JP4629987B2 - シーリング剤、リン酸塩処理鋼板の被覆方法及びリン酸塩処理鋼板 - Google Patents
シーリング剤、リン酸塩処理鋼板の被覆方法及びリン酸塩処理鋼板 Download PDFInfo
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- JP4629987B2 JP4629987B2 JP2004081331A JP2004081331A JP4629987B2 JP 4629987 B2 JP4629987 B2 JP 4629987B2 JP 2004081331 A JP2004081331 A JP 2004081331A JP 2004081331 A JP2004081331 A JP 2004081331A JP 4629987 B2 JP4629987 B2 JP 4629987B2
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- Prior art keywords
- sealing agent
- group
- mass
- steel sheet
- phosphate
- 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.)
- Expired - Lifetime
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- 238000007789 sealing Methods 0.000 title claims description 70
- 229910000831 Steel Inorganic materials 0.000 title claims description 65
- 239000010959 steel Substances 0.000 title claims description 65
- 239000003795 chemical substances by application Substances 0.000 title claims description 60
- 238000000576 coating method Methods 0.000 title claims description 49
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 68
- 229910019142 PO4 Inorganic materials 0.000 claims description 58
- -1 guanidine compound Chemical class 0.000 claims description 58
- 239000010452 phosphate Substances 0.000 claims description 58
- 239000011248 coating agent Substances 0.000 claims description 43
- ZRALSGWEFCBTJO-UHFFFAOYSA-N anhydrous guanidine Natural products NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims description 38
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims description 32
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims description 32
- 229920005989 resin Polymers 0.000 claims description 29
- 239000011347 resin Substances 0.000 claims description 29
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- 150000003839 salts Chemical class 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- ZILVNHNSYBNLSZ-UHFFFAOYSA-N 2-(diaminomethylideneamino)guanidine Chemical compound NC(N)=NNC(N)=N ZILVNHNSYBNLSZ-UHFFFAOYSA-N 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 14
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- 229910044991 metal oxide Inorganic materials 0.000 claims description 8
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- 125000003944 tolyl group Chemical group 0.000 claims description 8
- 125000003277 amino group Chemical group 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
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- 229920000642 polymer Polymers 0.000 claims description 6
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims description 5
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- 239000001257 hydrogen Substances 0.000 claims description 5
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- 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 claims description 4
