JP5235397B2 - 被覆鋼板 - Google Patents
被覆鋼板 Download PDFInfo
- Publication number
- JP5235397B2 JP5235397B2 JP2007323776A JP2007323776A JP5235397B2 JP 5235397 B2 JP5235397 B2 JP 5235397B2 JP 2007323776 A JP2007323776 A JP 2007323776A JP 2007323776 A JP2007323776 A JP 2007323776A JP 5235397 B2 JP5235397 B2 JP 5235397B2
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- JP
- Japan
- Prior art keywords
- steel sheet
- mass
- particles
- compound
- film
- 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.)
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- 229910000831 Steel Inorganic materials 0.000 title claims description 59
- 239000010959 steel Substances 0.000 title claims description 59
- 239000002245 particle Substances 0.000 claims description 134
- 229920005989 resin Polymers 0.000 claims description 60
- 239000011347 resin Substances 0.000 claims description 60
- 239000011248 coating agent Substances 0.000 claims description 57
- 238000000576 coating method Methods 0.000 claims description 49
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 36
- 239000002131 composite material Substances 0.000 claims description 29
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 26
- -1 phosphate compound Chemical class 0.000 claims description 25
- 229910000484 niobium oxide Inorganic materials 0.000 claims description 22
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 22
- 150000001875 compounds Chemical class 0.000 claims description 20
- 229920005749 polyurethane resin Polymers 0.000 claims description 18
- 210000004243 sweat Anatomy 0.000 claims description 17
- 150000003609 titanium compounds Chemical class 0.000 claims description 17
- 239000000805 composite resin Substances 0.000 claims description 14
- 229920006026 co-polymeric resin Polymers 0.000 claims description 13
- ZRALSGWEFCBTJO-UHFFFAOYSA-N anhydrous guanidine Natural products NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims description 11
- 150000003564 thiocarbonyl compounds Chemical class 0.000 claims description 11
- 150000003682 vanadium compounds Chemical class 0.000 claims description 11
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims description 10
- 125000005372 silanol group Chemical group 0.000 claims description 10
- 229920005648 ethylene methacrylic acid copolymer Polymers 0.000 claims description 9
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- 229920000515 polycarbonate Polymers 0.000 claims description 7
- 239000004417 polycarbonate Substances 0.000 claims description 7
- 125000005370 alkoxysilyl group Chemical group 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- 150000001735 carboxylic acids Chemical class 0.000 claims description 5
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 239000003112 inhibitor Substances 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 238000013329 compounding Methods 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 239000011856 silicon-based particle Substances 0.000 claims 1
- 238000012360 testing method Methods 0.000 description 24
- 238000005260 corrosion Methods 0.000 description 23
- 230000007797 corrosion Effects 0.000 description 23
- 238000000034 method Methods 0.000 description 22
