JPH0348271B2 - - Google Patents
Info
- Publication number
- JPH0348271B2 JPH0348271B2 JP2435785A JP2435785A JPH0348271B2 JP H0348271 B2 JPH0348271 B2 JP H0348271B2 JP 2435785 A JP2435785 A JP 2435785A JP 2435785 A JP2435785 A JP 2435785A JP H0348271 B2 JPH0348271 B2 JP H0348271B2
- Authority
- JP
- Japan
- Prior art keywords
- film
- chromium
- hydrophilicity
- ion exchange
- aluminum
- 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
Links
- 239000000463 material Substances 0.000 claims description 37
- 229910052782 aluminium Inorganic materials 0.000 claims description 33
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 33
- 239000003795 chemical substances by application Substances 0.000 claims description 29
- 238000005260 corrosion Methods 0.000 claims description 25
- 230000007797 corrosion Effects 0.000 claims description 25
- 239000003456 ion exchange resin Substances 0.000 claims description 20
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 20
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 15
- 150000001845 chromium compounds Chemical class 0.000 claims description 15
- 229920002125 Sokalan® Polymers 0.000 claims description 12
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 12
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 10
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 229940125904 compound 1 Drugs 0.000 claims 1
- 239000011347 resin Substances 0.000 description 18
- 229920005989 resin Polymers 0.000 description 18
- 238000000034 method Methods 0.000 description 16
- 239000011651 chromium Substances 0.000 description 9
- 238000011282 treatment Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 7
- 229910052804 chromium Inorganic materials 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000003729 cation exchange resin Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- 229940023913 cation exchange resins Drugs 0.000 description 4
- 229940117975 chromium trioxide Drugs 0.000 description 4
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- -1 etc.) Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000003957 anion exchange resin Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910001430 chromium ion Inorganic materials 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000010828 elution Methods 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 229960002050 hydrofluoric acid Drugs 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 239000004584 polyacrylic acid Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 description 2
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 description 2
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 description 1
- WVAFEFUPWRPQSY-UHFFFAOYSA-N 1,2,3-tris(ethenyl)benzene Chemical compound C=CC1=CC=CC(C=C)=C1C=C WVAFEFUPWRPQSY-UHFFFAOYSA-N 0.000 description 1
- SQKIRAVCIRJCFS-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.C=CC1=CC=CC=C1C=C SQKIRAVCIRJCFS-UHFFFAOYSA-N 0.000 description 1
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 description 1
- QLOKJRIVRGCVIM-UHFFFAOYSA-N 1-[(4-methylsulfanylphenyl)methyl]piperazine Chemical compound C1=CC(SC)=CC=C1CN1CCNCC1 QLOKJRIVRGCVIM-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- JHWIEAWILPSRMU-UHFFFAOYSA-N 2-methyl-3-pyrimidin-4-ylpropanoic acid Chemical compound OC(=O)C(C)CC1=CC=NC=N1 JHWIEAWILPSRMU-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- PMJNEQWWZRSFCE-UHFFFAOYSA-N 3-ethoxy-3-oxo-2-(thiophen-2-ylmethyl)propanoic acid Chemical compound CCOC(=O)C(C(O)=O)CC1=CC=CS1 PMJNEQWWZRSFCE-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NCNKLTFZTZEYLK-AHUNZLEGSA-H [Cr+3].[Cr+3].[O-]C(=O)\C=C/C([O-])=O.[O-]C(=O)\C=C/C([O-])=O.[O-]C(=O)\C=C/C([O-])=O Chemical compound [Cr+3].[Cr+3].[O-]C(=O)\C=C/C([O-])=O.[O-]C(=O)\C=C/C([O-])=O.[O-]C(=O)\C=C/C([O-])=O NCNKLTFZTZEYLK-AHUNZLEGSA-H 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- JOSWYUNQBRPBDN-UHFFFAOYSA-P ammonium dichromate Chemical compound [NH4+].[NH4+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O JOSWYUNQBRPBDN-UHFFFAOYSA-P 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 238000012093 association test Methods 0.000 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910021563 chromium fluoride Inorganic materials 0.000 description 1
- 229910000151 chromium(III) phosphate Inorganic materials 0.000 description 1
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 description 1
- IKZBVTPSNGOVRJ-UHFFFAOYSA-K chromium(iii) phosphate Chemical compound [Cr+3].[O-]P([O-])([O-])=O IKZBVTPSNGOVRJ-UHFFFAOYSA-K 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- JQVALDCWTQRVQE-UHFFFAOYSA-N dilithium;dioxido(dioxo)chromium Chemical compound [Li+].[Li+].[O-][Cr]([O-])(=O)=O JQVALDCWTQRVQE-UHFFFAOYSA-N 0.000 description 1
- GLGSRACCZFMWDT-UHFFFAOYSA-N dilithium;oxido-(oxido(dioxo)chromio)oxy-dioxochromium Chemical compound [Li+].[Li+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O GLGSRACCZFMWDT-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000010409 ironing Methods 0.000 description 1