- 125000000068 chlorophenyl group Chemical group 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 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 claims description 3
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 claims description 3
- HAMNKKUPIHEESI-UHFFFAOYSA-N aminoguanidine Chemical compound NNC(N)=N HAMNKKUPIHEESI-UHFFFAOYSA-N 0.000 claims description 3
- OKGXJRGLYVRVNE-UHFFFAOYSA-N diaminomethylidenethiourea Chemical compound NC(N)=NC(N)=S OKGXJRGLYVRVNE-UHFFFAOYSA-N 0.000 claims description 3
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- 239000007864 aqueous solution Substances 0.000 description 11
- 239000008397 galvanized steel Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 9
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 8
- 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 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
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- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 4
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- PEZSZSUYWAPYPQ-UHFFFAOYSA-K [NH4+].C(C(O)C)(=O)[O-].C(C(O)C)(=O)[O-].O[Zr+]O Chemical compound [NH4+].C(C(O)C)(=O)[O-].C(C(O)C)(=O)[O-].O[Zr+]O PEZSZSUYWAPYPQ-UHFFFAOYSA-K 0.000 description 1
- IFTLYVOSXXNBGD-UHFFFAOYSA-L [NH4+].[NH4+].O[Ti]O.CC(O)C([O-])=O.CC(O)C([O-])=O Chemical compound [NH4+].[NH4+].O[Ti]O.CC(O)C([O-])=O.CC(O)C([O-])=O IFTLYVOSXXNBGD-UHFFFAOYSA-L 0.000 description 1
- VIKACKSJNYKRGG-UHFFFAOYSA-L [NH4+].[NH4+].O[Zr]O.CC(O)C([O-])=O.CC(O)C([O-])=O Chemical compound [NH4+].[NH4+].O[Zr]O.CC(O)C([O-])=O.CC(O)C([O-])=O VIKACKSJNYKRGG-UHFFFAOYSA-L 0.000 description 1
- DOEDEOQXJFKNFA-UHFFFAOYSA-M [Zr]O Chemical compound [Zr]O DOEDEOQXJFKNFA-UHFFFAOYSA-M 0.000 description 1
- YDHWWBZFRZWVHO-UHFFFAOYSA-N [hydroxy(phosphonooxy)phosphoryl] phosphono hydrogen phosphate Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(=O)OP(O)(O)=O YDHWWBZFRZWVHO-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- PXAJQJMDEXJWFB-UHFFFAOYSA-N acetone oxime Chemical compound CC(C)=NO PXAJQJMDEXJWFB-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- XPNGNIFUDRPBFJ-UHFFFAOYSA-N alpha-methylbenzylalcohol Natural products CC1=CC=CC=C1CO XPNGNIFUDRPBFJ-UHFFFAOYSA-N 0.000 description 1
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 229940059265 ammonium lactate Drugs 0.000 description 1
- 235000019286 ammonium lactate Nutrition 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 229940010556 ammonium phosphate Drugs 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- RZOBLYBZQXQGFY-HSHFZTNMSA-N azanium;(2r)-2-hydroxypropanoate Chemical compound [NH4+].C[C@@H](O)C([O-])=O RZOBLYBZQXQGFY-HSHFZTNMSA-N 0.000 description 1
- AJGPQPPJQDDCDA-UHFFFAOYSA-N azanium;hydron;oxalate Chemical compound N.OC(=O)C(O)=O AJGPQPPJQDDCDA-UHFFFAOYSA-N 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- ADRVNXBAWSRFAJ-UHFFFAOYSA-N catechin Natural products OC1Cc2cc(O)cc(O)c2OC1c3ccc(O)c(O)c3 ADRVNXBAWSRFAJ-UHFFFAOYSA-N 0.000 description 1