- 239000002904 solvent Substances 0.000 description 22
- 239000006185 dispersion Substances 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 239000003513 alkali Substances 0.000 description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- 238000005299 abrasion Methods 0.000 description 14
- 229920000098 polyolefin Polymers 0.000 description 14
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 13
- 239000001993 wax Substances 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 12
- 238000007747 plating Methods 0.000 description 12
- 239000003973 paint Substances 0.000 description 11
- 230000003068 static effect Effects 0.000 description 11
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 9
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 229910052719 titanium Inorganic materials 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 7
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 7
- 230000007423 decrease Effects 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 235000011007 phosphoric acid Nutrition 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 229910001335 Galvanized steel Inorganic materials 0.000 description 6
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000008397 galvanized steel Substances 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- 125000003700 epoxy group Chemical group 0.000 description 5
- 230000003472 neutralizing effect Effects 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 229920005862 polyol Polymers 0.000 description 5
- 150000003077 polyols Chemical class 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 238000002296 dynamic light scattering Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- 230000002265 prevention Effects 0.000 description 4
- 125000002813 thiocarbonyl group Chemical group *C(*)=S 0.000 description 4
- 125000003944 tolyl group Chemical group 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000010954 inorganic particle Substances 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 229920000768 polyamine Polymers 0.000 description 3
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 2
- ZOTKGMAKADCEDH-UHFFFAOYSA-N 5-triethoxysilylpentane-1,3-diamine Chemical compound CCO[Si](OCC)(OCC)CCC(N)CCN ZOTKGMAKADCEDH-UHFFFAOYSA-N 0.000 description 2
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical class C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229920000298 Cellophane Polymers 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910008051 Si-OH Inorganic materials 0.000 description 2
- 229910006358 Si—OH Inorganic materials 0.000 description 2
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 2
- 125000005595 acetylacetonate group Chemical group 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 229920000180 alkyd Polymers 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001845 chromium compounds Chemical class 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000008119 colloidal silica Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229960002887 deanol Drugs 0.000 description 2
- 238000005237 degreasing agent Methods 0.000 description 2
- 239000013527 degreasing agent Substances 0.000 description 2
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 2