- 238000011866 long-term treatment Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pentâ4âenâ2âone Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229940044654 phenolsulfonic acid Drugs 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical group O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 150000003141 primary amines Chemical group 0.000 description 1
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 230000009291 secondary effect Effects 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- PXLIDIMHPNPGMH-UHFFFAOYSA-N sodium chromate Chemical compound [Na+].[Na+].[O-][Cr]([O-])(=O)=O PXLIDIMHPNPGMH-UHFFFAOYSA-N 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical group 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- XROWMBWRMNHXMF-UHFFFAOYSA-J titanium tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[Ti+4] XROWMBWRMNHXMF-UHFFFAOYSA-J 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- FTBATIJJKIIOTP-UHFFFAOYSA-K trifluorochromium Chemical compound F[Cr](F)F FTBATIJJKIIOTP-UHFFFAOYSA-K 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- OMQSJNWFFJOIMO-UHFFFAOYSA-J zirconium tetrafluoride Chemical compound F[Zr](F)(F)F OMQSJNWFFJOIMO-UHFFFAOYSA-J 0.000 description 1
- 239000004711 α-olefin Substances 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
- C23C22/37—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also hexavalent chromium compounds
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
Description
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ãè¡šã[Detailed Description of the Invention] [Industrial Application Field] The present invention provides a method for forming a film with excellent hydrophilicity, corrosion resistance, and plastic workability on the surface of aluminum and aluminum-containing materials (hereinafter simply referred to as "aluminum materials"). The present invention relates to a hydrophilic corrosion-resistant film-forming agent. [Conventional technology and problems] Aluminum materials are widely used for various purposes, but
Depending on the application, it is desired that the surface be so-called hydrophilic, meaning that it can be easily wetted by water. That is,
For example, in the case of heat exchangers, as performance increases and miniaturization progresses, attempts are being made to improve heat transfer performance by narrowing the fin spacing. However, in a heat exchanger, heat is exchanged with the atmosphere on the fin surface, and moisture in the atmosphere condenses on the fin surface. However, if the fin spacing is narrowed to, for example, 3 to 4 mm or less, Condensed water forms so-called bridges between the fins, which increases ventilation resistance and causes noise generation and a reduction in energy consumption efficiency. Therefore, attempts have been made to impart hydrophilicity to the fin surface to prevent the formation of bridges. In addition to heat exchangers, it is also used when you want to prevent dew condensation on the surface of aluminum materials in a humid atmosphere, when you want to prevent fogging on the surface of aluminum materials that require gloss, or when you want to increase the wettability of water and remove water from the surface of aluminum materials. In cases where it is desired to increase the amount of evaporation of aluminum, a hydrophilic film is formed on the surface of the aluminum material. As a means of imparting hydrophilicity, methods are taken depending on the aluminum material used, but a method of applying a treatment agent that imparts hydrophilicity is known. Additives such as silica powder and surfactants are known, but it is necessary to add a large amount of silica powder, which reduces the density of the inorganic film and reduces the corrosion resistance of the film. If the concentration of hexavalent chromium ions is increased to compensate, 6
Problems such as chromium ion leaching, dies wearing out when performing die molding after film formation, or surfactants leaching over time and deteriorating hydrophilicity. or,
If the hydrophilicity is increased, there are problems such as lowering the corrosion resistance of the aluminum material depending on the usage environment and deterioration of the hydrophilicity over time. )
is desired. [Means and effects for solving the problem] The present inventors have conducted repeated research in order to obtain a film-forming agent that can form a film that not only provides good hydrophilicity and corrosion resistance but also has excellent plastic workability. As a result, we have discovered that the object can be achieved by appropriately blending a chromium compound, fluoride, ion exchange resin, and acrylic acid polymer, and have accomplished the present invention. That is, in the present invention, a hexavalent chromium compound is added in an amount of 0.05 to 2 g/3 in terms of CrO 3 in an aqueous solution.
