtained by forming a precipitate of a titanium hydrate polymer, and then removing hydrogen and other dissolved components derived from at least a titanium-containing raw material solution (Japanese Patent Application Laid-Open 2000-247638, JP-A-2000-247639).
チタン化合物として加水分解性チタン化合物および／またはその低縮合物（以下、単に「加水分解性チタン化合物ａ」という）を用いるチタン含有水性液（Ａ）は、加水分解性チタン化合物ａを過酸化水素水と反応温度１〜７０℃で１０分間〜２０時間程度反応させることにより得ることができる。この加水分解性チタン化合物ａを用いたチタン含有水性液（Ａ）は、加水分解性チタン化合物ａと過酸化水素水とを反応させることにより、加水分解性チタン化合物ａが水で加水分解されて水酸基含有チタン化合物を生成し、次いで、この水酸基含有チタン化合物に過酸化水素が配位するものと考えられ、この加水分解反応および過酸化水素による配位が同時近くに起こることにより得られたものであり、室温域での安定性が極めて高く、長期の保存に耐えるキレート液を生成する。従来の製法で用いられる水酸化チタンゲルは、Ｔｉ−Ｏ−Ｔｉ結合により部分的に三次元化しており、このゲルと過酸化水素水を反応させたチタン含有水性液（Ａ）とは組成および安定性が本質的に異なる。 The titanium-containing aqueous liquid (A) using a hydrolyzable titanium compound and / or a low condensate thereof (hereinafter simply referred to as “hydrolyzable titanium compound a”) as the titanium compound is obtained by converting hydrolyzable titanium compound a to hydrogen peroxide. It can be obtained by reacting with water at a reaction temperature of 1 to 70 ° C. for about 10 minutes to 20 hours. In the titanium-containing aqueous liquid (A) using the hydrolyzable titanium compound a, the hydrolyzable titanium compound a is hydrolyzed with water by reacting the hydrolyzable titanium compound a with hydrogen peroxide. A product obtained by producing a hydroxyl group-containing titanium compound and then coordinating hydrogen peroxide to the hydroxyl group-containing titanium compound, and this hydrolysis reaction and coordination by hydrogen peroxide occur simultaneously. It produces a chelate solution that is extremely stable at room temperature and can withstand long-term storage. The titanium hydroxide gel used in the conventional production method is partially three-dimensional by Ti—O—Ti bond, and the titanium-containing aqueous liquid (A) obtained by reacting this gel with hydrogen peroxide solution is composition and stable. Sex is essentially different.
また、加水分解性チタン化合物ａを用いたチタン含有水性液（Ａ）を８０℃以上で加熱処理またはオートクレーブ処理すると、結晶化した酸化チタンの超微粒子を含む酸化チタン分散液が得られる。前記加熱処理またはオートクレーブ処理が８０℃未満では、酸化チタンの結晶化が十分に進まない。このようにして製造された酸化チタン分散液に含まれる酸化チタン超微粒子の平均粒子径は、好ましくは１０ｎｍ以下、より好ましくは１〜６ｎｍ程度である。酸化チタン超微粒子の平均粒子径が１０ｎｍより大きくなると造膜性が低下する（塗布後乾燥して皮膜とした場合、膜厚１μｍ以上でワレを生じる）ので好ましくない。この酸化チタン分散液の外観は半透明状のものである。このような酸化チタン分散液も、チタン含有水性液（Ａ）として使用することができる。 Further, when the titanium-containing aqueous liquid (A) using the hydrolyzable titanium compound a is heated or autoclaved at 80 ° C. or higher, a titanium oxide dispersion liquid containing ultrafine particles of crystallized titanium oxide is obtained. When the heat treatment or autoclave treatment is less than 80 ° C., crystallization of titanium oxide does not proceed sufficiently. The average particle diameter of the titanium oxide ultrafine particles contained in the titanium oxide dispersion thus produced is preferably 10 nm or less, more preferably about 1 to 6 nm. When the average particle diameter of the titanium oxide ultrafine particles is larger than 10 nm, the film forming property is deteriorated (when the film is dried after coating to form a film, cracking occurs at a film thickness of 1 μm or more), which is not preferable. The appearance of this titanium oxide dispersion is translucent. Such a titanium oxide dispersion can also be used as the titanium-containing aqueous liquid (A).
加水分解性チタン化合物ａを用いたチタン含有水性液（Ａ）を含む表面処理用組成物（Ｇ）を、めっき鋼板表面に塗布・乾燥（例えば、低温で加熱乾燥）することにより、それ自体で付着性に優れた緻密な酸化チタン含有皮膜（表面処理皮膜）を形成することができる。 By applying and drying the surface treatment composition (G) containing the titanium-containing aqueous liquid (A) using the hydrolyzable titanium compound a on the surface of the plated steel sheet (for example, heat drying at a low temperature), A dense titanium oxide-containing film (surface treatment film) having excellent adhesion can be formed.
表面処理用組成物（Ｇ）を塗布した後の加熱温度としては、例えば２００℃以下、特に１５０℃以下が好ましく、このような温度で加熱乾燥することにより、水酸基を若干含む非晶質（アモルファス）の酸化チタン含有皮膜が形成できる。また、上記したような８０℃以上の加熱処理またはオートクレーブ処理を経て得られた酸化チタン分散液をチタン含有水性液（Ａ）として用いた場合、表面処理用組成物（Ｇ）を塗布するだけで結晶性の酸化チタン含有皮膜が形成できるため、加熱処理できない材料のコーティング材として有用である。 The heating temperature after applying the surface treatment composition (G) is, for example, preferably 200 ° C. or less, particularly preferably 150 ° C. or less. ) Of titanium oxide-containing film can be formed. Moreover, when the titanium oxide dispersion obtained through the heat treatment or autoclave treatment as described above at 80 ° C. or more is used as the titanium-containing aqueous liquid (A), only the surface treatment composition (G) is applied. Since a crystalline titanium oxide-containing film can be formed, it is useful as a coating material for materials that cannot be heat-treated.
また、チタン含有水性液（Ａ）としては、酸化チタンゾルの存在下で、加水分解性チタン化合物ａと過酸化水素水とを反応させて得られるチタン含有水性液（Ａ１）を使用することもできる。 Further, as the titanium-containing aqueous liquid (A), a titanium-containing aqueous liquid (A1) obtained by reacting the hydrolyzable titanium compound a with hydrogen peroxide in the presence of a titanium oxide sol can also be used. .
前記酸化チタンゾルは、無定型チタニア微粒子または／およびアナタース型チタニア微粒子が水（必要に応じて、例えばアルコール系、アルコールエーテル系などの水性有機溶剤を添加してもよい）に分散したゾルである。この酸化チタンゾルとしては、従来公知のものを使用することができ、例えば、（ｉ）硫酸チタンや硫酸チタニルなどの含チタン溶液を加水分解して得られる酸化チタン凝集物、（ｉｉ）チタンアルコキシドなどの有機チタン化合物を加水分解して得られる酸化チタン凝集物、（ｉｉｉ）四塩化チタンなどのハロゲン化チタン溶液を加水分解または中和して得られる酸化チタン凝集物、などの酸化チタン凝集物を水に分散した無定型チタニアゾル、あるいは前記酸化チタン凝集物を焼成してアナタース型チタン微粒子とし、これを水に分散したゾルを使用することができる。 The titanium oxide sol is a sol in which amorphous titania fine particles and / or anatase type titania fine particles are dispersed in water (for example, an aqueous organic solvent such as an alcohol or alcohol ether may be added if necessary). As this titanium oxide sol, conventionally known ones can be used. For example, (i) a titanium oxide aggregate obtained by hydrolyzing a titanium-containing solution such as titanium sulfate or titanyl sulfate, (ii) titanium alkoxide, etc. Titanium oxide aggregates obtained by hydrolyzing organic titanium compounds of (ii), (iii) Titanium oxide aggregates obtained by hydrolyzing or neutralizing titanium halide solutions such as titanium tetrachloride, etc. Amorphous titania sol dispersed in water or a sol in which the titanium oxide aggregate is fired to form anatase titanium fine particles and dispersed in water can be used.