- 239000012972 dimethylethanolamine Substances 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- SUMDYPCJJOFFON-UHFFFAOYSA-N isethionic acid Chemical compound OCCS(O)(=O)=O SUMDYPCJJOFFON-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 150000003016 phosphoric acids Chemical class 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- MFWFDRBPQDXFRC-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;vanadium Chemical compound [V].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MFWFDRBPQDXFRC-LNTINUHCSA-N 0.000 description 1
- JAEZSIYNWDWMMN-UHFFFAOYSA-N 1,1,3-trimethylthiourea Chemical compound CNC(=S)N(C)C JAEZSIYNWDWMMN-UHFFFAOYSA-N 0.000 description 1
- OPNUROKCUBTKLF-UHFFFAOYSA-N 1,2-bis(2-methylphenyl)guanidine Chemical compound CC1=CC=CC=C1N\C(N)=N\C1=CC=CC=C1C OPNUROKCUBTKLF-UHFFFAOYSA-N 0.000 description 1
- BPXVHIRIPLPOPT-UHFFFAOYSA-N 1,3,5-tris(2-hydroxyethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound OCCN1C(=O)N(CCO)C(=O)N(CCO)C1=O BPXVHIRIPLPOPT-UHFFFAOYSA-N 0.000 description 1
- XSCLFFBWRKTMTE-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)cyclohexane Chemical compound O=C=NCC1CCCC(CN=C=O)C1 XSCLFFBWRKTMTE-UHFFFAOYSA-N 0.000 description 1
- NVHNGVXBCWYLFA-UHFFFAOYSA-N 1,3-diazinane-2-thione Chemical compound S=C1NCCCN1 NVHNGVXBCWYLFA-UHFFFAOYSA-N 0.000 description 1
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 description 1
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 1
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- SQZCAOHYQSOZCE-UHFFFAOYSA-N 1-(diaminomethylidene)-2-(2-methylphenyl)guanidine Chemical compound CC1=CC=CC=C1N=C(N)N=C(N)N SQZCAOHYQSOZCE-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 description 1
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- MBNRBJNIYVXSQV-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propane-1-thiol Chemical compound CCO[Si](C)(OCC)CCCS MBNRBJNIYVXSQV-UHFFFAOYSA-N 0.000 description 1
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 description 1
- IKYAJDOSWUATPI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propane-1-thiol Chemical compound CO[Si](C)(OC)CCCS IKYAJDOSWUATPI-UHFFFAOYSA-N 0.000 description 1
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- GHBRMZFUMLMOKO-UHFFFAOYSA-N 5-[diethoxy(methyl)silyl]pentane-1,3-diamine Chemical compound CCO[Si](C)(OCC)CCC(N)CCN GHBRMZFUMLMOKO-UHFFFAOYSA-N 0.000 description 1
- KHLRJDNGHBXOSV-UHFFFAOYSA-N 5-trimethoxysilylpentane-1,3-diamine Chemical compound CO[Si](OC)(OC)CCC(N)CCN KHLRJDNGHBXOSV-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
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- 239000005977 Ethylene Substances 0.000 description 1
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
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- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
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- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
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- 150000002334 glycols Chemical class 0.000 description 1
- VPVSTMAPERLKKM-UHFFFAOYSA-N glycoluril Chemical compound N1C(=O)NC2NC(=O)NC21 VPVSTMAPERLKKM-UHFFFAOYSA-N 0.000 description 1