1 to 18 g of chromium compounds in terms of CrO3 ,
This is a hydrophilic corrosion-resistant film-forming agent for aluminum materials, which contains 0.1 to 5 g of fluoride as F - , 1 to 100 g of ion exchange resin powder as solid content, and 1 to 20 g of acrylic acid polymer as solid content. Examples of the aluminum material in the present invention include:
Examples include formed materials such as plates and extruded materials made of aluminum and its alloys, aluminum-coated steel materials (plated materials, clad materials, etc.), and products with specific shapes and assemblies such as heat exchangers. . Examples of the source of the trivalent chromium compound constituting the film forming agent of the present invention include chromium hydroxide,
Inorganic acid salts such as chromium nitrate, chromium fluoride, chromium phosphate, chromium sulfate, organic acid salts such as chromium acetate, chromium maleate, etc. can generally be used as a source of hexavalent chromium compounds. is a chromate, such as chromium trioxide, ammonium chromate, potassium chromate, sodium chromate, lithium chromate, or ammonium dichromate, potassium dichromate, sodium dichromate, lithium dichromate. Dichromates such as dichromates may be commonly used. In addition to adding trivalent chromium in the form of a compound as described above, a hexavalent chromium compound such as chromium trioxide is used, and a portion of this is added in formalin, formalin, etc.
It is also possible to mix trivalent compounds by reducing them with an organic reducing agent such as phenol or polyhydric alcohol, and compared to the case of mixing trivalent chromium compounds and hexavalent compounds, trivalent chromium It is preferable to use it on the low concentration side. Therefore, the hexavalent chromium compound in the film forming agent is added in the range of 0.05 to 2 g/in terms of CrO3 , and if the amount added is less than 0.05 g/,
The corrosion resistance effect was not sufficient, and the crosslinking reaction of the acrylic acid polymer was not carried out to a sufficiently satisfactory extent.