前記無定形チタニアの焼成では、少なくともアナターゼの結晶化温度以上の温度、例えば、４００℃〜５００℃以上の温度で焼成すれば、無定形チタニアをアナターゼ型チタニアに変換させることができる。この酸化チタンの水性ゾルとしては、例えば、ＴＫＳ−２０１（商品名，テイカ社製，アナタース型結晶形，平均粒子径６ｎｍ）、ＴＡ−１５（商品名，日産化学社製，アナタース型結晶形）、ＳＴＳ−１１（商品名，石原産業社製，アナタース型結晶形）などが挙げられる。 In the firing of the amorphous titania, the amorphous titania can be converted into anatase titania by firing at a temperature of at least the crystallization temperature of anatase, for example, a temperature of 400 ° C. to 500 ° C. or more. Examples of the aqueous sol of titanium oxide include, for example, TKS-201 (trade name, manufactured by TEIKA CORPORATION, anatase crystal form, average particle diameter 6 nm), TA-15 (trade name, manufactured by NISSAN CHEMICAL CO., LTD., Anatase crystal form). STS-11 (trade name, manufactured by Ishihara Sangyo Co., Ltd., anatase type crystal form) and the like.
チタン含有水性液（Ａ１）において、上記酸化チタンゾルｘとチタン過酸化水素反応物ｙ（加水分解性チタン化合物ａと過酸化水素水との反応生成物）との質量比率ｘ／ｙは、１／９９〜９９／１、好ましくは約１０／９０〜９０／１０の範囲が適当である。質量比率ｘ／ｙが１／９９未満では、安定性、光反応性などの点において酸化チタンゾルを添加した効果が十分に得られず、一方、９９／１を超えると造膜性が劣るので好ましくない。 In the titanium-containing aqueous liquid (A1), the mass ratio x / y between the titanium oxide sol x and the titanium hydrogen peroxide reactant y (reaction product of the hydrolyzable titanium compound a and hydrogen peroxide solution) is 1 / A range of 99 to 99/1, preferably about 10/90 to 90/10 is suitable. If the mass ratio x / y is less than 1/99, the effect of adding the titanium oxide sol cannot be sufficiently obtained in terms of stability, photoreactivity, etc. Absent.
チタン含有水性液（Ａ１）は、酸化チタンゾルの存在下で加水分解性チタン化合物ａを過酸化水素水と反応温度１〜７０℃で１０分間〜２０時間程度反応させることにより得ることができる。チタン含有水性液（Ａ１）の生成形態やその特性は、さきに述べた加水分解性チタン化合物ａを用いたチタン含有水性液（Ａ）と同様であるが、特に、酸化チタンゾルを使用することにより、合成時に一部縮合反応が起きて増粘するのが抑えられる。その理由は、縮合反応物が酸化チタンゾルの表面に吸着され、溶液状態での高分子化が抑えられるためであると考えられる。 The titanium-containing aqueous liquid (A1) can be obtained by reacting the hydrolyzable titanium compound a with hydrogen peroxide at a reaction temperature of 1 to 70 ° C. for about 10 minutes to 20 hours in the presence of a titanium oxide sol. The production form and characteristics of the titanium-containing aqueous liquid (A1) are the same as those of the titanium-containing aqueous liquid (A) using the hydrolyzable titanium compound a described above, but in particular, by using a titanium oxide sol. , It is possible to suppress a partial condensation reaction during the synthesis to increase the viscosity. The reason is considered to be that the condensation reaction product is adsorbed on the surface of the titanium oxide sol, and polymerization in a solution state is suppressed.
また、チタン含有水性液（Ａ１）を８０℃以上で加熱処理またはオートクレーブ処理すると、結晶化した酸化チタンの超微粒子を含む酸化チタン分散液が得られる。この酸化チタン分散液を得るための温度条件、結晶化した酸化チタン超微粒子の粒子径、分散液の外観なども、さきに述べた加水分解性チタン化合物ａを用いたチタン含有水性液（Ａ）と同様である。このような酸化チタン分散液も、チタン含有水性液（Ａ１）として使用することができる。 Further, when the titanium-containing aqueous liquid (A1) is subjected to a heat treatment or autoclave treatment at 80 ° C. or higher, a titanium oxide dispersion containing ultrafine particles of crystallized titanium oxide is obtained. The titanium-containing aqueous liquid (A) using the hydrolyzable titanium compound a described above also describes the temperature conditions for obtaining this titanium oxide dispersion, the particle diameter of the crystallized titanium oxide ultrafine particles, the appearance of the dispersion, etc. It is the same. Such a titanium oxide dispersion can also be used as the titanium-containing aqueous liquid (A1).
さきに述べた加水分解性チタン化合物ａを用いたチタン含有水性液（Ａ）と同様、チタン含有水性液（Ａ１）を含む表面処理用組成物（Ｈ）を、めっき鋼板表面に塗布・乾燥（例えば、低温で加熱乾燥）することにより、それ自体で付着性に優れた緻密な酸化チタン含有皮膜（表面処理皮膜）を形成することができる。 Similar to the titanium-containing aqueous liquid (A) using the hydrolyzable titanium compound a described above, the surface treatment composition (H) containing the titanium-containing aqueous liquid (A1) is applied to the surface of the plated steel sheet and dried ( For example, by performing heat drying at a low temperature, a dense titanium oxide-containing film (surface treatment film) having excellent adhesion can be formed.
表面処理用組成物（Ｈ）を塗布した後の加熱温度としては、乾けば問題なく、例えば鋼板温度として２００℃以下、特に１５０℃以下が好ましく、このような温度で加熱乾燥することにより、水酸基を若干含むアナタース型の酸化チタン含有皮膜が形成できる。 The heating temperature after applying the surface treatment composition (H) is satisfactory if it is dried. For example, the steel sheet temperature is preferably 200 ° C. or lower, particularly preferably 150 ° C. or lower. An anatase-type titanium oxide-containing film containing a small amount of can be formed.
以上述べたように、チタン含有水性液（Ａ）の中でも、加水分解性チタン化合物ａを用いたチタン含有水性液（Ａ）やチタン含有水性液（Ａ１）は、貯蔵安定性、耐食性などに優れた性能を有するので、本発明ではこれらを使用することが特に好ましい。 As described above, of the titanium-containing aqueous liquid (A), the titanium-containing aqueous liquid (A) and the titanium-containing aqueous liquid (A1) using the hydrolyzable titanium compound a are excellent in storage stability, corrosion resistance, and the like. It is particularly preferable to use these in the present invention.
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、水酸化チタンの低縮合物の中から選ばれる少なくとも１種のチタン化合物に対する過酸化水素水の配合割合は、チタン化合物１０質量部に対して過酸化水素換算で０．１〜１００質量部とすることが好ましく、１〜２０質量部とすることがより好ましい。上記配合割合を０．１質量部以上とすれば、キレート形成が十分であり白濁沈殿が生じることがなく、一方、１００質量部以下であれば、未反応の過酸化水素が残存しにくく、貯蔵中に危険な活性酸素を放出しにくいため好ましい。 The compounding ratio of hydrogen peroxide water to at least one titanium compound selected from hydrolyzable titanium compounds, hydrolyzable titanium compound low condensates, titanium hydroxide, titanium hydroxide low condensates is titanium compounds It is preferable to set it as 0.1-100 mass parts in conversion of hydrogen peroxide with respect to 10 mass parts, and it is more preferable to set it as 1-20 mass parts. If the blending ratio is 0.1 parts by mass or more, chelate formation is sufficient and cloudy precipitation does not occur. On the other hand, if it is 100 parts by mass or less, unreacted hydrogen peroxide hardly remains and is stored. It is preferable because it is difficult to release dangerous active oxygen.
過酸化水素水の過酸化水素濃度は特に限定されないが、３〜３０質量％程度であることが、取り扱いやすさ、塗装作業性に関係する生成液の固形分の点で好ましい。 The hydrogen peroxide concentration of the hydrogen peroxide solution is not particularly limited, but it is preferably about 3 to 30% by mass from the viewpoint of ease of handling and the solid content of the product liquid related to coating workability.