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- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- GKQPCPXONLDCMU-CCEZHUSRSA-N lacidipine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C1=CC=CC=C1\C=C\C(=O)OC(C)(C)C GKQPCPXONLDCMU-CCEZHUSRSA-N 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
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- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 1
- WPCMRGJTLPITMF-UHFFFAOYSA-I niobium(5+);pentahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[Nb+5] WPCMRGJTLPITMF-UHFFFAOYSA-I 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- DPTATFGPDCLUTF-UHFFFAOYSA-N phosphanylidyneiron Chemical compound [Fe]#P DPTATFGPDCLUTF-UHFFFAOYSA-N 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
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- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- JCBJVAJGLKENNC-UHFFFAOYSA-M potassium ethyl xanthate Chemical compound [K+].CCOC([S-])=S JCBJVAJGLKENNC-UHFFFAOYSA-M 0.000 description 1
- BQFYGYJPBUKISI-UHFFFAOYSA-N potassium;oxido(dioxo)vanadium Chemical compound [K+].[O-][V](=O)=O BQFYGYJPBUKISI-UHFFFAOYSA-N 0.000 description 1
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- 238000012545 processing Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
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- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
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Description
しかし、今までのものではその発現レベルが十分とはいえないものであった。そこで、本発明は、耐汗性を上記性質を担保しながら更に付与することを目的とするものである。
めっき鋼板上に複合皮膜を被覆した被覆鋼板であって、それぞれ平均粒子径が20〜100nmであり、シラノール基及び/又はアルコキシシリル基を有する、ポリウレタン樹脂粒子(A−1)及びエチレン−不飽和カルボン酸共重合樹脂粒子(A−2)の両方、あるいは前記(A−2)単独から選択される樹脂を含み、更に酸化ケイ素粒子(A−3)と有機チタン化合物(A−4)を含む複合化樹脂(A)、及びバナジウム化合物(B)が複合化した皮膜で、皮膜量が0.5〜3g/m2であることを特徴とする耐汗性用に優れた被覆鋼板である。
即ち、本発明は、基本的に、上記(A−1)、(A−2)の両方を含み、あるいは(A−2)単独から選択される樹脂を含み、更に(A−3)、(A−4)を含み、それらが複合化してなる複合樹脂(A)からなる皮膜を有するものであるため、耐テープ剥離性、耐溶剤性、耐アルカリ性に優れたものである。
上記樹脂粒子(A−1)としては、平均粒子径が20〜100nmであり、シラノール基及び/又はアルコキシシリル基を有するポリウレタン樹脂であれば特に限定されないが、ポリカーボネート系ポリウレタンが好ましい。上記ポリカーボネート系ポリウレタン樹脂粒子は、イソシアネート基含有化合物とポリカーボネートポリオール、低分子量ポリオール、及び活性水素基と親水性基を含有する化合物とを反応させてポリウレタンプレポリマーを製造し、次いで上記親水性基を中和剤により中和したのち、この中和プレポリマーを、活性水素基を含有するアルコキシシラン類及びポリアミンを含んだ水中に分散させ、鎖延長させることにより得ることができる。
ス粒子(C)を含有するものである。ただし、ポリオレフィンワックス粒子(C)は、上
記複合皮膜の動摩擦係数を低下させ、表面の潤滑性を高めるが、皮膜の硬度低下や静摩擦
係数の低下も招くため、ポリオレフィンワックス粒子(C)だけでは、満足できる性能は
得られない。そのため、本発明の好ましい態様においては、更に、ポリオレフィンワック
ス粒子(C)に加えて、平均粒子径が50〜200nmである酸化ケイ素粒子(D)を組
み合わせて使用する。
即ち、上記複合化樹脂(A)の一部を構成する酸化ケイ素粒子(A−3)とは別に、粒
子径が大きい酸化ケイ素粒子(D)を有するものである。
製造例1
反応容器に4,4’−メチレンビス(シクロヘキシルイソシアネート)、分子量2000のポリカーボネートジオール、ネオペンチルグリコール、ジメチロールプロピオン酸、及び溶剤としてN−メチルピロリドンを仕込み、80℃において6時間撹拌後、ジメチルエタノールアミンで中和してポリウレタンプレポリマー溶液を得た。次に、ヒドラジン及びγ−(2−アミノエチル)アミノプロピルトリエトキシシランを含有する水中に、上記反応により得られたポリウレタンプレポリマー溶液をホモディスパーを用いて分散させることにより、シラノール基及び/又はエトキシシリル基を含有するポリウレタン樹脂粒子の水分散液を得た。固形分濃度は30質量%、動的光散乱法によって測定した平均粒子径は39nmであった。
上記製造例1と同様にして得られたポリウレタンプレポリマーを、ホモディスパーを用いて、ヒドラジン水溶液中に分散させることによりポリウレタン樹脂粒子の水分散液を得た。固形分濃度は30質量%、平均粒子径は36nmであった。
製造例3
反応容器にエチレン−メタクリル酸共重合樹脂(メタクリル酸の含有量が20質量%)、樹脂に対して5.6質量%相当の水酸化ナトリウム及び脱イオン水を加え、95℃で6時間攪拌することにより固形分20%の水分散樹脂液を得た。この水分散樹脂液に対して、さらにγ−グリシドキシプロピルトリメトキシシランを0.8質量%、グリセロールポリグリシジルエーテルを0.8質量%を加えて、85℃で2時間反応させることによって、シラノール基及び/又はメトキシシリル基を有するエチレン−メタクリル酸共重合樹脂粒子の水分散液を得た。固形分濃度は21質量%、平均粒子径は76nmであった。