In this case, hexavalent chromium is likely to be eluted from the film, causing a pollution problem, and as a result, the corrosion resistance of the film is reduced. The trivalent chromium compound is used to compensate for the decrease in the effectiveness of chromium due to the restriction on the amount of hexavalent chromium compound used, and is added in a range of 1 to 18 g/in terms of CrO3 . The purpose of the project cannot be fully achieved. It should be noted that if the total amount of chromium exceeds 20 g/min, the surface of the aluminum material will be colored, the chromium will be locally concentrated, the film will become non-uniform, and it is also economically disadvantageous. Thus, the chromium compound acts on the surface of the aluminum material in cooperation with the fluoride to form an inorganic layer with high corrosion resistance, and also crosslinks the acrylic acid polymer to make it insolubilized. Next, examples of fluorides include fluoric acid,
Silicon fluoride, boron fluoride, titanium fluoride, zirconium fluoride, zinc fluoride, etc. are mentioned, and such soluble fluoride is expressed as fluorine ion (F - ) in an amount of 0.1 to 5 g/, preferably 0.7
Add in a range of ~3.5g/. If F - is less than 0.1g/, good corrosion resistance of the inorganic layer, which is mainly composed of reaction products between aluminum material and chromium compound, cannot be obtained, and if it is more than 5g/, the elution of aluminum material becomes noticeable and the film becomes dense. The film-forming agent bath is difficult to control. Thus, the fluoride acts cooperatively with the chromium compound to form an inorganic layer with corrosion resistance and good plastic workability on the aluminum surface. Next, ion exchange resins include compounds that have hydrophilic atomic groups and can act as water-insoluble surfactants, and are commercially available as ion exchange resin particles and ion exchange resin membranes. It can be appropriately selected from resins, and has a total ion exchange capacity of 0.5 [mg equivalent/g-DryR] or more, more preferably 1 [mg equivalent/g-Dry-R].
The above are appropriate. That is, for example,
Condensation type ion exchange resins include phenolsulfonic acid type, ethyleneimine-epichlorohydrin type, epoxy type, etc. Polymerized type ion exchange resins include styrene-divinylbenzene type, vinyl-divinylbenzene type, methacrylic acid-divinylbenzene type. Cation exchange resins are available with hydrophilic groups such as sulfonic acid groups, phosphonic acid groups, phosphinic acid groups, quaternary ammonium, or primary or tertiary amines. Alternatively, it is commercially available as an anion exchange resin, and an appropriate one can be selected from these and used. In addition, amphoteric ion exchange resins such as strongly basic anion exchange resins polymerized with acrylic acid, or fluorine resins into which hydrophilic atomic groups are introduced are also commercially available, and any of these can be used. Among these ion exchange resins, cation exchange resins are preferred because they have excellent hydrophilicity, and sulfonic acid type strongly acidic cation exchange resins are most suitable. In addition, the ion exchange resin is not limited to one type, but can be used in appropriate proportions depending on the desired degree of hydrophilicity, such as strong acidic and weakly acidic cation exchange resins or strongly basic and weakly basic anion exchange resins. Two or more types can be used in combination. Furthermore, not only new products but also recycled products that have been used in other processes can be used in the same way. Therefore, ion exchange resin is used as a powder with a particle size that corresponds to the desired film thickness. If it is difficult to obtain particles of such a particle size, it may be finely ground using a grinder.In order to obtain uniform hydrophilicity, the solid content should be 1-100g/, preferably 3-60
If the amount is less than 1 g/g, it is difficult to obtain uniform hydrophilicity, and if it is more than 100 g/, it is difficult to obtain uniform hydrophilicity.
Repeated swelling of the ion exchange resin reduces the adhesion and water resistance of the film. Therefore, the ion exchange resin acts as a water-insoluble surfactant, and also gives the film hydrophilicity that does not change over time and plastic workability that does not cause die wear when plastic working aluminum materials. be. Next, as the acrylic acid polymer, water-soluble or water-dispersible polyacrylic acid or polyacrylic ester (hereinafter referred to as resin) is used,
For example, acrylic acid, methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, maleic acid A compound obtained by polymerization or copolymerization of compounds such as , itaconic acid, etc. is used. Note that water-soluble resins undergo a chelate reaction with divalent or higher metal species (chromium ions in the present invention) coexisting in the film-forming agent during a relatively low-temperature, short-time heat treatment process, resulting in water-insoluble resins. The average molecular weight of water-soluble resins is preferably 10,000 to 300,000. Examples of such resins include Primal A-1, A-3, and A-5 (trade name). , ROHM &
(manufactured by Haas) are commercially available. For water-dispersed emulsion type resins, the upper limit of the molecular weight is not limited to this. Further, the acid value of the resin should be determined in relation to the molecular weight, but it is preferably 5 or more, and if it is less than this, high temperature and long-term treatment will be required, which is economically disadvantageous. However, the amount of resin added is 1 to 20 in terms of solid content.