- 235000005487 catechin Nutrition 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- DQIPXGFHRRCVHY-UHFFFAOYSA-N chromium zinc Chemical compound [Cr].[Zn] DQIPXGFHRRCVHY-UHFFFAOYSA-N 0.000 description 1
- 229950001002 cianidanol Drugs 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000005237 degreasing agent Methods 0.000 description 1
- 239000013527 degreasing agent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000004663 dialkyl amino group Chemical group 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- NMGYKLMMQCTUGI-UHFFFAOYSA-J diazanium;titanium(4+);hexafluoride Chemical compound [NH4+].[NH4+].[F-].[F-].[F-].[F-].[F-].[F-].[Ti+4] NMGYKLMMQCTUGI-UHFFFAOYSA-J 0.000 description 1
- 229940116349 dibasic ammonium phosphate Drugs 0.000 description 1
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 description 1
- VKNUORWMCINMRB-UHFFFAOYSA-N diethyl malate Chemical compound CCOC(=O)CC(O)C(=O)OCC VKNUORWMCINMRB-UHFFFAOYSA-N 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical compound C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- 229940005667 ethyl salicylate Drugs 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229940074391 gallic acid Drugs 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 150000002483 hydrogen compounds Chemical class 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229960000448 lactic acid Drugs 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229940099690 malic acid Drugs 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 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
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229940057867 methyl lactate Drugs 0.000 description 1
- 229960001047 methyl salicylate Drugs 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- ICRFXIKCXYDMJD-UHFFFAOYSA-N n'-benzyl-n'-ethenyl-n-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN(C=C)CC1=CC=CC=C1 ICRFXIKCXYDMJD-UHFFFAOYSA-N 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 1
- NGTGENGUUCHSLQ-UHFFFAOYSA-N n-heptan-2-ylidenehydroxylamine Chemical compound CCCCCC(C)=NO NGTGENGUUCHSLQ-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229910000159 nickel phosphate Inorganic materials 0.000 description 1
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 1
- JOCJYBPHESYFOK-UHFFFAOYSA-K nickel(3+);phosphate Chemical compound [Ni+3].[O-]P([O-])([O-])=O JOCJYBPHESYFOK-UHFFFAOYSA-K 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- 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 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 235000020636 oyster Nutrition 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 238000007591 painting process Methods 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229960000969 phenyl salicylate Drugs 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- JTQPTNQXCUMDRK-UHFFFAOYSA-N propan-2-olate;titanium(2+) Chemical compound CC(C)O[Ti]OC(C)C JTQPTNQXCUMDRK-UHFFFAOYSA-N 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- DXIGZHYPWYIZLM-UHFFFAOYSA-J tetrafluorozirconium;dihydrofluoride Chemical compound F.F.F[Zr](F)(F)F DXIGZHYPWYIZLM-UHFFFAOYSA-J 0.000 description 1