チタン含有水性液（Ａ）には、必要に応じて、他のゾルや顔料を添加分散させることもできる。例えば、添加物としては、市販の酸化チタンゾルや酸化チタン粉末、マイカ、タルク、シリカ、バリタ、クレーなどが挙げられ、これらの１種以上を添加することができる。 Other sols and pigments can be added and dispersed in the titanium-containing aqueous liquid (A) as necessary. Examples of the additive include commercially available titanium oxide sol, titanium oxide powder, mica, talc, silica, barita, clay, and the like, and one or more of these can be added.
処理液の安定性を確保するために、表面処理用組成物（Ｇ），（Ｈ）中でのチタン含有水性液（Ａ）の含有量は、固形分の割合で１０質量％〜４５質量％とする。 In order to ensure the stability of the treatment liquid, the content of the titanium-containing aqueous liquid (A) in the surface treatment compositions (G) and (H) is 10% by mass to 45% by mass in terms of solid content. And
前記ニッケル化合物（Ｂ）は耐黒変性向上のために配合されるものであり、ニッケル化合物（Ｂ）としては、例えば、酢酸ニッケル、硝酸ニッケル、硫酸ニッケルなどの無機ニッケル化合物が挙げられ、これらの１種または２種以上を用いることができる。なかでも、酢酸ニッケルが耐黒変性向上の点から好適である。ニッケル化合物（Ｂ）の配合量は、組成物の固形分の割合で０．０１質量％〜１質量％である。０．０１質量％以上であれば十分な耐黒変性の改善が得られ、一方、１質量％以下であれば耐食性が劣化することもないからである。 The nickel compound (B) is blended for improving blackening resistance, and examples of the nickel compound (B) include inorganic nickel compounds such as nickel acetate, nickel nitrate, and nickel sulfate. 1 type (s) or 2 or more types can be used. Of these, nickel acetate is preferred from the viewpoint of improving blackening resistance. The compounding quantity of a nickel compound (B) is 0.01 mass%-1 mass% in the ratio of the solid content of a composition. If the content is 0.01% by mass or more, sufficient blackening resistance can be improved, while if the content is 1% by mass or less, the corrosion resistance is not deteriorated.
前記弗素含有化合物（Ｃ）は耐食性を向上させるために配合されるものであり、弗素含有化合物（Ｃ）としては、例えば、ジルコン弗化アンモニウム、ジルコン弗化カリウム、ジルコン弗化水素酸、チタン弗化アンモニウム、弗化水素酸、弗化水素酸アンモニウムなどの無機弗素含有化合物が挙げられ、これらの１種または２種以上を用いることができる。なかでも、ジルコン弗化アンモニウム、ジルコン弗化水素酸の中から選ばれる少なくとも１種を用いることが、耐食性の点から好ましい。 The fluorine-containing compound (C) is blended to improve corrosion resistance. Examples of the fluorine-containing compound (C) include zircon ammonium fluoride, zircon potassium fluoride, zircon hydrofluoric acid, titanium fluoride. Inorganic fluorine-containing compounds such as ammonium fluoride, hydrofluoric acid, and ammonium hydrofluoride can be used, and one or more of these can be used. Of these, it is preferable from the viewpoint of corrosion resistance to use at least one selected from zircon ammonium fluoride and zircon hydrofluoric acid.
弗素含有化合物（Ｃ）の配合量は、組成物の固形分の割合で１０質量％〜２０質量％である。１０質量％以上とすれば、スプレー処理時の反応性を適正に得ることができ、十分な耐食性を得ることができる。一方、２０質量％以下とすれば、反応性が高くなりすぎず、めっき表面のエッチング量を抑えて、十分な耐食性を得ることができる。 The compounding quantity of a fluorine-containing compound (C) is 10 mass%-20 mass% in the ratio of the solid content of a composition. If it is 10 mass% or more, the reactivity at the time of a spray process can be obtained appropriately, and sufficient corrosion resistance can be obtained. On the other hand, if the content is 20% by mass or less, the reactivity does not become too high, and the etching amount on the plating surface can be suppressed to obtain sufficient corrosion resistance.
前記有機リン酸化合物（Ｄ）としては、例えば、１−ヒドロキシメタン−１，１−ジホスホン酸、１−ヒドロキシエタン−１，１−ジホスホン酸、１−ヒドロキシプロパン−１，１−ジホスホン酸などのヒドロキシル基含有有機亜リン酸；２−ヒドロキシホスホノ酢酸、２−ホスホノブタン−１，２，４−トリカルボン酸などのカルボキシル基含有有機亜リン酸、およびこれらの塩などが好適なものとして挙げられ、これらの１種または２種以上を用いることができる。有機リン酸化合物（Ｄ）は、チタン含有水性液（Ａ）の貯蔵安定性を向上させる効果を有し、なかでも、１−ヒドロキシエタン−１，１−ジホスホン酸はその効果が特に大きいことから、これを使用するのが特に好ましい。 Examples of the organic phosphate compound (D) include 1-hydroxymethane-1,1-diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, 1-hydroxypropane-1,1-diphosphonic acid, and the like. Suitable examples include hydroxyl group-containing organic phosphorous acid; carboxyl group-containing organic phosphorous acid such as 2-hydroxyphosphonoacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, and salts thereof. These 1 type (s) or 2 or more types can be used. The organic phosphoric acid compound (D) has an effect of improving the storage stability of the titanium-containing aqueous liquid (A). Among them, 1-hydroxyethane-1,1-diphosphonic acid has a particularly large effect. It is particularly preferred to use this.
有機リン酸化合物（Ｄ）の配合量は、組成物の固形分の割合で４０質量％〜６０質量％である。有機リン酸化合物（Ｄ）の配合量が４０質量％以上であれば、十分な貯蔵安定性を得ることができ、かつ、合金化溶融亜鉛めっき鋼板とも適度な反応性を得ることが出来る。６０質量％以下であれば、十分な耐水性を得ることができる。 The compounding quantity of an organic phosphoric acid compound (D) is 40 mass%-60 mass% in the ratio of the solid content of a composition. If the compounding amount of the organic phosphate compound (D) is 40% by mass or more, sufficient storage stability can be obtained, and appropriate reactivity can be obtained with the galvannealed steel sheet. If it is 60 mass% or less, sufficient water resistance can be obtained.
前記バナジン酸化合物（Ｅ）としては、例えば、メタバナジン酸リチウム、メタバナジン酸カリウム、メタバナジン酸ナトリウム、メタバナジン酸アンモニウム、無水バナジン酸などが挙げられ、これらの１種または２種以上を用いることができる。十分な耐食性を確保するために、バナジン酸化合物（Ｅ）の配合量は、組成物の固形分の割合で０．１質量％〜３０質量％とする。なかでも、メタバナジン酸アンモニウムが耐水付着性などの点から好ましい。 Examples of the vanadate compound (E) include lithium metavanadate, potassium metavanadate, sodium metavanadate, ammonium metavanadate, and anhydrous vanadate, and one or more of these can be used. In order to ensure sufficient corrosion resistance, the compounding amount of the vanadic acid compound (E) is 0.1% by mass to 30% by mass in terms of the solid content of the composition. Of these, ammonium metavanadate is preferable from the viewpoint of water adhesion resistance.
前記炭素数４から６のエーテル系有機溶剤（Ｆ）としては、例えばエチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、エチレングリコールイソブチルエーテル、エチレングリコール−ｔｅｒｔ−ブチルエーテルなどのグリコールエーテル系有機溶剤が挙げられ、これらの１種または２種以上を用いることができる。炭素数が４以上であれば良好な皮膜の仕上がり状態を得ることができ、炭素数が６以下であれば、処理剤中で相溶性に優れるため、安定性に優れた処理剤を得ることができる。 Examples of the ether organic solvent (F) having 4 to 6 carbon atoms include glycol ether organics such as ethylene glycol monobutyl ether, propylene glycol monomethyl ether, diethylene glycol monoethyl ether, ethylene glycol isobutyl ether, and ethylene glycol tert-butyl ether. A solvent is mentioned, These 1 type (s) or 2 or more types can be used. If the carbon number is 4 or more, it is possible to obtain a finished state of a good film, and if the carbon number is 6 or less, it is excellent in compatibility in the processing agent, so that a processing agent having excellent stability can be obtained. it can.