g/, preferably in the range of 4 to 14 g/; below 1 g/and above 20 g/, the film tends to become uneven depending on the area, and the adhesion and corrosion resistance of the film also lacks uniformity. , the stability of the film former is also reduced. Further, when using an emulsion type resin, the amount is preferably 10 g/or less in view of the stability of the emulsion. In addition, the insolubilization of the water-soluble resin in the present invention is
As mentioned above, this is due to the formation of poorly soluble organic chromate compounds through a crosslinking reaction with coexisting chromium compounds, and the amount of chromium required for crosslinking is
() It is sufficient to add 0.2% or more, and the amount of the resin can be changed substantially arbitrarily as long as the content of the chromium compound of the present invention is met. Furthermore, it is also possible to improve the corrosion resistance of the film by adding a thermosetting water-soluble resin. The film forming agent of the present invention is prepared by blending these compounds within the above-mentioned range, and is
It is about 1.5 to 3. If desired, it is possible to add surfactants such as α-olefin sulfonate, sodium alkylnaphthalene sulfonate, etc. at a rate of about 0.5 to 1 g/as an initial hydrophilicity improver; acids, metaphosphoric acid, phosphorous acid, etc.
Addition of 0.1 to 50 g of PO 3-4 increases the uniform application of the film and further improves the long-term stability of hydrophilicity, so it can be used depending on the application method. In addition, silica powder such as silica sol or fumed silica can be used as a thickener for the film forming agent, a dispersant for ion exchange resins, or a hydrophilicity imparting aid.
There is no problem in adding about 0.5 to 4 g/approximately, or blending the total amount of additives such as antifungal agents and slip agents that are added to ordinary paints to about 0.01 to 0.5 g/approximately. As a method for preparing the film forming agent of the present invention, for example, a bath A in which ion exchange resin powder is uniformly dispersed in a resin liquid and a bath B in which a chromium compound and a fluoride are mixed and dissolved in water are separately prepared. A method in which both baths are prepared in advance or immediately before use and mixed together. Or A' bath in which ion exchange resin powder is uniformly dispersed in the resin liquid and trivalent chromium liquid is added;
A method in which fluoride and hexavalent chromium are mixed and prepared in bath B' immediately before use. or,
Mix all compounds immediately before use. Furthermore, any suitable method may be used, such as a method in which baths A and B or baths A' and B' are separately applied onto the surface of the aluminum material and mixed on the surface of the aluminum material. However, the film-forming agent of the present invention, like the conventional processing agents, requires complicated roll coating, spraying, etc. methods for forming materials with simple shapes such as continuous plates and extruded materials. In the case of a product having a specific shape, it can be applied to the aluminum surface by an appropriate method depending on the shape of the aluminum material, such as brushing, dipping, or spraying. That is, a film forming agent prepared to have a composition suitable for these application means is applied at a liquid temperature of 20 to 40°C in an application amount of 0.1 to 5 g/m 2 .