- YJVLWFXZVBOFRZ-UHFFFAOYSA-N titanium zinc Chemical compound [Ti].[Zn] YJVLWFXZVBOFRZ-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium(II) oxide Chemical compound [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 1
- 229940048102 triphosphoric acid Drugs 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- 229940077935 zinc phosphate Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/20—Use of solutions containing silanes
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Laminated Bodies (AREA)
- Sealing Material Composition (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
- Chemical Treatment Of Metals (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Description
上記シーリング剤は、更に、リン酸イオンを0.01〜30質量%含有することが好ましい。
上記シーリング剤は、更に、Ti、Zr、Al及びVからなる群より選択される少なくとも一種の元素を有する金属錯体を0.01〜30質量%含有することが好ましい。
上記シーリング剤は、更に、フィチン酸及び/又はポリフェノール化合物を0.01〜30質量%含有することが好ましい。
上記シーリング剤は、更に、Si、Al、Ti、Zr及びNbからなる群より選択される少なくとも一種の金属元素からなる金属酸化物粒子を0.01〜30質量%含有することが好ましい。
上記水性樹脂は、水性エポキシ樹脂及び/又は水性フェノール樹脂であることが好ましい。
上記グアニジン化合物は、下記一般式(1)
上記グアニジン化合物は、グアニジン、アミノグアニジン、グアニルチオ尿素、1,3−ジフェニルグアニジン、1,3−ジ−o−トリルグアニジン、1−o−トリルビグアニド、ポリヘキサメチレンビグアニジン、ポリヘキサエチレンビグアニジン、ポリペンタメチレンビグアニジン、ポリペンタエチレンビグアニジン、ポリビニルビグアニジン、ポリアリルビグアニジン、クロルヘキシルジン及びこれらの塩からなる群より選択される少なくとも一種であることが好ましい。
本発明は、上記リン酸塩処理鋼板の被覆方法により得られるものであることを特徴とするリン酸塩処理鋼板でもある。
本発明のシーリング剤は、リン酸塩皮膜を有するリン酸塩処理鋼板に塗布するものであって、クロムを使用することなく、リン酸塩皮膜上に良好な塗装密着性、未塗装耐食性、塗装後耐食性を有するシーリング皮膜を形成するものである。
上記グアニジン化合物としては、上記一般式(1)で表わされるグアニジン化合物を使用することが好ましい。
上記水性エポキシ樹脂及び/又は水性フェノール樹脂にアミノ基を導入する方法としては特に限定されず、例えば、溶媒中で上記樹脂とアミン化合物とを混合する方法等の通常の方法を挙げることができる。
また、本発明により得られたリン酸塩処理鋼板は、上述の性能に優れるため、建材、家電、自動車分野等に好適に用いることができる。
なお、実施例1〜18、20〜31、33、35、37〜68、70〜81、83、85、87〜90は、本明細書においては参考例となる。
攪拌機、温度調節器、滴下漏斗、及び、冷却器を備えたコルベンに、エポキシ当量190のビスフェノールFエピクロルヒドリン型エポキシ樹脂190質量部にジエタノールアミン30部、プロピレングリコールモノメチルエーテルアセテート110部を加え、100℃で2時間反応させ、不揮発分70%の変性エポキシ樹脂を得た。攪拌機、温度調節器、滴下漏斗、及び、冷却器を備えたコルベンに、NCOが13.3%、不揮発分75%のトリメチロールプロパンの2,4−トルエンジイソシアネートプレポリマーを100部、ノニルフェノール44部、ジメチルベンジルアミン5部、プロピレングリコールモノメチルエーテルアセテート65部を混合し、窒素雰囲気下80℃で3時間、反応させ、不揮発分70%、NCO%が20%のハーフブロック化ポリイソシアネートを得た。上記変性エポキシ樹脂70部と上記ハーフブロック化ポリイソシアネート30部を混合し、80℃で4時間攪拌して反応させた後、赤外線分光分析でNCO基の吸収が完全になくなることを確認した。その後、酢酸3部を混合し、さらにイオン交換水で希釈して不揮発分25%、pH4.1である水性エポキシ樹脂を得た。
攪拌機、温度調節器、滴下漏斗、及び、冷却器を備えたコルベンに、m−クレゾール108g、m−キシレングリコールジメチルエーテル5g、p−トルエンスルホン酸0.3gを仕込み、160℃で2時間反応させた。内温を100℃まで下げ、37%ホルムアルデヒド水溶液61gを1時間かけて添加し、100℃で2時間還流反応を行い、140℃まで常圧脱水反応を行った。次いで、真空脱水を行い、系内の温度が160℃まで昇温したところで重縮合反応を終了とした。次いで120℃まで温度を下げ、ブチルセルソルブ194gを添加し、重縮合物を完全に溶解させ、純水194gを100℃以下で添加し、系内の温度が50℃まで下がったところで、N−メチルアミノエタノール1モル75gを添加し、37%ヒルムアルデヒド水溶液81.1gを1時間かけて逐次添加し、50℃で1時間反応させ、更に90℃で1.5時間反応させ、不揮発分31%の変性フェノール樹脂を得た。上記変性フェノール樹脂100部に75%オルトリン酸23部を混合し、さらにイオン交換水で希釈して不揮発分25%、pH4.0である水性フェノール樹脂を得た。