炭素数４から６のエーテル系有機溶剤（Ｆ）の配合量は、（Ａ）、（Ｂ）、（Ｃ）、（Ｄ）および（Ｅ）の合計１００質量部に対する割合で５〜３０質量部である。この配合量が５質量部以上であれば、合金化溶融亜鉛めっき鋼板に塗装したときのはじきによる外観不良を防止することができ、一方、３０質量部以下であれば、耐食性が劣化することがない。特に、皮膜の仕上がり性を向上させ、皮膜の乾燥性を低下させない点で、エチレングリコールモノブチルエーテルを５〜２５質量部とすることが好ましい。 The blending amount of the ether-based organic solvent (F) having 4 to 6 carbon atoms is 5 to 30 parts by mass with respect to 100 parts by mass in total of (A), (B), (C), (D) and (E). It is. If this blending amount is 5 parts by mass or more, appearance defects due to repelling when coated on an alloyed hot-dip galvanized steel sheet can be prevented, while if it is 30 parts by mass or less, corrosion resistance may deteriorate. Absent. In particular, ethylene glycol monobutyl ether is preferably 5 to 25 parts by mass in terms of improving the finish of the film and not reducing the drying property of the film.
本発明の組成物の特徴の１つは、樹脂成分を含まないことである。表面処理用組成物に樹脂成分を含有させないことにより、スプレー塗布法で塗布した際に発泡しにくく、その後乾燥させて得た表面処理皮膜の外観（仕上がり状態）が損なわれることがない。 One of the characteristics of the composition of the present invention is that it does not contain a resin component. By not including the resin component in the surface treatment composition, foaming hardly occurs when applied by a spray coating method, and the appearance (finished state) of the surface treatment film obtained by subsequent drying is not impaired.
本発明の組成物のもう１つの特徴は、炭酸ジルコニウム化合物を含まないことである。表面処理用組成物に炭酸ジルコニウム化合物を含有させないことにより、合金化溶融亜鉛めっき鋼板のような表面凹凸の激しいめっき表面であっても、凹部でのクラック発生を抑制し、優れた耐食性が発現可能となる。 Another feature of the composition of the present invention is that it does not contain a zirconium carbonate compound. By not containing a zirconium carbonate compound in the surface treatment composition, cracks in the recesses can be suppressed and excellent corrosion resistance can be achieved even on plated surfaces with rugged surfaces such as galvannealed steel sheets. It becomes.
本発明の組成物には、さらに必要に応じて、例えば、シランカップリング剤、無機リン酸化合物などのエッチング剤、本発明が規定する成分以外の重金属化合物、増粘剤、界面活性剤、染料などを含有することができる。また、本発明の組成物は、必要に応じて、例えばメタノール、エタノール、イソプロピルアルコール、エチレングリコール系溶剤、プロピレングリコール系溶剤などの親水性溶剤で希釈して使用することができる。 In the composition of the present invention, if necessary, for example, etching agents such as silane coupling agents and inorganic phosphate compounds, heavy metal compounds other than the components defined by the present invention, thickeners, surfactants, dyes Etc. can be contained. Moreover, the composition of this invention can be diluted with hydrophilic solvents, such as methanol, ethanol, isopropyl alcohol, an ethylene glycol type solvent, a propylene glycol type solvent, for example as needed, and can be used.
（表面処理亜鉛めっき鋼板およびその製造方法）
本発明の表面処理亜鉛めっき鋼板の製造方法は、溶融亜鉛めっき鋼板または合金化溶融亜鉛めっき鋼板である亜鉛めっき鋼板の少なくとも片面に、これまで説明した組成物をスプレー塗布法にて塗布し、リンガーロールまたはエアーで塗布量を絞り、乾燥させることにより表面処理皮膜を形成することで得ることができる。こうして得た表面処理亜鉛めっき鋼板は、既述のとおり、皮膜に６価クロムを含まず、十分な耐食性および良好な皮膜外観（仕上がり状態）を呈する。
(Surface-treated galvanized steel sheet and manufacturing method thereof)
The method for producing a surface-treated galvanized steel sheet according to the present invention comprises applying the composition described so far to at least one surface of a galvanized steel sheet which is a hot dip galvanized steel sheet or an alloyed hot dip galvanized steel sheet by a spray coating method. It can be obtained by forming the surface treatment film by squeezing the coating amount with a roll or air and drying it. As described above, the surface-treated galvanized steel sheet thus obtained does not contain hexavalent chromium in the film, and exhibits sufficient corrosion resistance and good film appearance (finished state).
次に、本発明に適したスプレー塗布法の条件について説明する。スプレー塗布法では、鋼板の表面全面が液に接触するようなスプレー圧であれば問題なく、０．２ｋｇｆ／ｃｍ２以上とするのが好ましい。０．２ｋｇｆ／ｃｍ２以上であれば、液不足による外観不良が発生することがないと考えられるためである。スプレー塗布後はリンガーロールまたはエアーで液を絞る。リンガーロールの絞り圧またはエアーの圧力は、目標とする付着量が得られる範囲に調整すればよい。 Next, the conditions of the spray coating method suitable for the present invention will be described. In the spray coating method, there is no problem if the spray pressure is such that the entire surface of the steel sheet is in contact with the liquid, and it is preferably 0.2 kgf / cm 2 or more. This is because if it is 0.2 kgf / cm 2 or more, it is considered that an appearance defect due to insufficient liquid does not occur. After spraying, squeeze the liquid with a ringer roll or air. The squeezing pressure of the ringer roll or the air pressure may be adjusted within a range in which a target adhesion amount can be obtained.
本発明により形成される表面処理皮膜の片面当たりの付着量は、０．０５〜０．５ｇ／ｍ２が好ましい。皮膜付着量が０．０５ｇ／ｍ２以上であれば、耐食性をより確実に得ることができ、０．５ｇ／ｍ２以下であれば、皮膜が割れて耐食性が低下する可能性が低いからである。 The adhesion amount per one side of the surface treatment film formed according to the present invention is preferably 0.05 to 0.5 g / m 2 . By long film coating weight of 0.05 g / m 2 or more, the corrosion resistance can be obtained more reliably, if 0.5 g / m 2 or less, because there is less possibility that corrosion resistance decreases cracked film is there.
以下、実施例を用いて本発明をさらに詳細に説明するが、本発明は以下の実施例に何ら限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated further in detail using an Example, this invention is not limited to a following example at all.
（めっき鋼板）
表面処理鋼板のベース鋼板としては、表１に示すめっき鋼板を用いた。Ｎｏ．２，３が本発明例に用いる亜鉛めっき鋼板であり、残りは比較例に用いる亜鉛めっき鋼板である。
As the base steel plate of the surface-treated steel plate, the plated steel plate shown in Table 1 was used. No. Reference numerals 2 and 3 are galvanized steel sheets used in the examples of the present invention, and the rest are galvanized steel sheets used in the comparative examples.
（表面処理用組成物）
以下に、この実施例の組成物に用いた各成分（Ａ）〜（Ｆ），（Ｙ），（Ｚ）を示す。
［チタン含有水溶液（Ａ）の製造］
＜製造例１（チタン含有水性液Ｔ１）＞
四塩化チタン６０質量％溶液５ｃｃを蒸留水で５００ｃｃとした溶液にアンモニア水（１：９）を滴下し、水酸化チタンを沈殿させた。蒸留水で洗浄後、過酸化水素水３０質量％溶液を１０ｃｃ加えてかき混ぜ、チタンを含む黄色半透明の粘性のあるチタン含有水性液Ｔ１を得た。
＜製造例２（チタン含有水性液Ｔ２）＞
テトラｉｓｏ−プロポキシチタン１０部とｉｓｏ−プロパノール１０部の混合物を３０質量％過酸化水素水１０質量部と脱イオン水１００質量部の混合物中に２０℃で１時間かけて撹拌しながら滴下した。その後２５℃で２時間熟成し、黄色透明の少し粘性のあるチタン含有水性液Ｔ２を得た。
＜製造例３（チタン含有水性液Ｔ３）＞
製造例２で使用したテトラｉｓｏ−プロポキシチタンの代わりにテトラｎ−ブトキシチタンを使用した以外は製造例２と同様の製造条件で、チタン含有水性液Ｔ３を得た。
＜製造例４（チタン含有水性液Ｔ４）＞
製造例２で使用したテトラｉｓｏ−プロポキシチタンの代わりにテトラｉｓｏ−プロポキシチタンの３量体を使用した以外は製造例２と同様の製造条件で、チタン含有水性液Ｔ４を得た。
＜製造例５（チタン含有水性液Ｔ５）＞
製造例２に対して過酸化水素水を３倍量用い、５０℃で１時間かけて滴下し、さらに６０℃で３時間熟成した以外は製造例２と同様の製造条件で、チタン含有水性液Ｔ５を得た。
＜製造例６（チタン含有水性液Ｔ６）＞
製造例３で製造したチタン含有水性液Ｔ３を、さらに９５℃で６時間加熱処理することにより、白黄色の半透明なチタン含有水性液Ｔ６を得た。
＜製造例７（チタン含有水性液Ｔ７）＞
テトラｉｓｏ−プロポキシチタン１０質量部とｉｓｏ−プロパノール１０質量部の混合物を、「ＴＫＳ−２０３」（商品名，テイカ社製，酸化チタンゾル）５質量部（固形分）、３０質量％過酸化水素水１０質量部及び脱イオン水１００質量部の混合物中に１０℃で１時間かけて撹拌しながら滴下した。その後１０℃で２４時間熟成し、黄色透明の少し粘性のあるチタン含有水性液Ｔ７を得た。
(Surface treatment composition)
Below, each component (A)-(F), (Y), (Z) used for the composition of this Example is shown.