(dry film standard), then apply to
Heat treatment is performed at 250â for 10 seconds to 30 minutes to dry and bake the film. Note that if the film forming agent of the present invention is applied to the aluminum material while still retaining residual heat after rolling, extrusion, or other heat treatment, the subsequent heating and fixing process of the film can be omitted. You can use the residual heat. Furthermore, before the film is insolubilized, the film thickness can be increased by repeatedly applying the film forming agent of the present invention many times. Furthermore, coating can be applied not only after forming the aluminum material, but also because the resulting film has excellent press formability, so it can also be applied after forming the film.For example, it can be applied during press punching, etc. Secondary effects such as reducing die wear may also occur. The film obtained by applying the film-forming agent in this way consists of a lower layer consisting of an inorganic layer containing a chromium compound and highly corrosion resistant, and a resin layer mainly composed of an ion exchange resin that is highly hydrophilic and suppresses the elution of chromium compounds. It has a two-layer structure with an upper layer. This is thought to be the reason why the treatment agent permanently exhibited far superior hydrophilicity and corrosion resistance compared to conventional treatment agents. [Effects of the Invention] The present invention has a chromium compound, a fluoride, an ion exchange resin, and an acrylic acid polymer as constituent components,
Since we have blended a predetermined amount of each of these, when applied to the surface of an aluminum material, normal coating operations can be performed, and a film with little deterioration over time and excellent hydrophilicity and corrosion resistance can be formed. The resulting film has at least a two-layer structure, and the outer layer is a resin layer, so it has excellent processability after forming the film, and does not cause wear of processing dies or cracks in the film itself. Excellent effects are recognized, such as being able to prevent the elution of hexavalent chromium in the film. Next, examples of the present invention will be described. Example 1 (1) Preparation of hydrophilic corrosion-resistant film forming agent Water was added to a 20% by weight aqueous solution of polyacrylic acid (trade name Schurimar AC10H, manufactured by Nippon Pure Chemical Industries, Ltd.) so that the concentration of polyacrylic acid was 16 g/ml. After that, a sulfonic acid polyethylene cation exchange resin (trade name: Amberlite IR-120, manufactured by Rohm & Haas), which had been ground and dried to have an average particle size of 1 ÎŒm, was added at a rate of 16 g/ml and uniformly dispersed. solution (A bath) and chromium sulfate (Cr 2
(SO 4 ) 3ã»5H 2 O) 19.3 g/, chromium trioxide (CrO 3 ) 1.5 g/, hydrofluoric acid (46% HF) 2.1 g/
An aqueous solution (bath B) was prepared in advance, and when used, the same amounts of bath A and bath B were mixed together. (2) Film formation and press processing As the aluminum material, after degreasing and cleaning a 0.15 mm thick AA3102 aluminum alloy coil material with a weak alkaline cleaning solution, it was coated as described in the previous section (1) using a roll coating method.
A film-forming agent prepared by
Heat treatment at 150â for 20 minutes to make the film insoluble.
fixed. Next, using the obtained coil material, a cross fin material for a heat exchanger was manufactured by press punching and press ironing. (3) Evaluation test (a) Test method and evaluation of hydrophilicity and corrosion resistance (a) Test method of hydrophilicity (i) Initial performance: After immersing in deionized water, take it out and leave it for 30 seconds. It was measured. (ii) Long-term durability: relative humidity 95%, temperature 50â
The wetted area ratio was measured after being left in the atmosphere for 500 hours. (b) Corrosion resistance test method (i) Salt spray: The corrosion area rate was measured after 1000 hours based on the salt spray method according to JISZ2371 (1955). (ii) Acetic acid salt spray: The corrosion area rate was measured after 100 hours based on the Aluminum Surface Treatment Technology Research Association test standard ARS2132. (c) Evaluation The measurement results of the above test are shown in the attached table, and it can be seen that the film treatment agent of the present invention exhibits hydrophilicity equivalent to that of conventional treatment agents, and its corrosion resistance is significantly superior. Recognize. (b) Evaluation of press formability The processing die used to process the coil material treated with the film-forming agent of the present invention was processed at least 10 times as much as the treatment used for the comparative material treated with the conventional treatment agent. It was confirmed that the product could be used without any trouble even after reaching a certain amount, and that a film with a small amount of die wear could be obtained. This is also proven in the pressure ball abrasion test. Example 2 (1) Preparation of hydrophilic corrosion-resistant film forming agent Chromium acetate (Cr 2 (C 2 H 3 O) 6ã»2H 2 O)
g/, chromium trioxide (CrO 3 ) 1.42g/
, an aqueous solution (A bath) containing 1 g of hydrofluoric acid (46% HF) and 1 g of orthophosphoric acid (100% H 3 PO 4 ), and an acrylic acid polymer.