反応容器にエチレン−メタクリル酸共重合樹脂(メタクリル酸の含有量が20質量%)、樹脂に対して3.7質量%の水酸化ナトリウム、6.3質量%のアンモニア水(25質量%)、及び脱イオン水を加え、95℃で6時間攪拌することにより固形分20%の水分散樹脂液を得た。この水分散樹脂液に対して、さらにγ−グリシドキシプロピルトリエトキシシランを1.2質量%、ペンタエリスリトールポリグリシジルエーテルを0.6質量%を加えて、85℃で2時間反応させることによって、シラノール基及び/又はメトキシシリル基を有するエチレン−メタクリル酸共重合樹脂粒子の水分散液を得た。固形分濃度は21質量%、平均粒子径は84nmであった。
反応容器にエチレン−メタクリル酸共重合樹脂(メタクリル酸の含有量が20質量%)、樹脂に対して4.7質量%相当の水酸化ナトリウム及び脱イオン水を加え、95℃で2時間攪拌することにより固形分20%の水分散樹脂液を得た。この水分散樹脂液に対して、さらにγ−グリシドキシプロピルトリメトキシシランを1.2質量%、水添ビスフェノールAジグリシジルエーテルを1.2質量%加えて、85℃で2時間反応させることによって、シラノール基及び/又はメトキシシリル基を有するエチレン−メタクリル酸共重合樹脂粒子の水分散液を得た。固形分濃度は21%、平均粒子径は145nmであった。
試験板の作成
厚さ0.8mmの電気亜鉛めっき鋼板(亜鉛付着量:20g/m2)及び溶融亜鉛めっき鋼板(亜鉛付着量:60g/m2)を60℃のアルカリ脱脂剤(サーフクリーナー155、日本ペイント社製)2%水溶液を用いて30秒間スプレー処理して脱脂した。次に、上記製造例で得られた樹脂粒子及び表1〜6に示した物質を表7,8に示した処方で水性被覆剤を調製し、これをバーコーターで、乾燥皮膜量1g/m2になるように塗布し、雰囲気温度500℃の熱風乾燥炉を用いて到達板温150℃まで焼き付けて試験板を作成した。
基材密着性、耐テープ剥離性、塗装密着性、加工部耐食性、耐溶剤性(エタノール、メチルエチルケトン、ホワイトガソリンの3種)、耐アルカリ性、動摩擦係数、静摩擦係数、耐アブレージョン性、及び耐汗性を評価した。評価は下記の方法で行った。
試験板をエリクセンテスターにて8mm押し出し加工したのち、押し出し部にセロハンテープ(ニチバン社製)を貼り、強制剥離した。試験板をメチルバイオレット染色液に浸漬し、皮膜状態を観察し下記基準で評価した。
○:剥離なし
△:剥離面積10%未満
×:剥離面積10%以上
試験板にフィラメンテープ(スリオンテック社製)を貼り、40℃、湿度80%の条件で1週間放置したのち、テープを強制剥離した。皮膜状態を観察し下記基準で評価した。
○:剥離ほとんどなし
△:剥離面積50%未満
×:剥離面積50%以上
試験板表面にメラミンアルキッド塗料(スーパーラック100、日本ペイント社製)をバーコーターで乾燥膜厚20μmとなるように塗布し、120℃で25分間焼き付けて塗板を作製した。一昼夜放置後沸騰水中に30分間浸漬し、取り出して1日放置してから、1mm間隔の碁盤目カット疵を100個入れ、その部分にセロハンテープ(ニチバン製)を貼り、強制剥離した後の皮膜状態を観察し下記基準で評価した。
○:剥離個数0
△:剥離個数49以下
×:剥離個数50以上
試験板をエリクセンテスターにて7mm押し出した加工し、試験板のエッジと裏面をテープシールし、塩水噴霧試験SST(JIS−Z−2371)を行った。120時間後の白錆発生状況を観察し下記基準で評価した。
○:白錆ほとんどなし
△:白錆面積30%未満
×:白錆面積30%以上
試験板をラビングテスターに設置後、エタノール又はホワイトガソリンを含浸させた脱脂綿を0.5kgf/cm2の荷重で5回(往復)擦った後、試験板のエッジと裏面をテープシールし、塩水噴霧試験(JIS−Z−2371)を行った。72時間後の白錆発生状況を観察し下記基準で評価した。
○:白錆ほとんどなし
△:白錆面積30%未満
×:白錆面積30%以上
試験板を55℃のアルカリ脱脂剤(サーフクリーナー53、日本ペイント社製)2%水溶液(pH12.5)に攪拌しながら2分間浸漬した後、試験板のエッジと裏面をテープシールし、塩水噴霧試験(JIS−Z−2371)を行った。72時間後の白錆発生状況を観察し下記基準で評価した。
○:白錆ほとんどなし
△:白錆面積30%未満
×:白錆面積30%以上
試験板をHEIDON動摩擦係数測定装置にかけ、10mmφステンレス球摺動、荷重100g、摺動速度150mm/minn条件で動摩擦係数を測定した。
HEIDON静摩擦係数測定装置を用いて、0.5°/sec、平面圧子にバリを取り除いた面積25cm2の試験板を貼り付けて、重さ200gの条件で試験板同士の静摩擦係数を測定した。
試験板に、段ボール紙を介して10g/cm2の荷重をかけ、360回/minの楕円運動を加えて摺動部にアブレージョン(摩耗傷)を発生させた。10分間試験を行った後の試験板表面の状態を観察し下記基準で評価した。
○:黒化ほとんどなし
△:摺動部の50%未満の面積が黒化
×:摺動部の50%以上の面積が黒化
試験板に、人工汗液(JIS−L−0848 D法)を、1滴滴下後、65℃93%RHに48時間静置し下記基準で評価した。
<評価基準>
◎=外観変化なし
○=外観変化ほとんどなし
△=滴下部の30%未満の面積が変化
×=滴下部の30%以上の面積が変化
上記試験によって評価及び測定を行った結果を下記表7,8に示す。
Claims (5)
- めっき鋼板上に複合皮膜を被覆した被覆鋼板であって、
前記複合皮膜は、
それぞれ、平均粒子径が20〜100nmであり、シラノール基及び/又はアルコキシシリル基を有する、ポリウレタン樹脂粒子(A−1)及びエチレン−不飽和カルボン酸共重合樹脂粒子(A−2)の両方、あるいは前記(A−2)単独から選択される樹脂を含み、更に酸化ケイ素粒子(A−3)と有機チタン化合物(A−4)を含む複合化樹脂(A)、
及びバナジウム化合物(B)
が複合化した皮膜で、皮膜量が0.5〜3g/m2であることを特徴とする耐汗性に優れた被覆鋼板。 - 前記複合化樹脂(A)は、
ポリウレタン樹脂粒子(A−1)及びエチレン−不飽和カルボン酸共重合樹脂粒子(A−2)を質量比20:80〜90:10の割合で含み、更に平均粒子径が5〜50nmである酸化ケイ素粒子(A−3)と有機チタン化合物(A−4)を含み、
それらが複合化した複合化樹脂である請求項1記載の被覆鋼板。 - 前記酸化ケイ素粒子(A−3)が、前記ポリウレタン樹脂粒子(A−1)及び前記エチレン−不飽和カルボン酸共重合樹脂粒子(A−2)の合計量に対して5〜100質量%であり、チタン原子の含有率が皮膜全量に対して0.05〜3質量%である請求項1または2に記載の被覆鋼板。
- 前記複合皮膜は、
更に、リン酸化合物、チオカルボニル化合物、酸化ニオブ、及びグアニジン化合物からなる群から選択される少なくとも1種の防錆剤(E)
が複合化した化合物からなる皮膜である請求項1〜3のいずれかに記載の被覆鋼板。 - 前記ポリウレタン樹脂粒子(A−1)は、
ポリカーボネート基を有するものであり、エチレン−不飽和カルボン酸共重合樹脂粒子(A−2)はエチレン−メタクリル酸共重合樹脂のアルカリ金属、アンモニア及び/又はアミンによる中和物からの誘導体である請求項1〜4のいずれかに記載の被覆鋼板。
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