[Production of titanium-containing aqueous solution (A)]
<Production Example 1 (Titanium-containing aqueous liquid T1)>
Ammonia water (1: 9) was added dropwise to a solution in which 5 cc of a titanium tetrachloride 60 mass% solution was made 500 cc with distilled water to precipitate titanium hydroxide. After washing with distilled water, 10 cc of a 30% by mass hydrogen peroxide solution was added and stirred to obtain a yellow translucent viscous titanium-containing aqueous liquid T1 containing titanium.
<Production Example 2 (Titanium-containing aqueous liquid T2)>
A mixture of 10 parts of tetraiso-propoxytitanium and 10 parts of iso-propanol was dropped into a mixture of 10 parts by weight of 30% by weight hydrogen peroxide and 100 parts by weight of deionized water with stirring at 20 ° C. over 1 hour. Thereafter, aging was carried out at 25 ° C. for 2 hours to obtain a yellow transparent, slightly viscous titanium-containing aqueous liquid T2.
<Production Example 3 (Titanium-containing aqueous liquid T3)>
A titanium-containing aqueous liquid T3 was obtained under the same production conditions as in Production Example 2 except that tetra-n-butoxy titanium was used instead of tetraiso-propoxy titanium used in Production Example 2.
<Production Example 4 (Titanium-containing aqueous liquid T4)>
A titanium-containing aqueous liquid T4 was obtained under the same production conditions as in Production Example 2 except that tetramer of tetraiso-propoxytitanium used in Production Example 2 was used instead of tetraiso-propoxytitanium.
<Production Example 5 (Titanium-containing aqueous liquid T5)>
A titanium-containing aqueous liquid was produced under the same production conditions as in Production Example 2, except that hydrogen peroxide was used in 3 times the amount of Production Example 2, dropped at 50 ° C over 1 hour, and further aged at 60 ° C for 3 hours. T5 was obtained.
<Production Example 6 (Titanium-containing aqueous liquid T6)>
The titanium-containing aqueous liquid T3 produced in Production Example 3 was further heat-treated at 95 ° C. for 6 hours to obtain a white yellow translucent titanium-containing aqueous liquid T6.
<Production Example 7 (Titanium-containing aqueous liquid T7)>
A mixture of 10 parts by mass of tetraiso-propoxytitanium and 10 parts by mass of iso-propanol, 5 parts by mass (solid content) of “TKS-203” (trade name, manufactured by Teika Co., Ltd.), 30% by mass hydrogen peroxide solution The mixture was added dropwise to a mixture of 10 parts by mass and 100 parts by mass of deionized water with stirring at 10 ° C. over 1 hour. Thereafter, the mixture was aged at 10 ° C. for 24 hours to obtain a yellow transparent, slightly viscous titanium-containing aqueous liquid T7.
［ニッケル化合物（Ｂ）］
Ｂ１：酢酸ニッケル
Ｂ２：硝酸ニッケル
Ｂ３：硫酸ニッケル
[Nickel compound (B)]
B1: Nickel acetate B2: Nickel nitrate B3: Nickel sulfate
［弗素含有化合物（Ｃ）］
Ｃ１：ジルコン弗化アンモニウム
Ｃ２：ジルコン弗化水素酸
Ｃ３：ジルコン弗化ナトリウム
Ｃ４：ジルコン弗化カリウム
[Fluorine-containing compound (C)]
C1: Zircon ammonium fluoride C2: Zircon hydrofluoric acid C3: Zircon sodium fluoride C4: Zircon potassium fluoride
［有機リン酸化合物（Ｄ）］
Ｄ１：１−ヒドロキシエタン−１，１−ジホスホン酸
Ｄ２：１−ヒドロキシメタン−１，１−ジホスホン酸
[Organic Phosphate Compound (D)]
D1: 1-hydroxyethane-1,1-diphosphonic acid D2: 1-hydroxymethane-1,1-diphosphonic acid
［バナジン酸化合物（Ｅ）］
Ｅ１：メタバナジン酸アンモニウム
Ｅ２：メタバナジン酸ナトリウム
[Vanadate compound (E)]
E1: Ammonium metavanadate E2: Sodium metavanadate
［エーテル系有機溶剤（Ｆ）］
Ｆ１：エチレングリコールモノブチルエーテル（炭素数６）
Ｆ２：プロピレングリコールモノメチルエーテル（炭素数４）
Ｆ３：ジエチレングリコールモノエチルエーテル（炭素数６）
Ｆ４：エチレングリコールモノメチルエーテル（炭素数３）
Ｆ５：プロピレングリコールモノブチルエーテル（炭素数７）
[Ether-based organic solvent (F)]
F1: Ethylene glycol monobutyl ether (C6)
F2: Propylene glycol monomethyl ether (4 carbon atoms)
F3: Diethylene glycol monoethyl ether (carbon number 6)
F4: Ethylene glycol monomethyl ether (3 carbon atoms)
F5: Propylene glycol monobutyl ether (carbon number 7)
［炭酸ジルコニウム化合物（Ｙ）］
Ｙ１：炭酸ジルコニウムアンモニウム
Ｙ２：炭酸ジルコニウムナトリウム
[Zirconium carbonate compound (Y)]
Y1: Ammonium zirconium carbonate Y2: Sodium zirconium carbonate
［樹脂成分（Ｚ）］
Ｚ１：スーパーフレックスＥ−２５００（商品名，第一工業製薬（株）製，水性ポリウレタン樹脂，Ｔｇ：４２℃）
Ｚ２：バイロナールＭＤ−１１００（商品名，東洋紡績（株）製，水性ポリエステル樹脂）
Ｚ３：アデカレジンＥＭ−０７１８（商品名，（株）ＡＤＥＫＡ），水性エポキシ樹脂）
Ｚ４：ハイドランＡＰ−１０（商品名，大日本インキ化学工業（株）製，水性ポリウレタン樹脂，Ｔｇ：２７℃）
Ｚ５：ハイドランＡＰ−３０（商品名，大日本インキ化学工業（株）製，水性ポリウレタン樹脂，Ｔｇ：６１℃）
Ｚ６：ハイドランＨＷ−３４０（商品名，大日本インキ化学工業（株）製，水性ポリウレタン樹脂，Ｔｇ：７℃）
Ｚ７：ハイドランＨＷ−３５０（商品名，大日本インキ化学工業（株）製，水性ポリウレタン樹脂，Ｔｇ：５７℃）
Ｚ８：スーパーフレックス１１０（商品名，第一工業製薬（株）製，水性ポリウレタン樹脂，Ｔｇ：４６℃）
Ｚ９：スーパーフレックス１３０（商品名，第一工業製薬（株）製，水性ポリウレタン樹脂，Ｔｇ：９６℃）
Ｚ１０：スーパーフレックス６００（商品名，第一工業製薬（株）製，水性ポリウレタン樹脂，Ｔｇ：７０℃）
[Resin component (Z)]
Z1: Superflex E-2500 (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., aqueous polyurethane resin, Tg: 42 ° C.)