シーリング剤の調製
上記製造例1によって得られた水性エポキシ樹脂を固形分として7.5g採取し、ポリヘキサメチレンビグアニジンリン酸塩を0.1g、γ−グリシドキシプロピルトリメトキシシランを2.5g、タンニン酸を0.5g配合し、イオン交換水を加えて、固形分10%である実施例1のシーリング剤を調製した。
試験板作成
70mm×150mm×0.8mmの電気亜鉛めっき鋼板(めっき付着量:20g/m2、新日本製鐵製)を55℃のアルカリ脱脂剤(サーフクリーナー53、日本ペイント製)2%水溶液を用いて、60℃で1分間スプレー処理して脱脂、水洗した後、表面調整剤(サーフファイン5N−5、日本ペイント社製)による表面調整処理を行い、続けて、リン酸亜鉛処理液(サーフダインZS9100、日本ペイント社製)をスプレーにより塗布し、水洗、乾燥することによりリン酸塩処理亜鉛めっき鋼板を形成した。次に、作製したリン酸塩処理亜鉛めっき鋼板に上記シーリング剤をバーコーターで、所定の付着量になるように塗布し、20秒で鋼板到達温度が120℃になるように焼き付けて試験板を作製した。
素材として使用した亜鉛めっき鋼板の種類、めっき付着量、リン酸塩皮膜の付着量(処理温度、処理時間を変化させることで調整)、シーリング剤種類(水性樹脂、グアニジン化合物、シランカップリング剤、リン酸イオン、金属錯体、ポリフェノール化合物、金属酸化物粒子の種類と濃度を調整)を表3〜13に記載したように変えたこと以外は、実施例1と同様にして、試験板を作成した。なお、亜鉛めっき鋼板の種類は表1に、シーリング剤に使用した水性樹脂の種類を表2に示した。
未塗装耐食性、塗装密着性、塗装後耐食性を評価した。その結果を表3〜13に記載する。評価は下記の方法にしたがって行った。
<未塗装耐食性>
試験板の平板の端面部及び裏面部をテープでシールし、JIS Z 2371に基づく塩水噴霧試験を24時間施した後の白錆発生面積率を下記の評価基準で評価した。
◎:白錆発生なし
○:白錆発生面積が10%未満
△:同10%以上30%未満
×:同30%以上
試験板を脱脂処理(サーフクリーナー53、日本ペイント製、2%水溶液、60℃、1分間スプレー)した後、水洗、乾燥し、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分間焼き付けて塗装板を作製した。その後、塗装板に1mm間隔の碁盤目を100個刻み、この部分にセロテープ(ニチバン製)を貼り、強制剥離した後の塗膜状態を下記の評価基準で評価した。
◎:剥離なし
○:カット部に沿って塗膜が少量剥離
△:碁盤目の1マス以上の塗膜が剥離
×:碁盤目内の塗膜が全面剥離
試験板を脱脂処理(サーフクリーナー53、日本ペイント製、2%水溶液、60℃、1分間スプレー)した後、水洗、乾燥し、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分間焼き付けて塗装板を作製した。その後、塗装板を沸騰水中に30分間浸漬し、24時間放置後、塗装板に1mm間隔の碁盤目を100個刻み、この部分にセロテープ(ニチバン製)を貼り、強制剥離した後の塗膜状態を下記の評価基準で評価した。
◎:剥離なし
○:カット部に沿って塗膜が少量剥離
△:碁盤目の1マス以上の塗膜が剥離
×:碁盤目内の塗膜が全面剥離
試験板を脱脂処理(サーフクリーナー53、日本ペイント製、2%水溶液、60℃、1分間スプレー)した後、水洗、乾燥し、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分間焼き付けて塗装板を作製した。この塗装板上の塗膜を貫通して素地面に達する×状の切り傷をカッターナイフで付けた後、端面部及び裏面部をテープでシールし、JIS Z 2371に基づく塩水噴霧試験を240時間施した。この試験板の切り傷部にセロテープ(ニチバン製)を貼り、強制剥離した後の塗膜状態を下記の評価基準で評価した。
◎:切り傷部の片幅最大剥離幅5mm未満
○:切り傷部の片幅最大剥離幅5mm以上8mm未満
△:切り傷部の片幅最大剥離幅8mm以上10mm未満
×:切り傷部の片幅最大剥離幅10mm以上
Claims (9)
- リン酸塩処理鋼板に塗布するシーリング剤であって、
シーリング剤中の濃度として、
水性樹脂を1〜50質量%、グアニジン化合物を0.01〜30質量%及びシランカップリング剤を1〜50質量%含有し、更に、金属元素がNbである金属酸化物粒子を0.01〜30質量%含有することを特徴とするシーリング剤。 - 更に、リン酸イオンを0.01〜30質量%含有する請求項1記載のシーリング剤。
- シーリング剤中の濃度として、更に、Ti、Zr、Al及びVからなる群より選択される少なくとも一種の元素を有する金属錯体を0.01〜30質量%含有する請求項1又は2記載のシーリング剤。
- シーリング剤中の濃度として、更に、フィチン酸及び/又はポリフェノール化合物を0.01〜30質量%含有する請求項1、2又は3記載のシーリング剤。
- 水性樹脂は、水性エポキシ樹脂及び/又は水性フェノール樹脂である請求項1、2、3又は4記載のシーリング剤。
- グアニジン化合物は、下記一般式(1)
で表わされ、質量平均分子量が59〜1000000である化合物及び/又はその塩である請求項1、2、3、4又は5記載のシーリング剤。 - グアニジン化合物は、グアニジン、アミノグアニジン、グアニルチオ尿素、1,3−ジフェニルグアニジン、1,3−ジ−o−トリルグアニジン、1−o−トリルビグアニド、ポリヘキサメチレンビグアニジン、ポリヘキサエチレンビグアニジン、ポリペンタメチレンビグアニジン、ポリペンタエチレンビグアニジン、ポリビニルビグアニジン、ポリアリルビグアニジン、クロルヘキシルジン及びこれらの塩からなる群より選択される少なくとも一種である請求項1、2、3、4、5又は6記載のシーリング剤。
- シーリング剤をリン酸塩処理鋼板に塗布してシーリング皮膜を形成するリン酸塩処理鋼板の被覆方法であって、
前記シーリング剤は、請求項1、2、3、4、5、6又は7記載のシーリング剤からなることを特徴とするリン酸塩処理鋼板の被覆方法。 - 請求項8記載のリン酸塩処理鋼板の被覆方法により得られるものであることを特徴とするリン酸塩処理鋼板。
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