A 25% by weight aqueous solution (trade name: Primer A-1, manufactured by Rohm & Haas) was diluted with water to give an acrylic acid polymer concentration of 15.4 g/cm, and then a sulfonic acid type ion exchange resin with an average particle size of 0.5 to 1 ÎŒm was prepared. (Product name: R-120B, manufactured by Organo) in solid content.
An aqueous solution (bath B) was prepared in advance by mixing and uniformly dispersing 50 g of each, and equal amounts of each were mixed before use. (2) Formation of film and press processing Thickness of aluminum material treated with Triclean degreasing
It was coated on a 0.12 mm AA1050 alloy aluminum plate using a roll coater in the same manner as in Example 1,
Similarly, the film was made insoluble and fixed to form a film with a thickness of 1 ÎŒm. Then, press working was performed in the same manner as in Example 1. (3) Evaluation test The same test method as in Example 1 was conducted. These results are shown in the table below, and the corrosion resistance is significantly superior to that of conventional treatment agents, and the plastic workability shows no trouble at all even when the throughput is more than 10 times that of conventional treatment agents. Ta. Comparative example Commercially available acrylic resin paint (trade name Watersol 727, manufactured by Dainippon Ink Co., Ltd.), melamine resin paint (trade name Watersol S695, manufactured by Dainippon Ink Co., Ltd.), and colloidal silica (trade name Snotex, manufactured by Nissan Chemical Co., Ltd.) A mixture of 48 parts, 12 parts, and 40 parts of solids was prepared, and the same tests were conducted by coating, fixing by baking, and pressing under the same conditions as in the example. Ta. The results are shown in the attached table. ãtableã
Claims (1)
ç®ã§0.05ãïŒïœïŒãïŒäŸ¡ã®ã¯ãã ååç©ã
CrO3æç®ã§ïŒã18ïœïŒãããåç©ãF-ãšããŠ
0.1ãïŒïœïŒãã€ãªã³äº€ææš¹èç²æ«ãåºåœ¢åã§
ïŒã100ïœïŒãã¢ã¯ãªã«é žããªããŒãåºåœ¢åã§
ïŒã20ïœïŒé åããŠãªãããšãç¹åŸŽãšããã¢ã«
ãæçšèŠªæ°Žæ§èé£ç®è圢æå€ã1 In an aqueous solution, add 0.05 to 2 g of a hexavalent chromium compound (calculated as CrO 3 ) and a trivalent chromium compound
1 to 18g/ in terms of CrO3 , fluoride as F-
A hydrophilic corrosion-resistant film forming agent for aluminum material, characterized in that it contains 0.1 to 5 g/solid content of ion exchange resin powder, and 1 to 100 g/solid content of acrylic acid polymer.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2435785A JPS61186481A (en) | 1985-02-13 | 1985-02-13 | Hydrophilic corrosion-resisting film-forming material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2435785A JPS61186481A (en) | 1985-02-13 | 1985-02-13 | Hydrophilic corrosion-resisting film-forming material |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS61186481A JPS61186481A (en) | 1986-08-20 |
JPH0348271B2 true JPH0348271B2 (en) | 1991-07-23 |
Family
ID=12135940
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2435785A Granted JPS61186481A (en) | 1985-02-13 | 1985-02-13 | Hydrophilic corrosion-resisting film-forming material |
Country Status (1)
Country | Link |
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JP (1) | JPS61186481A (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
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JP4652592B2 (en) * | 2001-03-15 | 2011-03-16 | æ¥æ¬ãã€ã³ãæ ªåŒäŒç€Ÿ | Metal surface treatment agent |
-
1985
- 1985-02-13 JP JP2435785A patent/JPS61186481A/en active Granted
Also Published As
Publication number | Publication date |
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JPS61186481A (en) | 1986-08-20 |
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