Z2: Bayronal MD-1100 (trade name, manufactured by Toyobo Co., Ltd., water-based polyester resin)
Z3: Adeka Resin EM-0718 (trade name, ADEKA Co., Ltd., aqueous epoxy resin)
Z4: Hydran AP-10 (trade name, manufactured by Dainippon Ink & Chemicals, water-based polyurethane resin, Tg: 27 ° C.)
Z5: Hydran AP-30 (trade name, manufactured by Dainippon Ink and Chemicals, water-based polyurethane resin, Tg: 61 ° C.)
Z6: Hydran HW-340 (trade name, manufactured by Dainippon Ink & Chemicals, water-based polyurethane resin, Tg: 7 ° C.)
Z7: Hydran HW-350 (trade name, manufactured by Dainippon Ink & Chemicals, water-based polyurethane resin, Tg: 57 ° C.)
Z8: Superflex 110 (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., water-based polyurethane resin, Tg: 46 ° C.)
Z9: Superflex 130 (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., water-based polyurethane resin, Tg: 96 ° C.)
Z10: Superflex 600 (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., water-based polyurethane resin, Tg: 70 ° C.)
これらの成分を所定量配合し、複数種の表面処理用組成物を作製した。各組成物の配合を表２に示す。なお、表２において、＊１〜＊１０は以下の内容を示す。
＊１ 明細書本文に記載のチタン含有水溶液Ｔ１〜Ｔ７
＊２ 明細書本文に記載のニッケル化合物Ｂ１〜Ｂ３
＊３ 明細書本文に記載の弗素含有化合物Ｃ１〜Ｃ４
＊４ 明細書本文に記載の有機リン酸化合物Ｄ１，Ｄ２
＊５ 明細書本文に記載のバナジン酸化合物Ｅ１，Ｅ２
＊６ 明細書本文に記載のエーテル系有機溶剤Ｆ１〜Ｆ５
＊７ 明細書本文に記載の炭酸ジルコニウム化合物Ｙ１，Ｙ２
＊８ 明細書本文に記載の樹脂成分Ｚ１〜Ｚ１０
＊９ 表面処理用組成物（水性処理液）中の固形分割合（質量％）
＊１０ 明細書本文に記載の成分（Ａ）〜（Ｅ）の合計１００質量部に対する配合割合(質量部)
A predetermined amount of these components was blended to prepare a plurality of types of surface treatment compositions. Table 2 shows the composition of each composition. In Table 2, * 1 to * 10 indicate the following contents.
* 1 Titanium-containing aqueous solution T1 to T7 described in the specification text
* 2 Nickel compounds B1 to B3 described in the specification text
* 3 Fluorine-containing compounds C1 to C4 described in the main text of the specification
* 4 Organophosphate compounds D1 and D2 described in the specification text
* 5 Vanadic acid compounds E1, E2 described in the main text of the specification
* 6 Ether-based organic solvents F1 to F5 described in the main text of the specification
* 7 Zirconium carbonate compounds Y1 and Y2 described in the specification text
* 8 Resin components Z1 to Z10 described in the main text of the specification
* 9 Solid content ratio (mass%) in the composition for surface treatment (aqueous treatment liquid)
* 10 Mixing ratio (mass part) with respect to 100 parts by mass in total of components (A) to (E) described in the specification text
（塗布方法）
表１に記載のいずれかのめっき鋼板の表面（片面）に、表２に記載の組成物を塗布し、３０〜１００℃で乾燥させ、供試材（表面処理めっき鋼板）とした。塗布は以下に示す方法で行い、片面当たりの皮膜付着量は０．２ｇ／ｍ２とした。
塗布方法１：組成物をスプレー圧１ｋｇｆ／ｃｍ２でスプレーして塗布した後に、リンガーロールで絞った後の液膜厚が２μｍとなるように余分な液を搾り取る。
塗布方法２：組成物をロールコーターにて塗布し、液膜厚が５μｍとなるように各ロール荷重を調整して組成物を鋼板側へ転写することにより行った。
(Application method)
The composition described in Table 2 was applied to the surface (one side) of any of the plated steel sheets described in Table 1 and dried at 30 to 100 ° C. to obtain test materials (surface-treated plated steel sheets). The coating was performed by the method shown below, and the coating amount per side was 0.2 g / m 2 .
Application method 1: After the composition is applied by spraying at a spray pressure of 1 kgf / cm 2 , excess liquid is squeezed out so that the liquid film thickness after squeezing with a Ringer roll is 2 μm.
Application method 2: The composition was applied by a roll coater, and each roll load was adjusted so that the liquid film thickness was 5 μm, and the composition was transferred to the steel sheet side.
（評価基準）
各供試材について、以下の試験方法により皮膜の仕上がり状態、耐食性を評価した。加えて、耐黒変性、耐水性、貯蔵安定性も評価した。その結果を、各供試材に適用した組成物の種類および塗布条件とともに表３および表４に示す。なお、表３および表４において、＊１１，＊１２は以下の内容を示す。
＊１１ 明細書本文に記載の塗布方法
＊１２ 表１に記載のめっき鋼板のＮｏ．１〜８
(Evaluation criteria)
About each test material, the finishing state of the film | membrane and corrosion resistance were evaluated with the following test methods. In addition, blackening resistance, water resistance, and storage stability were also evaluated. The results are shown in Tables 3 and 4 together with the type of composition applied to each test material and the application conditions. In Tables 3 and 4, * 11 and * 12 indicate the following contents.
* 11 Coating method described in the text of the specification * 12 No. of the coated steel sheet described in Table 1 1-8
（１）皮膜の仕上がり状態
皮膜の仕上がり状態は、以下の基準で判定した。
○（良好）：泡の乾き跡などの凹凸が目視で確認されず、指で擦ったときに皮膜の欠落が生じない平滑で均一な皮膜である。
△（やや不良）：凹凸が目視で確認されるか、指で擦ったときに皮膜の欠落が生じるかのいずれかである。
×（不良）：凹凸が目視で確認され、かつ、指で擦ったときに皮膜の欠落が生じる。
(1) Finished state of film The finished state of the film was determined according to the following criteria.
○ (good): Unevenness such as dry marks of bubbles is not visually confirmed, and the film is smooth and uniform with no film missing when rubbed with a finger.
Δ (slightly defective): Either unevenness is visually confirmed or the film is missing when rubbed with a finger.
X (defect): Concavities and convexities are confirmed visually, and a film is missing when rubbed with a finger.
（２）耐食性
端部と裏面をテープシールした供試材に対してＪＩＳ−Ｚ−２３７１−２０００に準拠した塩水噴霧試験を行い、白錆発生面積率が５％となる試験時間を測定した。その評価基準は以下のとおりである。
◎＋：９６時間以上
◎：７２時間以上、９６時間未満
○：４８時間以上、７２時間未満
△：２４時間以上、４８時間未満
×：２４時間未満
(2) Corrosion resistance A salt spray test based on JIS-Z-2371-2000 was performed on the specimens whose end portions and back surface were tape-sealed, and the test time at which the white rust generation area ratio was 5% was measured. The evaluation criteria are as follows.
◎ +: 96 hours or more ◎: 72 hours or more, less than 96 hours ○: 48 hours or more, less than 72 hours Δ: 24 hours or more, less than 48 hours ×: less than 24 hours
（３）耐黒変性
供試材を温度８０℃、相対湿度９５％に制御された恒温恒湿機に２４時間静置した際の白色度（Ｌ値）の変化をΔＬ（試験後のＬ値−試験前のＬ値）で算出した。その算出基準は以下の通りである。
○：ΔＬ≧−１０
△：−１０＞ΔＬ≧−１５
×：−１５＞ΔＬ
(3) Blackening resistance The change in whiteness (L value) when the test material was allowed to stand for 24 hours in a thermo-hygrostat controlled at a temperature of 80 ° C. and a relative humidity of 95% was ΔL (L value after the test). -L value before test). The calculation standard is as follows.
○: ΔL ≧ −10
Δ: −10> ΔL ≧ −15
×: −15> ΔL
（４）耐水性
供試材にイオン交換水１００μＬを滴下し、室温にて１５分間放置した後、１００℃に設定した炉にて滴下した水を乾燥し、試験前後での外観変化を目視観察して評価した。その評価基準は以下のとおりである。
○：変化なし
△：水滴のふち部分のみ色調変化
×：水滴の内側の色調変化
(4) Water resistance After adding 100 μL of ion-exchanged water to the test material and leaving it to stand at room temperature for 15 minutes, the water dropped in a furnace set at 100 ° C. is dried and the appearance change before and after the test is visually observed. And evaluated. The evaluation criteria are as follows.
○: No change △: Color tone change only at the edge of water drop ×: Color tone change inside water drop
（５）貯蔵安定性
濃度１２質量％に調整した組成物を４０℃の恒温槽内に３０日静置し、組成物の状態を目視で評価した。
○：組成物の状態の変化は見られない。
△：組成物の粘度上昇がみられる。
×：組成物が粘度上昇かつ組成物中にゲル状態の不溶物が生成するもの。
(5) Storage stability The composition adjusted to a concentration of 12% by mass was left in a constant temperature bath at 40 ° C. for 30 days, and the state of the composition was visually evaluated.
○: No change in the state of the composition is observed.
(Triangle | delta): The viscosity rise of a composition is seen.
X: The composition has a viscosity increase and a gel insoluble matter is generated in the composition.
表３および表４より以下のことがわかる。まず、比較例４０〜４４に示すとおり、炭酸ジルコニウム化合物を含む組成物を用いてスプレー塗布法で表面処理皮膜を形成した場合、合金化溶融亜鉛めっき鋼板の耐食性が劣る結果となった。 Table 3 and Table 4 show the following. First, as shown in Comparative Examples 40 to 44, when a surface treatment film was formed by spray coating using a composition containing a zirconium carbonate compound, the corrosion resistance of the galvannealed steel sheet was inferior.
次に、比較例１５〜２７に示すように、樹脂成分を含む組成物を用いてスプレー塗布法で表面処理皮膜を形成した場合、溶融亜鉛めっき鋼板の皮膜の仕上がり状態が悪くなるとともに、耐食性も十分ではなくなった。また、比較例４５に示すように、合金化溶融亜鉛めっき鋼板についても、皮膜の仕上がり状態が悪くなるとともに、耐食性も十分ではなくなった。 Next, as shown in Comparative Examples 15 to 27, when a surface treatment film is formed by a spray coating method using a composition containing a resin component, the finished state of the film of the hot dip galvanized steel sheet is deteriorated and the corrosion resistance is also improved. It was not enough. In addition, as shown in Comparative Example 45, the alloyed hot-dip galvanized steel sheet also had a poor coating finish and corrosion resistance was not sufficient.
さらに、比較例１〜１４，２８〜３９に示すように、組成物の成分（Ａ）〜（Ｆ）のいずれかが本発明で規定する含有量の範囲外となった場合、溶融亜鉛めっき鋼板または合金化溶融亜鉛めっき鋼板の皮膜の仕上がり、耐食性、耐黒変性、耐水性、貯蔵安定性の少なくとも１つが劣る結果となった。 Furthermore, as shown in Comparative Examples 1 to 14 and 28 to 39, when any one of the components (A) to (F) of the composition falls outside the content range defined in the present invention, the hot dip galvanized steel sheet Alternatively, at least one of the finish of the alloyed galvanized steel sheet, corrosion resistance, blackening resistance, water resistance, and storage stability was inferior.
また、比較例４６〜４８に示すとおり、炭素数が３以下または７以上であるエーテル系有機溶剤を用いると、溶融亜鉛めっき鋼板または合金化溶融亜鉛めっき鋼板の皮膜の仕上がり状態が悪くなり、さらに炭素数が７以上の場合、耐食性および耐水性も劣る結果となった。 Moreover, as shown in Comparative Examples 46 to 48, when an ether organic solvent having 3 or less carbon atoms or 7 or more carbon atoms is used, the finished state of the film of the hot dip galvanized steel sheet or the galvannealed steel sheet becomes worse. When the carbon number was 7 or more, the corrosion resistance and water resistance were inferior.
一方、発明例１〜６４に示すとおり、本発明の範囲内に含まれる組成物を用いてスプレー塗布法で表面処理皮膜を形成した場合、溶融亜鉛めっき鋼板および合金化溶融亜鉛めっき鋼板のどちらも、皮膜の仕上がり、耐食性、耐黒変性、耐水性、貯蔵安定性の全てが良好であった。特に耐食性に関しては、合金化溶融亜鉛めっき鋼板に塗布した場合に非常に良好であった。 On the other hand, as shown in Invention Examples 1 to 64, when the surface treatment film is formed by the spray coating method using the composition included in the scope of the present invention, both the hot-dip galvanized steel sheet and the alloyed hot-dip galvanized steel sheet are used. The film finish, corrosion resistance, blackening resistance, water resistance, and storage stability were all good. In particular, the corrosion resistance was very good when applied to galvannealed steel sheets.
また、発明例１〜１９，２２〜５１，５４〜６４と、発明例２０，２１，５２，５３とを比較すると、弗素含有化合物（Ｃ）が、ジルコン弗化アンモニウム、ジルコン弗化水素酸から１種または２種を含む場合、耐食性が特に良好となることも分かった。 Further, when Invention Examples 1 to 19, 22 to 51, 54 to 64 are compared with Invention Examples 20, 21, 52 and 53, the fluorine-containing compound (C) is obtained from zircon ammonium fluoride and zircon hydrofluoric acid. It has also been found that the corrosion resistance is particularly good when one or two are included.
なお、比較例５７，５８に参考に示すように、溶融亜鉛めっき鋼板にロールコート法で塗布した場合には、組成物の成分（Ａ）または（Ｃ）が本発明の範囲に含まれなくても耐食性が劣ることはなかった。さらに、比較例５９，６０に参考に示すように、ロールコート法で塗布した場合には、組成物に樹脂が含まれていても、皮膜の仕上がりが劣ることはなかった。また、比較例６１に参考に示すように、合金化溶融亜鉛めっき鋼板にロールコート法で塗布した場合には、組成物中にグリコールエーテル系有機溶剤の少なくとも１種を含有していなくても、皮膜仕上がりが低下することはなく、皮膜の耐食性も良好であった。このことから、耐食性または皮膜仕上がりが劣るという問題は、スプレー塗布法にて塗布する場合に特有のものであることがわかった。 In addition, as shown in Comparative Examples 57 and 58 for reference, when applied to a hot-dip galvanized steel sheet by a roll coating method, the component (A) or (C) of the composition is not included in the scope of the present invention. However, the corrosion resistance was not inferior. Furthermore, as shown in Comparative Examples 59 and 60 for reference, when applied by the roll coating method, the finish of the film was not inferior even if the composition contained a resin. In addition, as shown in Reference in Comparative Example 61, when applied to the alloyed hot-dip galvanized steel sheet by a roll coating method, even if the composition does not contain at least one glycol ether organic solvent, The film finish did not decrease and the corrosion resistance of the film was good. From this, it was found that the problem that the corrosion resistance or the film finish is inferior is peculiar to the case of applying by the spray coating method.
また、比較例４９〜５４に示すとおり、溶融亜鉛めっき鋼板または合金化溶融亜鉛めっき鋼板以外の亜鉛めっき鋼板に、本発明で規定する成分組成を満たす組成物をスプレー塗布法で塗布しても、十分な耐食性を得ることができなかった。よって、本発明は、これらの組成物により溶融亜鉛めっき鋼板または合金化溶融亜鉛めっき鋼板に対して表面処理皮膜を形成した場合に特有のものであることがわかった。 Moreover, as shown in Comparative Examples 49 to 54, even when a composition satisfying the component composition defined in the present invention is applied to a galvanized steel sheet other than the hot dip galvanized steel sheet or the galvannealed steel sheet by a spray coating method, Sufficient corrosion resistance could not be obtained. Therefore, it turned out that this invention is peculiar when forming a surface treatment film | membrane with respect to a hot-dip galvanized steel plate or an alloyed hot-dip galvanized steel plate with these compositions.
なお、比較例５５，５６に参考に示すとおり、溶融亜鉛めっき鋼板または合金化溶融亜鉛めっき鋼板に何ら塗装しない場合、耐食性、耐黒変性、耐水性のいずれも不十分である。 In addition, as shown in Comparative Examples 55 and 56 for reference, when nothing is applied to a hot-dip galvanized steel sheet or an alloyed hot-dip galvanized steel sheet, all of corrosion resistance, blackening resistance, and water resistance are insufficient.
本発明によれば、溶融亜鉛めっき鋼板または合金化溶融亜鉛めっき鋼板の表面にスプレー塗布法で塗布して表面処理皮膜を形成する場合に十分な耐食性および良好な皮膜外観（仕上がり状態）を呈することが可能な、６価クロムを全く含まない環境適用型の表面処理用組成物を提供することができた。 According to the present invention, sufficient corrosion resistance and good coating appearance (finished state) are exhibited when a surface-treated coating is formed on a surface of a hot dip galvanized steel plate or an alloyed hot dip galvanized steel plate by a spray coating method. It was possible to provide an environmentally applicable surface treatment composition containing no hexavalent chromium.
Claims (3)
炭素数４から６のエーテル系有機溶剤（Ｆ）を、前記（Ａ）、（Ｂ）、（Ｃ）、（Ｄ）および（Ｅ）の合計１００質量部に対する割合で５〜３０質量部含有し、
樹脂成分および炭酸ジルコニウム化合物を含まない組成物であって、
前記弗素含有化合物（Ｃ）は、ジルコン弗化アンモニウム、ジルコン弗化水素酸、ジルコン弗化ナトリウム、ジルコン弗化カリウムの中から選ばれる１種または２種以上であり、
溶融亜鉛めっき鋼板または合金化溶融亜鉛めっき鋼板である亜鉛めっき鋼板の少なくとも片面にスプレー塗布法にて塗布して表面処理皮膜を形成するために用いることを特徴とするスプレー塗布表面処理用組成物。 Titanium obtained by mixing at least one titanium compound selected from hydrolyzable titanium compounds, low-condensates of hydrolyzable titanium compounds, titanium hydroxide, and low-condensates of titanium hydroxide with hydrogen peroxide water 10 to 45% by mass of the aqueous solution (A) in solid content, 0.01 to 1% by mass of the nickel compound (B) in solid content, and the solid content of the fluorine-containing compound (C). 10 to 20% by mass, 40 to 60% by mass of the organic phosphoric acid compound (D) in the proportion of solids, and 0.1 to 30% by mass of the vanadic acid compound (E) in the proportion of solids, Contains,
5-30 mass parts of C4-C6 ether organic solvent (F) is contained in the ratio with respect to a total of 100 mass parts of said (A), (B), (C), (D) and (E). ,
A composition containing no resin component and zirconium carbonate compound,
The fluorine-containing compound (C) is one or more selected from zircon ammonium fluoride, zircon hydrofluoric acid, sodium zircon fluoride, and potassium zircon fluoride,
A composition for spray coating surface treatment, which is used for forming a surface treatment film by applying at least one surface of a galvanized steel plate which is a hot dip galvanized steel plate or an alloyed hot dip galvanized steel plate by a spray coating method.
The spray coating surface treatment composition according to claim 1 or 2 is applied to at least one surface of a galvanized steel sheet or a galvanized steel sheet that is a galvannealed steel sheet or an alloyed hot dip galvanized steel sheet using a ringer roll or air. A method for producing a surface-treated galvanized steel sheet, characterized in that a surface-treated film is formed by reducing the amount applied and drying.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012255599A JP6092591B2 (en) | 2012-11-21 | 2012-11-21 | Spray-coated surface treatment composition, method for producing surface-treated galvanized steel sheet, and surface-treated galvanized steel sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012255599A JP6092591B2 (en) | 2012-11-21 | 2012-11-21 | Spray-coated surface treatment composition, method for producing surface-treated galvanized steel sheet, and surface-treated galvanized steel sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2014101562A JP2014101562A (en) | 2014-06-05 |
| JP6092591B2 true JP6092591B2 (en) | 2017-03-08 |
Family
ID=51024324
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2012255599A Active JP6092591B2 (en) | 2012-11-21 | 2012-11-21 | Spray-coated surface treatment composition, method for producing surface-treated galvanized steel sheet, and surface-treated galvanized steel sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6092591B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| MY186811A (en) | 2016-10-11 | 2021-08-23 | Jfe Steel Corp | Surface-treatment solution for zinc or zinc alloy coated steel sheet, method of producing zinc or zinc alloy coated steel sheet with surface-coating layer, and zinc or zinc alloy coated steel sheet with surface-coating layer |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5410244A (en) * | 1977-06-27 | 1979-01-25 | Kansai Paint Co Ltd | Metal surface treating solution |
| JP5097311B2 (en) * | 2007-02-26 | 2012-12-12 | Ｊｆｅスチール株式会社 | Surface-treated steel sheet and organic resin-coated steel sheet |
| JP2008274419A (en) * | 2007-03-30 | 2008-11-13 | Jfe Steel Kk | Surface treated steel sheet having excellent corrosion resistance, electrodeposition coating adhesion and weldability |
| JP5317516B2 (en) * | 2007-04-27 | 2013-10-16 | Ｊｆｅスチール株式会社 | Surface-treated molten Zn-Al alloy-plated steel sheet |
| JP5101271B2 (en) * | 2007-12-28 | 2012-12-19 | Ｊｆｅスチール株式会社 | Surface-treated steel sheet |
| JP2010156020A (en) * | 2008-12-27 | 2010-07-15 | Jfe Steel Corp | Surface-treated steel plate |
-
2012
- 2012-11-21 JP JP2012255599A patent/JP6092591B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2014101562A (en) | 2014-06-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5555179B2 (en) | Surface treatment agent for galvanized steel sheet, surface treatment method for galvanized steel sheet, and galvanized steel sheet | |
| JP4972240B2 (en) | Surface-treated steel sheet | |
| JP5446057B2 (en) | Zinc-based galvanized steel sheet for chemical conversion treatment, method for producing the same, and chemical conversion treated steel sheet | |
| JP4575047B2 (en) | Metal surface treatment composition and metal surface treatment steel plate | |
| JP2792324B2 (en) | Multi-layer galvanized steel sheet | |
| JP5431721B2 (en) | Surface treatment composition for zinc-based plated steel sheet or aluminum-based plated steel sheet and surface-treated steel sheet | |
| JP2008231418A (en) | Coating material for forming titanium-zirconium film, method for forming titanium-zirconium film, metal substrate coated with titanium-zirconium film | |
| JP2004238638A (en) | Surface treatment composition and surface-treated metal strip | |
| JP5317516B2 (en) | Surface-treated molten Zn-Al alloy-plated steel sheet | |
| JP2010156020A (en) | Surface-treated steel plate | |
| JP5577782B2 (en) | Surface-treated steel sheet | |
| JP3952198B2 (en) | Metal surface treatment method and galvanized steel sheet | |
| JP2013060646A (en) | Composition for spray coating surface treatment, method for producing surface-treated hot-dip galvanized steel sheet, and the surface-treated hot-dip galvanized steel sheet | |
| JP5447218B2 (en) | Surface-treated plated steel sheet and surface treatment liquid | |
| JP2009287078A (en) | Highly corrosion resistant surface-treated steel sheet | |
| JP5097311B2 (en) | Surface-treated steel sheet and organic resin-coated steel sheet | |
| JP6092591B2 (en) | Spray-coated surface treatment composition, method for producing surface-treated galvanized steel sheet, and surface-treated galvanized steel sheet | |
| JP5222491B2 (en) | Surface-treated steel sheet | |
| JP2003193088A (en) | Surface-finishing composition for metallic material | |
| JP4916913B2 (en) | Surface-treated steel sheet and organic resin-coated steel sheet | |
| JP2003193255A (en) | Surface treatment composition for metallic material | |
| JP2003213457A (en) | Fuel tank made of resin coated metal | |
| JP2004052056A (en) | Surface treatment method of zinc or zinc alloy plated material | |
| JP5101271B2 (en) | Surface-treated steel sheet | |
| JP2003213456A (en) | Resin-coated metallic tube material and production method therefor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20150723 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20160413 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20160419 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20160614 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20161129 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20170120 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20170207 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20170209 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6092591 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |