JPH04502647A - How to impregnate aluminum surface formed with anode - Google Patents
How to impregnate aluminum surface formed with anodeInfo
- Publication number
- JPH04502647A JPH04502647A JP2501034A JP50103489A JPH04502647A JP H04502647 A JPH04502647 A JP H04502647A JP 2501034 A JP2501034 A JP 2501034A JP 50103489 A JP50103489 A JP 50103489A JP H04502647 A JPH04502647 A JP H04502647A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- ych
- compound
- so3h
- sealing
- 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.)
- Pending
Links
- 229910052782 aluminium Inorganic materials 0.000 title claims description 23
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims description 23
- 238000007789 sealing Methods 0.000 claims description 59
- 150000001875 compounds Chemical class 0.000 claims description 56
- 238000000034 method Methods 0.000 claims description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 238000005470 impregnation Methods 0.000 claims description 23
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 15
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 239000003945 anionic surfactant Substances 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- -1 alkali metal salts Chemical class 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 229910000838 Al alloy Inorganic materials 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 150000002148 esters Chemical class 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 5
- 150000003460 sulfonic acids Chemical class 0.000 claims description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 3
- 125000004429 atom Chemical group 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- 229910006069 SO3H Inorganic materials 0.000 claims 10
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims 10
- 229910018828 PO3H2 Inorganic materials 0.000 claims 4
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims 1
- 229910052783 alkali metal Inorganic materials 0.000 claims 1
- 150000001342 alkaline earth metals Chemical class 0.000 claims 1
- 150000003863 ammonium salts Chemical class 0.000 claims 1
- 239000010408 film Substances 0.000 description 30
- 238000000576 coating method Methods 0.000 description 22
- 238000012360 testing method Methods 0.000 description 21
- 239000011248 coating agent Substances 0.000 description 20
- 239000002253 acid Substances 0.000 description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 10
- 150000003009 phosphonic acids Chemical class 0.000 description 10
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 7
- 239000003112 inhibitor Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 6
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 6
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 6
- 239000005642 Oleic acid Substances 0.000 description 6
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 6
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 6
- 125000006353 oxyethylene group Chemical group 0.000 description 6
- 238000006277 sulfonation reaction Methods 0.000 description 6
- GYGAZRPDUOHMAF-UHFFFAOYSA-N acetic acid elaidylester Natural products CCCCCCCCC=CCCCCCCCCOC(C)=O GYGAZRPDUOHMAF-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000004040 coloring Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000002932 luster Substances 0.000 description 5
- GYGAZRPDUOHMAF-KHPPLWFESA-N oleyl acetate Chemical compound CCCCCCCC\C=C/CCCCCCCCOC(C)=O GYGAZRPDUOHMAF-KHPPLWFESA-N 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- RZXLPPRPEOUENN-UHFFFAOYSA-N Chlorfenson Chemical compound C1=CC(Cl)=CC=C1OS(=O)(=O)C1=CC=C(Cl)C=C1 RZXLPPRPEOUENN-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000011552 falling film Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- LKOVPWSSZFDYPG-WUKNDPDISA-N trans-octadec-2-enoic acid Chemical compound CCCCCCCCCCCCCCC\C=C\C(O)=O LKOVPWSSZFDYPG-WUKNDPDISA-N 0.000 description 4
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 3
- 238000002048 anodisation reaction Methods 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- XQRLCLUYWUNEEH-UHFFFAOYSA-N diphosphonic acid Chemical compound OP(=O)OP(O)=O XQRLCLUYWUNEEH-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000003311 flocculating effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- BARWIPMJPCRCTP-UHFFFAOYSA-N oleic acid oleyl ester Natural products CCCCCCCCC=CCCCCCCCCOC(=O)CCCCCCCC=CCCCCCCCC BARWIPMJPCRCTP-UHFFFAOYSA-N 0.000 description 3
- 229940055577 oleyl alcohol Drugs 0.000 description 3
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 3
- BARWIPMJPCRCTP-CLFAGFIQSA-N oleyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCCOC(=O)CCCCCCC\C=C/CCCCCCCC BARWIPMJPCRCTP-CLFAGFIQSA-N 0.000 description 3
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 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
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 239000007832 Na2SO4 Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- QUBQYFYWUJJAAK-UHFFFAOYSA-N oxymethurea Chemical compound OCNC(=O)NCO QUBQYFYWUJJAAK-UHFFFAOYSA-N 0.000 description 2
- 229950005308 oxymethurea Drugs 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000010186 staining Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- BVQJQTMSTANITJ-UHFFFAOYSA-N tetradecylphosphonic acid Chemical group CCCCCCCCCCCCCCP(O)(O)=O BVQJQTMSTANITJ-UHFFFAOYSA-N 0.000 description 2
- ZENZJGDPWWLORF-UHFFFAOYSA-N (Z)-9-Octadecenal Natural products CCCCCCCCC=CCCCCCCCC=O ZENZJGDPWWLORF-UHFFFAOYSA-N 0.000 description 1
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 1
- CCCUCKBCNVRZKC-UHFFFAOYSA-N 1-hydroxydodecylphosphonic acid Chemical compound CCCCCCCCCCCC(O)P(O)(O)=O CCCUCKBCNVRZKC-UHFFFAOYSA-N 0.000 description 1
- YIPNWNIEMZTKBC-UHFFFAOYSA-N 1-hydroxyoctadec-1-ene-1-sulfonic acid Chemical compound CCCCCCCCCCCCCCCCC=C(O)S(=O)(=O)O YIPNWNIEMZTKBC-UHFFFAOYSA-N 0.000 description 1
- NMHJNWFBOIBENU-UHFFFAOYSA-N 12-hydroxy-12-phosphonooctadecanoic acid Chemical compound OC(CCCCCCCCCCC(=O)O)(CCCCCC)P(=O)(O)O NMHJNWFBOIBENU-UHFFFAOYSA-N 0.000 description 1
- OFOWUDSDZLONKT-UHFFFAOYSA-N 12-oxo-octadecanoic acid Chemical compound CCCCCCC(=O)CCCCCCCCCCC(O)=O OFOWUDSDZLONKT-UHFFFAOYSA-N 0.000 description 1
- SXAMGRAIZSSWIH-UHFFFAOYSA-N 2-[3-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,2,4-oxadiazol-5-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NOC(=N1)CC(=O)N1CC2=C(CC1)NN=N2 SXAMGRAIZSSWIH-UHFFFAOYSA-N 0.000 description 1
- SDGNNLQZAPXALR-UHFFFAOYSA-N 3-sulfophthalic acid Chemical compound OC(=O)C1=CC=CC(S(O)(=O)=O)=C1C(O)=O SDGNNLQZAPXALR-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical class [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- 241001676573 Minium Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- XIUNAJHNBHZWJR-UHFFFAOYSA-N [N].O=S=O Chemical compound [N].O=S=O XIUNAJHNBHZWJR-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000007743 anodising Methods 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 230000001010 compromised effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- VDQVEACBQKUUSU-UHFFFAOYSA-M disodium;sulfanide Chemical compound [Na+].[Na+].[SH-] VDQVEACBQKUUSU-UHFFFAOYSA-M 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229940093915 gynecological organic acid Drugs 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- MYWUZJCMWCOHBA-VIFPVBQESA-N methamphetamine Chemical class CN[C@@H](C)CC1=CC=CC=C1 MYWUZJCMWCOHBA-VIFPVBQESA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 125000005064 octadecenyl group Chemical group C(=CCCCCCCCCCCCCCCCC)* 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical group OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 1
- 238000005954 phosphonylation reaction Methods 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 1
- 229960003656 ricinoleic acid Drugs 0.000 description 1
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229950000244 sulfanilic acid Drugs 0.000 description 1
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 1
- CICKVIRTJQTMFM-UHFFFAOYSA-N sulfuric acid;tin Chemical compound [Sn].OS(O)(=O)=O CICKVIRTJQTMFM-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- MYOWBHNETUSQPA-UHFFFAOYSA-N tetradecane-1-sulfonic acid Chemical group CCCCCCCCCCCCCCS(O)(=O)=O MYOWBHNETUSQPA-UHFFFAOYSA-N 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/18—After-treatment, e.g. pore-sealing
- C25D11/24—Chemical after-treatment
- C25D11/246—Chemical after-treatment for sealing layers
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/18—After-treatment, e.g. pore-sealing
- C25D11/24—Chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるため要約のデータは記録されません。 (57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】 陽極で形成されたアルミニウム表面を含浸する方法本発明は、陽極で形成された 着色していることのあるアルミニウム及び／又はアルミニウム合金表面の含浸方 法に関する。本発明において、上記表面は特定のアニオン性界面活性化合物の水 溶液と接触される。[Detailed description of the invention] Method of impregnating an aluminum surface formed with an anode How to impregnate aluminum and/or aluminum alloy surfaces that may be colored Regarding the law. In the present invention, the surface is water of a specific anionic surfactant compound. contacted with the solution.
陽極で形成される酸化物フィルムは、天候および他の腐食性媒体の影響から表面 を保護するので、特に建築物において、腐食保護の目的から装飾アルミニウム表 面に適用されることが多い。陽極で形成される酸化物フィルムは、さらに、より 硬質の表面を得、アルミニウムの耐摩耗性を向上させるためにも適用される。酸 化物フィルムは比較的着色が容易なので特に装飾効果を得ることができる。The oxide film formed at the anode protects the surface from the effects of weather and other corrosive media. decorative aluminum surfaces for corrosion protection purposes, especially in buildings. Often applied to surfaces. The oxide film formed at the anode is even more It is also applied to obtain a hard surface and improve the wear resistance of aluminum. acid Since compound films can be colored relatively easily, decorative effects can be particularly obtained.
陽極で形成される装飾的な酸化物フィルムをアルミニウム及び／又はアルミニウ ム合金表面に適用する多くの方法が知られている。The decorative oxide film formed at the anode is replaced with aluminum and/or aluminum. Many methods are known for application to aluminum alloy surfaces.
例えば、硫酸溶液中、直流を重畳した交流を用いて酸化物フィルムを形成するこ とができる。しかしながら、例えば、スルホフタル酸またはスル２アニル酸のよ うな有機酸の溶液またはそれらと硫酸との混合物が用いられことが多い。けれど も、このように適用された酸化物フィルムは、開孔性構造を有するので、腐食防 止に関するすべての要求は満たさない。この理由により、酸化物フィルムを「強 化」する必要がある。この強化は、通常、温水または沸騰水を用いて行われ、「 封孔」として知られている。プロセス中に、孔が封鎖され、その結果腐食防止が 促進される。For example, an oxide film can be formed using alternating current superimposed with direct current in a sulfuric acid solution. I can do it. However, for example, sulfophthalic acid or sulfanilic acid Solutions of organic acids such as sulfuric acid or their mixtures with sulfuric acid are often used. However Also, the oxide film applied in this way has an open structure and therefore provides corrosion protection. All requirements regarding suspension are not met. For this reason, oxide films are There is a need to "transform" This fortification is usually done using warm or boiling water and is It is known as a "sealing hole". During the process, the pores are sealed, resulting in corrosion protection. promoted.
陽極で適用された酸化物フィルムの強化中、表面の孔が特に封鎖され、同時に酸 化物フィルムの改造が行われる。しかしながら、さらに、幾分ビロード状の水和 酸化アルミニウムの問題となる塗膜、いわゆる「封孔塗膜」が全領域に形成され 、それが、このアルミニウム部分の接着力を更に低下させ、拡大した有効表面故 にその後の汚れおよび腐食を促進する。During the reinforcement of the oxide film applied at the anode, the pores on the surface are especially sealed and at the same time the acid Modification of the chemical film is carried out. However, in addition, the somewhat velvety hydration A problematic coating film of aluminum oxide, so-called “sealing coating film”, is formed on the entire area. , which further reduces the adhesion of this aluminum part and due to the enlarged effective surface. to promote subsequent staining and corrosion.
西ドイツ公開特許２２ １１ ５５３は、表面における問題となる水酸化アルミ ニウム塗膜の形成をほとんど防止し、水の硬度を上昇させる塩による問題を避け るために、アルミニウムまたはアルミニウム合金の表面を、特定のホスホン酸を 用いて更にカルシウムイオンを添加して封孔する方法を記載している。この方法 のために、二価金属と錯体を形成する短鎖ホスホン酸またはその水溶性塩が特に 効果的であると教示されている。West German Published Patent No. 22 11 553 discloses that aluminum hydroxide is a problem on the surface. Virtually prevents the formation of paint films and avoids problems caused by salts that increase water hardness The surface of aluminum or aluminum alloys is treated with certain phosphonic acids to A method is described for sealing the pores by adding calcium ions. this method Short-chain phosphonic acids or their water-soluble salts that form complexes with divalent metals are particularly useful for taught to be effective.
ヨーロッパ公開特許０ １２２ １２９は、陽極で形成したアルミニウム表面を 、封孔助剤の存在下にｐＨを少なくとも７として水溶液で処理する方法を記載し ている。封孔塗膜抑制剤としても知られている封孔助剤の例は、デキストリン、 アクリル酸、メタクリル酸、アクリル酸またはメタクリル酸リグノスルホネート の水溶性ポリマー、環状脂肪族または芳香族ポリカルボン酸およびシクロヘキサ ン−ヘキサカルボン酸、二価金属と錯体を形成する水溶性短鎖ホスホン酸、スル ホン化芳香族化合物とアルデヒド及び／又はジメチロール尿素との反応生成物ま たはホルムアルデヒドと尿素との混合物である。European Published Patent No. 0 122 129 discloses an aluminum surface formed with an anode. describes a method of treatment with an aqueous solution at a pH of at least 7 in the presence of a sealing aid. ing. Examples of sealing aids, also known as sealing film inhibitors, are dextrins, Acrylic acid, methacrylic acid, acrylic acid or methacrylic acid lignosulfonate water-soluble polymers, cycloaliphatic or aromatic polycarboxylic acids and cyclohexa -hexacarboxylic acids, water-soluble short chain phosphonic acids that form complexes with divalent metals, sulfur Reaction products of phonated aromatic compounds and aldehydes and/or dimethylol urea or or a mixture of formaldehyde and urea.
封孔塗膜抑制剤としてホスホン酸を含む種々の有機化合物を用いることが、ゲー ハウゼン（Ｈ，Ｊ 、 Ｇｏｅｈａｕｓｅｎ）およびシエーナ−（Ｇ。The use of various organic compounds containing phosphonic acid as sealing film inhibitors has been Goehausen (H, J.) and Siena (G.
Ｃ，５Ｃ１１ｏｅｎｅｒ）、インダストリアル・フィニツソング（Ｉ ｎｄｕｓ ｔｒｉａｌＦ ｉｎｉｓｈｉｎｇ）、１９８２年、特別版、に記載されている。C, 5C11oener), Industrial Finitsong (Indus trialF initiating), 1982, special edition.
英国特許出願公開２ １３９６４６は、光沢のある塗膜を形成せずに迅速かつ効 率的な封孔を達成するために封孔塗膜抑制剤の存在下に少なくとも７のｐＨで封 孔浴において陽極酸化アルミニウム表面を封孔する方法を記載している。デキス トリン、ホスホネート、カルボン酸およびアルデヒドまたはジメチロール尿素の 反応生成物は使用可能な封孔塗膜抑制剤の例である。封孔塗膜抑制剤の本質的特 性は、二価金属カチオンと錯体を形成することである。これらは特に封孔浴の水 硬度の低下に役立つ。British Patent Application No. 2 139646 is a quick and effective method without forming a glossy coating. Sealing at a pH of at least 7 in the presence of a sealing film inhibitor to achieve efficient sealing. A method for sealing anodized aluminum surfaces in a pore bath is described. dex of trines, phosphonates, carboxylic acids and aldehydes or dimethylol urea The reaction products are examples of sealing film inhibitors that can be used. Essential characteristics of sealing film inhibitor property is to form complexes with divalent metal cations. These are especially important for the water in the sealing bath. Helps reduce hardness.
アルミニウムまたはアルミニウム合金の表面を処理する方法が、西ドイツ公開特 許２６ ５０ ９８９から知られており、そこで、封孔は、分子内に４〜６個の カルボキシル基を含む環状脂肪族または芳香族ポリカルボン酸の存在下に行われ る。A method for treating the surface of aluminum or aluminum alloys was published in a West German publication special. 26 50 989, where the sealing is caused by the presence of 4 to 6 molecules in the molecule. carried out in the presence of a cycloaliphatic or aromatic polycarboxylic acid containing carboxyl groups. Ru.
これに対し、本発明の目的は、陽極で形成されたアルミニウム表面を含浸する方 法を利用することである。本発明の出発点は、アルミニウムおよびアルミニウム 合金の表面が屋外耐候試験において充分な耐性を有さないことであった［シュル ツ（Ｓ ｃｈｕｌｚ）ら、「アルミナム（Ａｌｕｍｉｎｕｍ）Ｊ 、第６４巻（ １９８８年）、３８４〜３９２頁、参照］。特に、従来技術により得られたアル ミニウム表面は凝縮水に対する耐性が不充分であることがわかった。In contrast, the object of the present invention is to impregnate the aluminum surface formed by the anode. It is to use the law. The starting point of the invention is aluminum and aluminum The surface of the alloy did not have sufficient resistance in outdoor weathering tests [Shur Schulz et al., “Aluminum J, Vol. 64 ( 1988), pp. 384-392]. In particular, aluminum obtained by conventional techniques The minium surface was found to be insufficiently resistant to condensed water.
すなわち、上述の目的は、アルミニウム及び／又はアルミニウム合金の陽極で形 成された表面を含浸する方法であって、着色または未着色表面を、スルホン酸基 、ホスホン酸基及び／又は亜ホスホン酸基の少なくとも一つを含む下記アニオン 性界面活性化合物（Ｉ）〜（■）の一種以上を含む水溶液に接触させることを特 徴とする方法によって達成される： 式： Ａ−Ｒ（Ｉ） 〔式中、ＡはＣＨｘ（ＣＨ２）、ＣＨ（ＯＨＸＣＨ２）ｙＣＨ（Ｓ○３ＨＸＣＨ ７）、−及び／又はＣＨｓ （ＣＨ２） −ＣＨ（Ｓ Ｏｓ Ｈ） （ＣＨ２） −ＣＨ（ＯＨ）（ＣＨ２）、−またはＨＯｓＳ−ＣＨｚ（ＣＨｚ）−ＣＨ（Ｏ ＨＸＣＨ２）−一及び／又はＨＯ−ＣＨ２（ＣＨ２）、ＣＨ（ＳＯｘＨ）（ＣＨ ｚ）、−［ここで、Ｘ、Ｚ＝Ｏ〜１７、ｙ＝１または２、ｘ十ｙ十ｚ＝７〜１６ 、ｑ＝４〜１７コ、およびＲは ＣＨｚＯ（Ｃ，Ｈｚ−０）、Ｈｌ−ＣＨ２０（ Ｃ。That is, the above-mentioned object is formed with an anode of aluminum and/or aluminum alloy. A method of impregnating colored or uncolored surfaces with sulfonic acid groups. , the following anion containing at least one of a phosphonic acid group and/or a phosphonous acid group In particular, contacting with an aqueous solution containing one or more of the surfactant compounds (I) to (■) This is achieved by the following method: Formula: A-R(I) [In the formula, A is CHx(CH2), CH(OHXCH2)yCH(S○3HXCH 7), - and/or CHs (CH2) -CH (S Os H) (CH2) -CH(OH)(CH2), - or HOsS-CHz(CHz)-CH(O HXCH2)-1 and/or HO-CH2(CH2), CH(SOxH)(CH z), - [where X, Z = O ~ 17, y = 1 or 2, x + y + z = 7 ~ 16 , q=4~17, and R are CHzO (C, Hz-0), Hl-CH20 ( C.
Ｈ２Ｉ、Ｏ）、Ｃｏ−Ａ、−ＣＯＯＲ”または−ＣＨ３にこで、Ｒ”＝Ｈまたは Ｃ１〜Ｃ４アルキル、ｎ＝２〜４およびｐ＝０〜５〕を表す。〕で示される化合 物および水分子の形式的分離によりＡから得られる化合物、 式： Ｒ’ ＰＯｓＨ２（ＩＩ） 〔式中、Ｒ１は８〜２２個の炭素原子を含む直鎖及び／又は分岐状の飽和または −及び／又は多不飽和アルキル基［直鎖状アルキル基においてアルファおよびベ ータ位は置換されておらず、さらに、要すれば、一つ及び／又はそれ以上のホス ホン酸、カルボン酸、スルホン酸、エステル、ヒドロキシル、ハロゲン及び／又 は遊離もしくはＮ、Ｎ−アルキル化アミノ基を有する］および６〜２２個の炭素 原子を含むアルキルアリール基を表す。〕で示される化合物、 式： Ｒ” Ｃｏ ＮＨ−Ｃ（Ｒ’２）ＰＯｓＨ２（ｍ）〔式中、Ｒ２は５〜２ １個の炭素原子を含む直鎖及び／又は分岐状アルキル基およびＲ３は水素及び／ 又は０１〜Ｃ４アルキル基を表す。〕で示される化合物、 式： Ｒ’−（ＯＣＲ２ＣＥ２）、Ｎ（ＣＢ２ＰＯＪ２）（ＣＨ２Ｃ１（２０Ｂ ） （ＩＶ）〔式中、Ｒ］は上記と同意義、およびａはＯ〜１０の整数を表す。H2I, O), Co-A, -COOR" or -CH3, R"=H or C1-C4 alkyl, n=2-4 and p=0-5]. ] compounds obtained from A by formal separation of compounds and water molecules, Formula: R' POsH2(II) [wherein R1 is a linear and/or branched saturated or - and/or polyunsaturated alkyl groups [alpha and base in linear alkyl groups] The data positions are unsubstituted and optionally one and/or more host positions are substituted. Phonic acid, carboxylic acid, sulfonic acid, ester, hydroxyl, halogen and/or has a free or N,N-alkylated amino group] and 6 to 22 carbons Represents an alkylaryl group containing atoms. ] A compound represented by Formula: R” Co NH-C(R’2)POsH2(m) [wherein R2 is 5 to 2 Straight-chain and/or branched alkyl groups containing one carbon atom and R3 are hydrogen and/or Or represents an 01-C4 alkyl group. ] A compound represented by Formula: R'-(OCR2CE2), N(CB2POJ2)(CH2C1(20B ) (IV) [In the formula, R] has the same meaning as above, and a represents an integer of O to 10.
〕で示される化合物、 式： Ｒ’−（ＯＣＲ２ＣＥ２）、ＮＲ’（ＣＨｘ）ＪＲ’Ｃ１１２Ｐ０３Ｅ２ （Ｖ）〔式中、Ｒ１は上記と同意義、Ｒ４は水素またはＣＨ２ＰＯ３Ｈ２およ びｂは２〜６の整数を表す。〕 で示される化合物、 式： Ｈ２Ｎ（ＣＨ２）、Ｃ（ＯＨＸＰＯ３Ｈ２）２ （ＶＩ）〔式中、Ｃは４ 〜１６の整数を表す。〕で示される化合物、 式： ＨＯＯＣ（ＣＨｚ）ｄ−ＰＯ−Ｈｚ （Ｖｌｌ）〔式中、ｄは５〜１７の 整数およびｅは２または３を表す。〕で示される化合物、 式： ＣＨ３−（Ｃ１１１ｚ）＋−Ｃ（ＯＢＸＰＯｓｌｌｌｔ）−（Ｃ１ｈ）、 −ＣＯＯＨ（■）〔式中、（ｆ＋９）は９〜１９の整数を表す。〕で示される化 合物。] A compound represented by Formula: R'-(OCR2CE2), NR'(CHx)JR'C112P03E2 (V) [In the formula, R1 has the same meaning as above, R4 is hydrogen or CH2PO3H2 and and b represent an integer of 2 to 6. ] A compound represented by Formula: H2N(CH2), C(OHXPO3H2)2 (VI) [wherein C is 4 Represents an integer between ~16. ] A compound represented by Formula: HOOC (CHz) d-PO-Hz (Vll) [wherein d is 5 to 17] The integer and e represent 2 or 3. ] A compound represented by Formula: CH3-(C111z)+-C(OBXPOslllt)-(C1h), -COOH(■) [In the formula, (f+9) represents an integer from 9 to 19. ] Compound.
アルミニウムおよびアルミニウム合金の屋外耐候挙動は、本発明により向上させ ることができる。このようにして、現行技術と比較して向上した前記表面の耐凝 縮水性を連成することができる。The outdoor weathering behavior of aluminum and aluminum alloys is improved by the present invention. can be done. In this way, the anti-fogging resistance of said surface is improved compared to current technology. Can be coupled with water shrinkage.
少なくとも一つのスルホン酸基、ホスホン酸基及び／又は少なくとも一つの亜ホ スホン酸基を有する本発明で用いられる界面活性化合物（１）〜（■）は、封孔 プロセスに続いて用いる、すなわち、既知の封孔浴中で表面を処理した後に用い る、またはそのような封孔浴中において用いることさえできる。すなわち化合物 （Ｉ）〜（■）は同時に含浸添加剤および封孔助剤として、すなわち封孔塗膜抑 制剤として用いることができ、そのような封孔浴は要すれば特に西ドイツ公開特 許２６ ５０ ９８９に開示されたような更なる封孔助剤を含んでよい。at least one sulfonic acid group, phosphonic acid group and/or at least one subphosphonic acid group Surface-active compounds (1) to (■) used in the present invention having sulfonic acid groups are pore-sealing compounds. used subsequent to the process, i.e. after treating the surface in a known sealing bath. or even be used in such a sealing bath. i.e. compound (I) to (■) are simultaneously used as impregnating additives and sealing aids, that is, as sealing coating film inhibitors. It can be used as a sealing agent, and such a sealing bath can be used, if necessary, especially in the West German Open Special. Further sealing aids such as those disclosed in US Pat. No. 2,650,989 may be included.
化合物（Ｉ）において、Ｒが一〇 Ｈ２０（Ｃ−Ｈ２−○）９Ｈを表す場合、イ ソオレイル（エーテル）スルホネートが得られる。その製造法は西ドイツ特許出 願Ｐ ３７ ２５ ０３０．２に記載されている。In compound (I), when R represents 10H20(C-H2-○)9H, Sooleyl (ether) sulfonate is obtained. The manufacturing method was patented in West Germany. It is described in Application P 37 25 030.2.
イソオレイルオレエート−ジスルホネートから誘導された界面活性化合物が西ド イツ特許出願Ｐ ３８ ０９ ８２２．９に記載されている。Surfactant compounds derived from isooleyl oleate-disulfonate It is described in the Japanese patent application P 38 09 822.9.
オレイン酸スルホネートは英国特許出願公開１．２７８．４２１号により製造す ることができる。Oleic acid sulfonate is manufactured according to British Patent Application No. 1.278.421. can be done.
モノホスホン酸（ＩＩ）は、既知の方法により、相当するハロゲン化アルキルを トリアルキルホスフィツトと反応させ、続いて加水分解することにより製造する ことができる。ハロゲン化物とトリアルキルホスフィツトとの反応は文献におい てミハエリスーアルブソフ（Ｍｉｃｈａｅｌｉｓ−Ａｒｂｕｓｏｖ）反応として 知られている〔例えば、ホーベンーヴエイル（Ｈｏｕｂｅｎ−Ｗｅｙｌ）、ｒメ トーデン・デル・オルガニツシェン・ヘミ−（Ｍｅｔｈｏｄｅｎ ｄｅｒ ｏｒ ｇａｎｉｓｃｈｅｎ Ｃｈｅｍｉｅ）Ｊ、第４版、（１９６３年）、第１２巻、 ４３３頁、参照〕。Monophosphonic acid (II) can be converted to the corresponding alkyl halide by known methods. Produced by reaction with trialkyl phosphite followed by hydrolysis be able to. The reaction of halides with trialkyl phosphites has been described in the literature. As a Michaelis-Arbusov reaction known [e.g. Houben-Weyl, R. Methoden der Chemie) J, 4th edition, (1963), Volume 12, See page 433].
アシルアミド−アルキルホスホン酸（ＩＩ［）は、溶媒としての氷酢酸中、ケト ンの存在下に相当する酸アミドと三塩化燐との反応により合成することができる 。Acylamide-alkylphosphonic acid (II[) was prepared in glacial acetic acid as solvent. can be synthesized by the reaction of the corresponding acid amide with phosphorus trichloride in the presence of .
ホスホン酸（ＴＶ）および（Ｖ）は、メードリツ７−（Ｋ、 Ｍｏｅｄｒｉｔｚ ｅｒ）およびイラニ（Ｂ、Ｉｒａｎｉ）によりジャーナル・オブ・オーガニ・ン ク・ケミストリー（Ｊ ｏｕｒｎａｌ ｏｆ Ｏｒｇａｎｉｃ Ｃｈｅｍｉｓｔ ｒｙ）、第３１巻、（１９６６年）、１６０３頁、に記載されているように、ア ミンのメチレン−ホスホニル化により製造される。上述の場合、アルキル化アル カノールアミンが被処理物質として用いられる。Phosphonic acids (TV) and (V) are Moedritz 7-(K, Moedritz er) and Irani (B.) in the Journal of Organism. KU Chemistry (J-own of Organic Chemist) ry), Vol. 31, (1966), p. 1603, Produced by methylene-phosphonylation of amine. In the above case, alkylated alkaline Canolamine is used as the substance to be treated.
ジホスホン酸（ＶＩ）の合成が特にヨーロッパ公開特許００３９０３３に記載さ れている。The synthesis of diphosphonic acid (VI) is described in particular in European Published Patent No. 0039033. It is.
化合物（■）は、末端不飽和カルボン酸にＨ３ＰＯｓ、ＰＣｌ３またはＨ３ＰＯ ２を付加することにより得られる。Compound (■) is a terminally unsaturated carboxylic acid containing H3POs, PCl3 or H3PO It is obtained by adding 2.
化合物（■）は、氷酢酸中でケトアルカンカルボン酸とＰＣｌ３とを反応させ、 続いて加水分解することにより得られる。分子内ケト基の位置は通常ここでは不 確定である。例えば、リシノール酸は、その後上述のように反応して１２−ヒド ロキシ−１２−ホスホノステアリン酸になる１２−ケトステアリン酸に転移する ことができる。Compound (■) is obtained by reacting a ketoalkanecarboxylic acid with PCl3 in glacial acetic acid, It is obtained by subsequent hydrolysis. The position of the keto group in the molecule is usually irrelevant here. It is certain. For example, ricinoleic acid can then be reacted with 12-hydrogen as described above. Transfers to 12-ketostearic acid, which becomes roxy-12-phosphonostearic acid be able to.
封孔浴に通常含まれる短鎖ホスホン酸は、屋外耐候試験において表面の挙動に影 響を与えないが、本発明で用いられる長鎖界面活性化合物は封孔酸化物フィルム 上に残り、表面の永続的装飾外観に好ましい影響を及ぼす。封孔浴における添加 剤としてのホスホン酸及び／又はスルホン酸の使用が従来技術において既に提案 されていたとしても、長鎖ホスホン酸が屋外耐候塗膜に優れた抑制効果を示すこ とまたは屋外耐候試験において装飾的外観を維持することは従来技術においてま だ知られていなかった。本発明による含浸は、酸化物フィルムを保護し、装飾的 外観を損なう汚れの形成を防止する。Short-chain phosphonic acids, commonly contained in sealing baths, have an effect on surface behavior during outdoor weathering tests. Although the long-chain surfactant compounds used in the present invention do not affect the pore-sealing oxide film, remains on the surface and positively influences the permanent decorative appearance of the surface. Addition in sealing bath The use of phosphonic and/or sulfonic acids as agents has already been proposed in the prior art. However, long-chain phosphonic acids have shown excellent inhibitory effects on outdoor weathering coatings. Maintaining the decorative appearance during weathering and outdoor weathering tests is difficult in the prior art. It was unknown. Impregnation according to the invention protects the oxide film and provides decorative Prevents the formation of unsightly stains.
さらに、光沢性のある塗膜および凝集水による色むらがほとんど防止される。こ れらの利益は特に屋外耐候試験において見ることができる。本発明により処理さ れた酸化アルミニウム表面には明らかに指紋が付きにくいこともわかった。Furthermore, glossy coatings and color unevenness due to coagulated water are almost completely prevented. child These benefits can be seen especially in outdoor weathering tests. treated according to the invention It was also found that fingerprints are clearly less likely to stick to the aluminum oxide surface.
本発明の好ましい態様によれば、封孔プロセス後の表面に化合物（Ｉ）〜（■） を接触させる。ここで、封孔アルミニウム表面を封孔プロセスと別の工程におい て上記アニオン性界面活性化合物の水溶液に導入する。本発明によれば、以下の パラメーターが用いられる； アニオン性界面活性化合物の濃度： ０．０１〜５０ｇ／ｌｌ、好ましくは０， ０５〜１０ｇ／／、特に０．１〜１ ｙ／ｌ。According to a preferred embodiment of the present invention, compounds (I) to (■) are added to the surface after the sealing process. contact. Here, the sealed aluminum surface is subjected to a separate process from the sealing process. and introduced into the aqueous solution of the anionic surface-active compound. According to the present invention, the following parameters are used; Concentration of anionic surfactant compound: 0.01 to 50 g/ll, preferably 0, 05-10 g//, especially 0.1-1 y/l.
水溶液の温度＝２０〜１００℃、好ましくは４０〜１００℃、特に４０〜６０℃ 。Temperature of aqueous solution = 20-100°C, preferably 40-100°C, especially 40-60°C .
水溶液のｐＨ＋９まで、好ましくは６〜８゜処理時間：１０秒〜１時間、好まし くは１〜３分。ここで、短い処理時間の場合は通常高い濃度が選択され、長い処 理時間の場合は通常低い濃度が選択される。Until the pH of the aqueous solution is +9, preferably 6-8° Treatment time: 10 seconds to 1 hour, preferably 1 to 3 minutes. Here, a higher concentration is usually selected for short treatment times and A lower concentration is usually chosen for the treatment time.
本発明のさらに好ましい態様は、化合物（Ｉ）〜（■）を封孔浴中で表面に接触 させることを含んでなる陽極で形成されたアルミニウム及び／又はアルミニウム 合金表面を含浸する方法からなる。ここで、本発明により用いられる化合物が、 要すれば既知の封孔助剤、すなわち封孔塗膜抑制剤と共に既知の封孔浴中で使用 される。この場合、本発明により用いられる化合物は上記濃度でそれらの浴に添 加される。In a further preferred embodiment of the present invention, compounds (I) to (■) are brought into contact with the surface in a sealing bath. Aluminum and/or aluminum formed with an anode comprising It consists of a method of impregnating the alloy surface. Here, the compound used according to the present invention is Used in known sealing baths, optionally with known sealing aids, i.e. sealing film inhibitors. be done. In this case, the compounds used according to the invention are added to their baths at the concentrations mentioned above. added.
いわゆる「熱封孔」の場合、封孔および含浸浴の温度は９０〜１００℃に調節さ れ、浴のｐＨは５〜９、好ましくは６〜８に調節される。封孔すなわち含浸は、 陽極で形成された酸化物フィルム厚１ミクロン当たり１〜３分間行われる。In the case of so-called "thermal sealing", the temperature of the sealing and impregnation bath is adjusted to 90-100°C. The pH of the bath is adjusted to 5-9, preferably 6-8. Sealing or impregnation is This is carried out for 1 to 3 minutes per micron of oxide film thickness formed at the anode.
いわゆる「冷封孔］の場合、封孔または含浸浴の温度は２０〜４０℃に調節され 、浴のｐＨは５〜８に調節される。封孔すなわち含浸は、フィルム厚１ミクロン 当たり１０秒〜２分間行われる。In the case of so-called "cold sealing", the temperature of the sealing or impregnation bath is adjusted to 20-40℃. , the pH of the bath is adjusted to 5-8. Sealing or impregnation is done with a film thickness of 1 micron. This is done for 10 seconds to 2 minutes per session.
後者のプロセス変数の利点は、新規プロセス工程が全体としてプロセスに導入さ れないことである。The advantage of the latter process variable is that the new process step is introduced into the process as a whole. This is something that cannot be done.
本発明によれば、酸性基のアルファ位が置換されていない化合物（Ｉ）〜（■） が使用される。一つの例は、テトラデシルスルホネートである。アルファ位が置 換されている、従って本発明で使用されない化合物の例は、２−ヒドロキシ−ド デシルスルホネート−１および１−カルボキン−トリデシルスルホネート−２で ある。According to the present invention, compounds (I) to (■) in which the alpha position of the acidic group is not substituted is used. One example is tetradecyl sulfonate. Alpha position is An example of a compound which has been converted and is therefore not used in the present invention is the 2-hydroxy-dolphin with decylsulfonate-1 and 1-carboxine-tridecylsulfonate-2 be.
−（モノ）不飽和でアルファ位が置換されていない分子内スルホン酸基を有する アニオン性界面活性化合物のオレイン酸スルホネートが本発明における好ましい 例である。後者は、市販のオレイン酸を前述の方法によりスルホン化することに より得られる。オレイン酸分子内のＳＯ，Ｈ基の正確な位置は、スルホン化条件 によって異性化が起こるので定まっていない。本発明において好ましい更なるア ニオン性界面活性化合物は、西ドイツ特許出願Ｐ ３７ ２５０３０．２に従っ て製造される１〜ヒドロキシ−オクタデセニル−スルホネート−９である。- (Mono)unsaturated and has an intramolecular sulfonic acid group that is not substituted at the alpha position The anionic surfactant compound oleic acid sulfonate is preferred in the present invention. This is an example. The latter was obtained by sulfonating commercially available oleic acid using the method described above. More can be obtained. The exact positions of SO and H groups in the oleic acid molecule are determined by the sulfonation conditions. It is not determined because isomerization occurs due to Further preferred embodiments of the present invention The ionic surface-active compounds were prepared according to West German patent application P 37 25030.2. 1-Hydroxy-octadecenyl-sulfonate-9 produced by
本発明の好ましい態様によれば、既に定義した化合物（Ｉ）のうち以下の化合物 が用いられる： ＡがＨＯＩＳ ＣＨｚ（ＣＨｚ）、ＣＨ（ＯＨＸＣＨ２）−−及び／又１ｔＨＯ −ＣＨ２（ＣＨｓ）アＣＨ（Ｓ Ｏｓ Ｈ） （ＣＨ２）。−にこで、ｑ＝４〜 １４、ｙ＝１または２コおよびＲが−ＣＨ３を表すスルホン酸（Ｄ。According to a preferred embodiment of the present invention, the following compounds among the already defined compounds (I) is used: A is HOIS CHz (CHz), CH (OHXCH2) -- and/or 1tHO -CH2(CHs)aCH(SOsH)(CH2). -Nikode, q=4~ 14, sulfonic acid (D) in which y=1 or 2 and R represents -CH3.
テトラデシルスルホネート−１が一例である。Tetradecyl sulfonate-1 is an example.
ＡがＣＨｓ（ＣＨ２）、 ＣＨ（ＯＨＸＣＨｚ）、ＣＨ（Ｓ ＣｈＨＸＣＲ２） −一及び／又１ｔＣＨ３（ＣＨ２）、ＣＨ（Ｓ０３ＨＸＣＨ２）、ＣＨ（ＯＨＸ ＣＨ２）、−にこで、）Ｈ＋ｙ＋ｚ＝１２〜１４、ｙ＝１または２、Ｘ、ｚ＝Ｏ 〜１３コおよびＲが−Ｃ：Ｈ，Ｏ（Ｃ，Ｒ２，Ｏ）、ＨＥｐ＝Ｏコ、−ＣＨ２０ （Ｃ，Ｈｚ、ＯＬＨ［ｎ＝’２、ｐ＝５３または−ＣＯＯＲ”（Ｒ”＝Ｈコのう ちの一つを表すスルホン酸（Ｉ）。A is CHs (CH2), CH (OHXCHz), CH (S ChHXCR2) -1 and/or 1tCH3(CH2), CH(S03HXCH2), CH(OHX CH2), - Nicode,) H+y+z=12-14, y=1 or 2, X, z=O ~13 and R are -C:H,O(C,R2,O), HEp=O, -CH20 (C, Hz, OLH [n='2, p=53 or -COOR" (R"=H Sulfonic acid (I) represents one of the following.
例は、１．−ヒドロキシ−オクタデセニル−スルホネート（分子内）、オクタデ セニルペンタ（オキシエチレン）エーテルスルホネート、オクタデセン酸スルホ ネートである。Examples are 1. -Hydroxy-octadecenyl-sulfonate (intermolecular), octade Cenylpenta(oxyethylene)ether sulfonate, octadecenoic acid sulfonate It's Nate.
本発明の好ましい態様によれば、既に定義した以下の化合物（ｎ）〜（■）が用 いられる： Ｒ１が８〜２２個の炭素原子を含む直鎖飽和アルキル基を表すホスホン酸（ＩＩ ）。一つの例は、テトラデシルモノホスホン酸である。According to a preferred embodiment of the present invention, the following compounds (n) to (■) previously defined are used. You can stay: Phosphonic acid (II ). One example is tetradecyl monophosphonic acid.
Ｒ２が７〜１７個の炭素原子を含む直鎖または分岐状で飽和または不飽和のアル キル基、およびＲ３がメチル基を表すホスホン酸＜ｍ）。例として、インノナノ イルアミド−１，１−ジメチルメタン−ホスホン酸およびヤン油脂肪酸アミドー １．１−ジメチルメタン−ホスホン酸が挙げられる。R2 is a linear or branched saturated or unsaturated alkali containing 7 to 17 carbon atoms; kill group, and phosphonic acids in which R3 represents a methyl group <m). As an example, Innonano ylamide-1,1-dimethylmethane-phosphonic acid and Yang oil fatty acid amide 1.1-dimethylmethane-phosphonic acid is mentioned.
Ｒ１が８〜２２個の炭素原子を含む直鎖飽和アルキル基およびａが２〜４の整数 を表すホスホン酸（ＩＶ）。ＣＩ ２／＋ ４−アルキルエーテル−エタノール アミン−メチレンホスホン酸が一つの例である。R1 is a straight chain saturated alkyl group containing 8 to 22 carbon atoms and a is an integer of 2 to 4 Phosphonic acid (IV) representing CI 2/+ 4-alkyl ether-ethanol Amine-methylenephosphonic acid is one example.
Ｒ１が８〜２２個の炭素原子を含む直鎖飽和アルキル基、Ｒ４が水素または−Ｃ Ｈ！ Ｐ Ｏｓ Ｈ２、ａが２〜４の整数およびｂが２．４または６を表すホス ホン酸（Ｖ）。Ｎ−Ｃ＋ａｚｕ−アルキル−へキサメチレン−ジアミン−メチレ ンホスホン酸が一つの例である。R1 is a straight chain saturated alkyl group containing 8 to 22 carbon atoms, R4 is hydrogen or -C H! P Os H2, a phosphorus in which a is an integer of 2 to 4 and b is 2.4 or 6 Phonic acid (V). N-C+azu-alkyl-hexamethylene-diamine-methylene One example is phosphonic acid.
Ｃが８〜１２の整数を表すホスホン酸（Ｖｉ［）。１１−アミノ−１−ヒドロキ シウンデカン−１，１−ジホスホン酸が一例である。Phosphonic acid (Vi[) in which C represents an integer of 8 to 12. 11-amino-1-hydroxy Cyundecane-1,1-diphosphonic acid is an example.
ｄが７〜１１の整数およびｅが３を表すホスホン酸（■）。アルファカルボキシ ウンデカン−ω−ホスホン酸が一例である。A phosphonic acid (■) in which d represents an integer of 7 to 11 and e represents 3. alpha carboxy Undecane-ω-phosphonic acid is an example.
ｆと９の合計が１３〜１７の整数を表すホスホン酸（■）。１２−ヒドロキシ− １２−ホスホノステアリン酸が一例である。Phosphonic acid (■) in which the sum of f and 9 represents an integer of 13 to 17. 12-hydroxy- 12-phosphonostearic acid is an example.
上記遊離酸に加えて、本発明において、もちろん、その水溶性アルカリ塩および アルカリ土類金属塩ならびにそれらのアンモニウムおよびアミン塩、特に、メチ ルアミン、ジェタノールアミンまたはピリジンから誘導される塩を用いることが できる。上記スルホン酸、ホスホン酸および亜ホスホン酸のナトリウム塩を用い ることが特に好ましい。In addition to the above-mentioned free acids, of course the water-soluble alkali salts thereof and Alkaline earth metal salts and their ammonium and amine salts, especially meth Salts derived from oleamine, jetanolamine or pyridine can be used. can. Using the sodium salts of the above sulfonic acids, phosphonic acids and phosphorous acids It is particularly preferable that
アニオン性界面活性化合物を従来技術から知られている封孔助剤と共に表面に接 触させることにより含浸のプロセスを行う場合、用いられる封孔助剤の例は、Ｒ ３−アルメコジール（ａｌｍｅｃｏｓｅａｌ ：登録商標）ＳＬ［ドイツ国ヘン ケル社（Ｈｅｎｋｅｌ ＫＧａＡ）製〕、Ｒ３−アルメコジールＣ１（ドイツ国 ヘンケル社製）またはジールザルッ（Ｓｅａｌｓａｌｚ） Ａ Ｓ ［スイス国 すンド社（Ｓ ａｎｄｏｚ）製〕であり、各々０．５〜４９／ｌの濃度で用いら れる。Anionic surfactant compounds are applied to the surface together with sealing aids known from the prior art. When carrying out the process of impregnation by contacting, examples of sealing aids used are R 3-almecoseal (registered trademark) SL [Hen, Germany] manufactured by Henkel KGaA], R3-Almecosil C1 (Germany) Henkel) or Sealsalz AS [Switzerland] (manufactured by S andoz) and used at a concentration of 0.5 to 49/l, respectively. It will be done.
封孔プロセスおよび含浸が別の工程で行われる場合、同じ封孔助剤を用いること ができる。If the sealing process and impregnation are done in separate steps, the same sealing aid should be used. Can be done.
実施例 Ａ）凝縮水試験環境における比較試験 以下の実施例において、Ａｌ１９．８５を圧延した光沢のあるサンプルシート（ ７５ｍｍＸ １０５ｍｍＸ ０．５ｍｍ）を用いた。Example A) Comparative test in condensed water test environment In the following examples, a glossy sample sheet rolled from Al19.85 ( 75 mm x 105 mm x 0.5 mm) were used.
シートは、３重量％のＲ３−アルメコ １８（ボレート、カーボネート、ホスフ ェートおよび非イオン性界面活性剤を含むアルカリ性清浄化剤）を含む水溶液中 、７０℃の温度で浸漬時間を２分として清浄化した。The sheet contains 3% by weight of R3-Almeco 18 (borate, carbonate, phosphide). alkaline detergents, including esters and non-ionic surfactants). , and a immersion time of 2 minutes at a temperature of 70°C.
プロセスの各工程後、被処理材を脱イオン水で充分に濯いだ。After each step of the process, the treated material was thoroughly rinsed with deionized water.
直流／硫酸プロセスにより以下の陽極酸化を行った。The following anodization was performed using a direct current/sulfuric acid process.
組成：硫酸２００ｇ／４ニアルミニウム１０ｇ／＃、空気吹込量：８ ｍ’／ａ ２／ｈＳ温度：１８℃、直流：１６Ｖ０陽極酸化時間はフィルム形成１ミクロン 当たり約３分とした、すなわち以下の実施例において３ミクロンの酸化物フィル ムの形成のために要した合計陽極酸化時間は９〜１０分であった。Composition: sulfuric acid 200g/4 Ni aluminum 10g/#, air blowing amount: 8 m'/a 2/hS temperature: 18℃, DC: 16V0 anodic oxidation time is 1 micron film formation approximately 3 minutes per minute, i.e. 3 micron oxide film in the following examples. The total anodization time required for the formation of the film was 9-10 minutes.
脱イオン水でさらに充分に濯いだ後、以下の電解着色処理を行った； 浴組成；Ｒ３−アルメコロール（Ａ １ｍｅｃｏｌｏｒ ：登録商標）ｐ（硫酸 錫（ｎ）、錫５５％含有）２ Ｃｈ／ｌ、 Ｐ ３−アルメコロールＳ（鉄（Ｉ Ｉ）塩および有機スルホン酸＞２５ｑ／１、硫酸１８ｗ／／：交流、２０〜２５ ℃で１６ｖ：着色時間１分。After further rinsing thoroughly with deionized water, the following electrolytic coloring treatment was performed; Bath composition: R3-almecolor (A1mecolor: registered trademark) p (sulfuric acid Tin (n), containing 55% tin) 2 Ch/l, P 3-almecolol S (iron (I I) Salts and organic sulfonic acids>25q/1, sulfuric acid 18w//: AC, 20-25 16V at °C: coloring time 1 minute.
このシートを再度濯いだ後、浴温度９８〜１００℃、浸漬時間１分、封孔塗膜抑 制剤濃度０．２重量％として、西ドイツ公開特許２６ ５０ ９８９号の封孔助 剤を添加して温水中で封孔した。次に本発明による後処理を行った。After rinsing this sheet again, the bath temperature was 98-100°C, the immersion time was 1 minute, and the pore-sealing coating was inhibited. With a drug concentration of 0.2% by weight, the sealing assistant of West German Published Patent No. 2650989 was used. agent was added and the holes were sealed in warm water. Next, post-treatment according to the present invention was performed.
水溶液中のアニオン性界面活性化合物の濃度を０．１ｙ／Ａ、溶液の温度を６０ ℃および処理時間を１分とした。実施例３においてのみサンプルを１００℃で３ 分間後処理し、実施例４では濃度を５ｑ／ｌに上昇させた。各実施例において含 浸溶液のｐＨは溶解により所定の濃度に調整した。ｐＨが５〜９の値でない場合 、酢酸およびアンモニア溶液によりｐＨをその範囲の値に調節した。The concentration of anionic surfactant compound in the aqueous solution was 0.1y/A, and the temperature of the solution was 60%. ℃ and treatment time were 1 minute. Only in Example 3, samples were heated at 100°C. After treatment for 1 minute, the concentration was increased to 5 q/l in Example 4. In each example, The pH of the immersion solution was adjusted to a predetermined concentration by dissolution. If the pH is not between 5 and 9 , the pH was adjusted to values in that range with acetic acid and ammonia solution.
保護フィルムの品質は、ＤＩＮ ５００１７ ＫＫによる凝縮水試験環境におい て１３日かけて決めた。未処理シートの場合、凝縮水の影響下に表面に対する腐 食攻撃が時間の経過と共に増加した。The quality of the protective film is determined in the condensate test environment according to DIN 50017 KK. It took me 13 days to decide. In the case of untreated sheets, corrosion to the surface under the influence of condensed water Food attack increased over time.
このことは、汚れ発生の場合、装飾的外観が損なわれ、その結果、無光沢マット の平坦塗膜が光沢のある外観となる。すなわち影響を受ける表面の広さは、腐食 攻撃の程度の指標となる、または処理表面を比較のために凝集水試験環境におい て試験したときの本発明による剤の保護効果の指標として役立ち得る。This means that in case of staining, the decorative appearance will be compromised and the result will be a matte matte finish. The flat coating has a glossy appearance. That is, the extent of the affected surface is To provide an indication of the degree of attack or to compare treated surfaces in a flocculating water test environment. may serve as an indicator of the protective effect of the agent according to the invention when tested in the following manner.
実施例１ 含浸はテトラデシルスルホネート−１を用いて上記条件により行った。Example 1 Impregnation was carried out using tetradecyl sulfonate-1 under the above conditions.
表１に、凝縮水試験環境において３．６．８．１０および１３日後に得られたデ ータを未処理サンプルと比較して示す。Table 1 shows the data obtained after 3.6.8.10 and 13 days in the condensate test environment. The data are shown in comparison to the untreated sample.
比較例１ 含浸は、２−ヒドロキシドデシルスルホネート−１を用いて上記条件下に実施し た。Comparative example 1 Impregnation was carried out using 2-hydroxydodecyl sulfonate-1 under the above conditions. Ta.
表１に、凝集水試験環境において３．６．８．１０および１３日後に得られたデ ータを未処理サンプルと比較して示す。Table 1 shows the data obtained after 3.6.8.10 and 13 days in the flocculating water test environment. The data are shown in comparison to the untreated sample.
比較例２ 含浸に、１−カルボキシ一トリデンルスルホ不−トー２を用いて上記条件に従っ て実施した。Comparative example 2 For impregnation, 1-carboxy tridenyl sulfonate 2 was used and according to the above conditions. It was carried out.
表１は、凝縮水試験環境において３．６．８．１０および１３日後に得られたデ ータを未処理サンプルと比較して示す。Table 1 shows the data obtained after 3.6.8.10 and 13 days in the condensate test environment. The data are shown in comparison to the untreated sample.
攻撃面積の割合（％） 実施例 ３日後 ６日後 ８日後 １０日後 １３日後１ ０’３３ ３９ ６ ４ ６６ 比較例１ ２９ ４２ ７３ ９２ ９３比較例２ ５７ ７８ ７８ ９２ ９２未処理 ５６ ７２ ７８ ９２ １００含浸は、１−ヒドロキシ−オクタ デセニルスルホネートを用いて上記条件に従って実施した。Percentage of attack area (%) Example 3 days later 6 days later 8 days later 10 days later 13 days later 1 0'33 39 6 4 66 Comparative example 1 29 42 73 92 93 Comparative example 2 57 78 78 92 92 Untreated 56 72 78 92 100 Impregnated with 1-hydroxy-octa It was carried out according to the above conditions using decenyl sulfonate.
表２に、凝縮水試験環境において３．６．８．１０および１３日後に得られたデ ータを未処理サンプルと比較して示す。Table 2 shows the data obtained after 3.6.8.10 and 13 days in the condensate test environment. The data are shown in comparison to the untreated sample.
１−ヒドロキシ−オクタデセニル−スルホネート１．１ 酢酸オレイル（工業用 ） 工業用オレイルアルコール［）（Ｄ−オセノール（ＯｃｅｎｏＥ ：登録商標） ９０／９５、ヨウ素価９４、ヒドロキシル価２１０〕を無水酢酸（２０モル％過 剰）と１１８℃で４時間反応させた。次に反応混合物を氷水に注ぎ、有機相を水 で複数回洗った。得られた粗エステルを乾燥し、蒸留により清浄化した。得られ たエステルのヨウ素価は８３であり、残留ヒドロキシル価は０．９であった。1-Hydroxy-octadecenyl-sulfonate 1.1 Oleyl acetate (industrial use) ) Industrial oleyl alcohol [) (D-ocenoE: registered trademark) 90/95, iodine number 94, hydroxyl number 210] was dissolved in acetic anhydride (20 mol% filtrate). (residue) at 118°C for 4 hours. The reaction mixture was then poured into ice water and the organic phase was poured into water. I washed it multiple times. The crude ester obtained was dried and purified by distillation. obtained The iodine value of the obtained ester was 83, and the residual hydroxyl value was 0.9.
１、 ２ ヒドロキシスルホネートの製造１．２．Ｉ ＳＯ３１モルによるスル ホン化１、 １からの酢酸オレイル３１０ｇ（１モル）を、冷却用ジャケットを 有する８００１１１静置反応器に仕込み、ＳＯｓ８０ｇ（１モル）を用いて３０ ℃でスルホン化した。ＳＯ３は相当量の発煙硫酸から加熱により誘導し、Ｎ２で ５体積％の濃度に希釈し、反応混合物の温度を冷却により４０℃以下に維持しつ つ酢酸オレイルに３２分間導入した。 スルホン化後、反応混合物を撹拌下に水 酸化ナトリウム８４９（２，１）モルの水１５００９中希薄溶液に混入した。次 に、この混合物を、スチーム浴上、９５〜１００℃の温度で４時間加水分解した 。２０℃に冷却後、反応混合物のｐＨを塩酸溶液の添加により７．０に調節した 。1, 2 Production of hydroxysulfonate 1.2. I Sulfur with 1 mol of SO3 Honification 1, 310 g (1 mol) of oleyl acetate from 1 was placed in a cooling jacket. 800111 static reactor with 800111, and using 80 g (1 mol) of SOs, 30 Sulfonation was carried out at °C. SO3 is derived from a considerable amount of oleum by heating and then extracted with N2. dilute to a concentration of 5% by volume and maintain the temperature of the reaction mixture below 40°C by cooling. oleyl acetate for 32 minutes. After sulfonation, the reaction mixture was poured into water with stirring. 849 (2,1) moles of sodium oxide were mixed into a dilute solution in 15,009 moles of water. Next The mixture was hydrolyzed on a steam bath for 4 hours at a temperature of 95-100°C. . After cooling to 20 °C, the pH of the reaction mixture was adjusted to 7.0 by addition of hydrochloric acid solution. .
アニオン性界面活性剤（ＤＧＦ−Ｈ−１１１−１０）：０、７２３ｍｖａｌ／ｅ 不飽和成分（ＤＧＦ７Ｇ−１１１−６ｂ）：２．０重量％ Ｎａ２ＳＯ４： ２．Ｏ重量％ ＣＨ，Ｃ○○Ｎａ： ４．Ｑ重量％ １、 ２． ２ 流下液膜式反応器における製造連続的に操作されている流下液 膜式反応器において、（１，１による）酢酸オレイル３．１ｋｇ（１０モル）を 処理量１０９／分として３０℃で、量比酢酸オレイル： Ｓｏ、＝１ ：１．３ としてＳ０３と反応させた。粗スルホン化生成物を連続的に水酸化ナトリウム希 薄水溶液に撹拌混入し、１．２．１に従って加水分解および処理した。得られた 生成物は以下の特性を有していた。Anionic surfactant (DGF-H-111-10): 0, 723 mval/e Unsaturated component (DGF7G-111-6b): 2.0% by weight Na2SO4: 2. O weight% CH, C○○Na: 4. Q weight% 1, 2. 2 Production in a falling film reactor Continuously operated flowing liquid In a membrane reactor, 3.1 kg (10 moles) of oleyl acetate (according to 1,1) At 30°C with a throughput of 109/min, the quantitative ratio of oleyl acetate: So, = 1: 1.3 It was reacted with S03 as The crude sulfonation product is continuously diluted with sodium hydroxide. Stir into a dilute aqueous solution, hydrolyze and process according to 1.2.1. obtained The product had the following properties:
アニオン性界面活性剤（ＤＧＦ−Ｈ−１１１−１０）：１、４９８ｍｖａｌ／ｇ 未スルホン化成分（ＤＧＦ−Ｇ−１１１−５ｂ）：５．０重量％ ＮａｚＳＯ４二 １．Ｏ重量％ ＣＨｘＣＯＯＮａ ５．０重量％ 実施例３ 分子内オクタデカン酸スルホネートを用い、上記条件により含浸を行った。濃度 は０．１９／Ａ’１処理時間は３時間および温度は１０含浸のためにここで分子 内オクタデセン酸スルホネートも用いたが、実施例３とは対照的に、濃度を５ｑ ／ｌとした。Anionic surfactant (DGF-H-111-10): 1, 498 mval/g Unsulfonated component (DGF-G-111-5b): 5.0% by weight NazSO42 1. O weight% CHxCOONa 5.0% by weight Example 3 Impregnation was performed using intramolecular octadecanoic acid sulfonate under the above conditions. concentration is 0.19/A'1 where the treatment time is 3 hours and the temperature is 10 for impregnation. Octadecenoic acid sulfonate was also used, but in contrast to Example 3, the concentration was reduced to 5q /l.
表２に、実施例３および４において凝集水試験環境において３．６．８、ｌＯお よび１３日後に得られたデータを未処理サンプルと比較して示す。Table 2 shows that in Examples 3 and 4, 3.6.8, 1O and The data obtained after 1 and 13 days are shown in comparison with the untreated sample.
オクタデセン酸スルホネートの製造 加熱および冷却ジャケットを有する連続的に操作されている流下液膜式反応器（ 容量約６００ｅ／ｈ）において、工業用オレイン酸を空気希釈Ｓ０３ガス（空気 中５体積％５Ｏ３）と反応させた。ＳＯ８対オレイン酸の量比は１．０：１．０ であった。主反応生成物を過酸化水素で連続的に漂白し、水酸化ナトリウム水溶 液で中和および加水分解した。生成物は下記特性を有していた：アニオン性界面 活性剤（ＤＧＦ−Ｈ−ＩＴＩ−１０）＋ ５２．８％未スルホン化成分（ＤＧＦ −Ｇ −Ｉ Ｉ Ｉ −６ｂ） ： ５．０％Ｎａ２ＳＯ４： ２．０％ 水含量： ４０．０％ 実施例５ 分子内オクタデセニル−ペンタ（オキシエチレン）ニーチル−スルホネートを用 いて、上記条件に従って含浸を実施した。Production of octadecenoic acid sulfonate Continuously operated falling film reactor with heating and cooling jackets ( At a capacity of about 600 e/h), industrial oleic acid was mixed with air diluted S03 gas (air 5% by volume of 5O3). The ratio of SO8 to oleic acid is 1.0:1.0 Met. The main reaction product is continuously bleached with hydrogen peroxide and then dissolved in sodium hydroxide. Neutralized and hydrolyzed with liquid. The product had the following properties: anionic interface Activator (DGF-H-ITI-10) + 52.8% unsulfonated component (DGF -G -I I I -6b): 5.0% Na2SO4: 2.0% Water content: 40.0% Example 5 Using intramolecular octadecenyl-penta(oxyethylene)neethyl-sulfonate The impregnation was carried out according to the above conditions.
表２に、凝集水試験環境において３．６．８．１０および１３日後に得られたデ ータを未処理サンプルと比較して示す。Table 2 shows the data obtained after 3.6.8.10 and 13 days in the flocculating water test environment. The data are shown in comparison to the untreated sample.
オクタデセニル−ペンタ（オキシエチレン）ニーチル−スルホネートの製造 オレイル−ペンタ（オキシエチレン）−アセテート実施例２と同様に、エチレン オキシド５モルを工業用オレイルアルコールに（実施例２のように）添加した。Production of octadecenyl penta(oxyethylene) nityl sulfonate Oleyl-penta(oxyethylene)-acetate Similar to Example 2, ethylene 5 moles of oxide were added to technical oleyl alcohol (as in Example 2).
次にオキシエチレントを実施例２のようにアセテートに転化した。The oxyethylene was then converted to acetate as in Example 2.
エーテルスルホネートの製造 オレイル−ペンタ（オキシエチレン）−アセテート３２０ｇを１１分間で導入し 、オレイル−ペンタ（オキシエチレン）−アセテート１モル当たり１．３モルの Ｓ０３を用いて実施例２のようにスルホン化し、実施例２に従って処理すること により、下記特性を有するエーテルスルホネートを得た： アニオン性界面活性剤（ＤＧＦ−Ｈ−Ｉ Ｉ ｌ−１０）・０、３６２ｍｖａｌ ／ｇ 未スルホン化成分（ＤＧＦ−Ｇ−Ｉ １１−６ｂ）：６．０重量％ Ｎａ２Ｓ ０４ ： ３．０重量％ ＣＨ３ＣＯＯＮａ： ３．０重１に％ 分子内オクタデセニルーデカ（オキシエチレン）エーテル−スルホネートを用い て、上記条件に従って含浸を行った。Production of ether sulfonates 320 g of oleyl-penta(oxyethylene)-acetate was introduced in 11 minutes. , 1.3 mol per mol of oleyl-penta(oxyethylene)-acetate Sulfonation as in Example 2 using S03 and processing as in Example 2. An ether sulfonate with the following properties was obtained: Anionic surfactant (DGF-H-I Il-10)・0, 362mval /g Unsulfonated component (DGF-G-I 11-6b): 6.0% by weight Na2S 04: 3.0% by weight CH3COONa: 3.0% to 1% Using intramolecular octadecenyludeca(oxyethylene)ether-sulfonate Then, impregnation was carried out according to the above conditions.
表２に、凝縮水拭環境において３．６．８．１０および１３日後に得られたデー タを未処理サンプルと比較して示す。Table 2 shows the data obtained after 3.6.8.10 and 13 days in a condensate wipe environment. The data are shown in comparison with the untreated sample.
オレイルアルコール１モル当たり１０モルのエチレンオキシドを用いて実施例４ と同様に製造を行った。Example 4 using 10 moles of ethylene oxide per mole of oleyl alcohol Manufactured in the same way.
比較例４ 分子内オクタデセニル−エイコサ（オキシエチレン）エーテル−スルホネートを 用いて、上記条件に従って含浸を実施した。Comparative example 4 Intramolecular octadecenyl-eicosa(oxyethylene) ether-sulfonate Impregnation was carried out according to the conditions described above.
表２に、凝縮水試験環境において３．６．８．１０および１３日後に得られたデ ータを未処理サンプルと比較して示す：実施例６ 分子内オクタデセン酸−オクタデセニルエステル−ジスルホネートを用いて、上 記条件に従って含浸を実施した。Table 2 shows the data obtained after 3.6.8.10 and 13 days in the condensate test environment. Example 6 Using intramolecular octadecenic acid-octadecenyl ester-disulfonate, Impregnation was carried out according to the conditions described above.
表２に、凝縮水試験環境において３．６．８．１０および１３日後に得られたデ ータを未処理サンプルと比較して示す。Table 2 shows the data obtained after 3.6.8.10 and 13 days in the condensate test environment. The data are shown in comparison to the untreated sample.
オクタデセン酸−オクタデセニルエステル−ジスルホネートの製勇 流下液膜式反応器におけるオレイルオレエートのスルホン化流下液膜式反応器は 、ガラス製であり加熱および冷却ジャケットにより包囲されている長さ１１００ ｍｍおよび内径５ｍｍのパイプを有していた。反応器の頂部にエステル出発物質 のための供給機構およびガス導入バイブが設けられていた。発煙硫酸の加熱によ り得られた気体二酸化硫黄を窒素との混合物（二酸化硫黄５体積％）として用い た。Production of octadecenic acid-octadecenyl ester-disulfonate Sulfonation of oleyl oleate in a falling film reactor The falling film reactor is , length 1100, made of glass and surrounded by heating and cooling jackets. mm and had a pipe with an internal diameter of 5 mm. Ester starting material at the top of the reactor A supply mechanism and gas introduction vibrator were provided for. By heating fuming sulfuric acid Using the gaseous sulfur dioxide obtained as a mixture with nitrogen (5% by volume of sulfur dioxide) Ta.
オレイルオレエート混合物１０９／分の一定速度で添加した。二酸化硫黄−窒素 含有混合物の供給は、オレイルオレエート：二酸化硫黄の量比が１：２（２重結 合当たり二酸化硫黄１モル）となるように調節した。主反応混合物を過酸化水素 で連続的に漂白し、水酸化ナトリウムで中和し、次に、実施例１のように混合物 を加水分解し、処理した。The oleyl oleate mixture was added at a constant rate of 109/min. sulfur dioxide - nitrogen The mixture containing oleyl oleate: sulfur dioxide is supplied in a quantitative ratio of 1:2 (double solids). The amount of sulfur dioxide was adjusted to be 1 mol per mol of sulfur dioxide. The main reaction mixture is hydrogen peroxide. and neutralize with sodium hydroxide, then bleach the mixture as in Example 1. was hydrolyzed and treated.
生成物特性： アニオン性界面活性剤 ５２重量％ （０、９２ｍｖａｌ／ ｅ） 未スルホン化成分： １１重量％ スルフェート（硫酸ナトリウムとして）＝ ４重量％水（ツイツタ＋ −（Ｆ １ｓｃｈｅｒ）による）＝ ３３重量％表２ 攻撃面積の割合（％） 実施例 ３日後 ６日後 ８日後 １０日後 １３日後比較例３ ３６ ７８ ７８ ９２ １００比較例４ ７５ ７５ ７５ ８３ １００分子内オクタデ セン酸−スルホ不一トおよび同時に０．５ｑ／ｌのＰ３−アルメコジール（登録 商標）ＳＬを９８〜１００℃の温度で３分間用いることにより、含浸および同時 に封孔を行った。Product characteristics: Anionic surfactant 52% by weight (0, 92mval/e) Unsulfonated component: 11% by weight Sulfate (as sodium sulfate) = 4% by weight water (Tsitsuta + - (F) 1scher) = 33% by weight Table 2 Percentage of attack area (%) Example 3 days later 6 days later 8 days later 10 days later 13 days later Comparative example 3 36 78 78 92 100 Comparative Example 4 75 75 75 83 100 Octade in the molecule senic acid-sulfonate and at the same time 0.5 q/l of P3-almecodil (Reg. Impregnation and simultaneous The hole was sealed.
表３に、４．８．１０および１３日後に得られたデータを未処理サンプルと比較 して示す。Table 3 compares the data obtained after 4.8.10 and 13 days with the untreated sample. and show.
表呈 攻撃面積の割合（％） 実施例 ４日後 ８日後 １０日後 １３日後下記ホスホン酸を用いて、上記条 件に従って含浸を行った。表４に、凝縮水試験環境において４．６．１１および １３日後審＝得られたデータを未処理サンプルと比較して示す。expression Percentage of attack area (%) Example 4 days later 8 days later 10 days later 13 days later Using the following phosphonic acid, the above conditions were Impregnation was carried out according to the requirements. Table 4 shows 4.6.11 and 13-day post-examination = Data obtained are shown in comparison with untreated samples.
実施例８： テトラデシルモノホスホン酸実施例９： イソノナノイルアミド− １，１−ジメチルメタンホスホン酸 実施例１０： ヤシ油脂肪酸アミド−１，１−ジメチルメタンホスホン酸 実施例１１ ： ＣＩ２／＋４−アルキルエーテルエタノールアミン−メチレン ホスホン酸 実施例１２ ： Ｎ−Ｃｌ６／Ｉ８−アルキル−へキサメチレンジアミン−メチ レン−ホスホン酸 実施例１３： １１−アミノ−１−ヒドロキシウンデカン−１゜１−ジホスホン 酸 比較例５： １−ヒドロキシデカン−１，１−ジホスホン酸Ｎａ。Example 8: Tetradecyl monophosphonic acid Example 9: Isononanoylamide 1,1-dimethylmethanephosphonic acid Example 10: Coconut oil fatty acid amide-1,1-dimethylmethanephosphonic acid Example 11: CI2/+4-alkyl ether ethanolamine-methylene phosphonic acid Example 12: N-Cl6/I8-alkyl-hexamethylenediamine-methy Ren-phosphonic acid Example 13: 11-amino-1-hydroxyundecane-1°1-diphosphone acid Comparative Example 5: Sodium 1-hydroxydecane-1,1-diphosphonate.
塩 比較例６： １−ヒドロキシドデカン−１−ホスホン酸告ｌ 攻撃面積の割合（％） 実施例 ４日後 ６日後 １１日後 １３日後比較例５ ６２ ９３ ９７ １ ００ 比較例６ ９６ ９６ ９６ ９６ 未処理 ５６ ７２ ９２ １００ 以下の実施例において、ＡｆＭｇｓ材料（ＤＴＮ３３ ５３５による）のサンプ ルンー）（１０ＱｍｍＸ ２０ ＱｍｍＸ ２闘）を用いた。陽極酸化の前に、 シートを脱脂し、酸洗し、税スケールした。salt Comparative Example 6: 1-hydroxydodecane-1-phosphonic acid Percentage of attack area (%) Example 4 days later 6 days later 11 days later 13 days later Comparative example 5 62 93 97 1 00 Comparative example 6 96 96 96 96 Unprocessed 56 72 92 100 In the following examples, samples of AfMgs material (according to DTN33 535) (10 Qmm x 20 Qmm x 2 fights) was used. Before anodizing, The sheets were degreased, pickled and tax scaled.
脱脂・３重量％のＰ３−アルメコ（登録商標）１８（ボレート、カーボネート、 ホスフェートおよび非イオン性界面活性剤を含んでなるアルカリ性クリーナー） を含む水溶液中、７０℃の温度で＆置時間１０分として行った。Degreased and 3% by weight of P3-Almeco (registered trademark) 18 (borate, carbonate, alkaline cleaners comprising phosphates and nonionic surfactants) The test was carried out in an aqueous solution containing the following at a temperature of 70° C. and for a standing time of 10 minutes.
酸洗：ＮａＯＨおよびＰ３−アルメコ（登録商標）４６（アルカリ、アルコール および無機酸の塩を含む酸洗添加剤）の３：１混合物を含む濃度８重量％の水溶 液中、５４〜５６℃の温度で浸漬時間を１０分として行った。Pickling: NaOH and P3-Almeco (registered trademark) 46 (alkali, alcohol and pickling additives containing salts of inorganic acids) at a concentration of 8% by weight. The immersion was carried out in the liquid at a temperature of 54 to 56°C for 10 minutes.
脱スケール：２５％硝酸中、２０℃で浸漬時間を１ｏ分として行った。Descaling: Descaling was carried out in 25% nitric acid at 20° C. for 10 min.
プロセスの各工程後、シートを脱イオン水で充分に濯いだ。次に、既述したよう に、それらを直流−硫酸プロセスに従って陽極酸化した。ここで、以下の実施例 における２０〜２２ミクロンの酸化物フィルム厚を得るための合計陽極酸化時間 は６０分であった。After each step of the process, the sheets were thoroughly rinsed with deionized water. Next, as mentioned above Then, they were anodized according to the DC-sulfuric acid process. Here, the following example Total anodization time to obtain an oxide film thickness of 20-22 microns in was 60 minutes.
さらに脱イオン水で充分に濯いだ後、やはり上述のように電解着色処理を行った 。しかしながら、〔オイラス（ＥＵＲＡＳ）色チャートによる〕Ｃ３４の色調が 得られるまでの着色時間は７分であった。After further rinsing thoroughly with deionized water, electrolytic coloring was performed as described above. . However, the color tone of C34 [according to the EURAS color chart] is The coloring time until the coloring was obtained was 7 minutes.
このように予備処理した暗青銅色／−トを、浴温を９８〜１００℃、］）Ｈを５ ，５〜７、フィルム厚１ミクロン当たり３分の封孔時間として、上述のように封 孔した。The dark bronze color pretreated in this way was heated to a bath temperature of 98 to 100°C, ]) , 5-7, the sealing time was 3 minutes per 1 micron of film thickness, and the sealing was performed as described above. I made a hole.
実施例１４ 封孔路は、含浸添加剤として分子内オクタデセン酸スルボネート０．１９／Ａ’ を含んでいたが、他の封孔助剤は含んでぃなかった。Example 14 The sealing channel was made using intramolecular octadecenoic acid sulfonate 0.19/A' as an impregnating additive. but did not contain other sealing aids.
実施例１５ 一封孔浴は、含浸添加剤として１２−ヒドロキシ−１２−ポスボッ−ステアリン 酸−Ｎａ３−塩０．０５９／ｌを含んでいたが、他の封孔助剤は含んでいなかっ た。Example 15 One sealing bath uses 12-hydroxy-12-posbo-stearin as an impregnating additive. Contained 0.059/l of acid-Na3-salt, but no other sealing aids. Ta.
実施例１６ 封孔路は、含浸添加剤は含まなかったが、西ドイツ公開特許２６５０ ９８９に よる封孔助剤は含んでいた。次に、テトラチンルー１−ホスホン酸０．１ｇ／／ を含む別の含浸浴中において処理を行った。Example 16 The sealing channel did not contain impregnating additives, but was Contains a sealing aid. Next, 0.1 g of tetratine-1-phosphonic acid// The treatment was carried out in a separate impregnation bath containing:
比較例７ 上述のようにして西ドイツ公開特許２６５０ ９８９にょる封孔助剤を用いて封 孔を行ったが、含浸添加剤は用いず、含浸浴における後処理は行わなかった。Comparative example 7 Sealing was performed using the sealing aid according to West German Published Patent Application No. 2650-989 as described above. Although holes were made, no impregnating additives were used and no post-treatment in an impregnating bath was performed.
次に、試験シートを、腐食試験スタンド上でシートを４５″傾斜させて南に向け て屋外気象にさらした。下記表５に、それぞれ１．２．３．４および６ケ月後の 試験シートの表面の装飾的外観の評価結果を示す。Next, place the test sheet on a corrosion test stand with the sheet tilted 45″ and facing south. exposed to outdoor weather. Table 5 below shows the results after 1, 2, 3, 4 and 6 months respectively. The evaluation results of the decorative appearance of the surface of the test sheet are shown.
表５ 試験シートの屋外耐候試験における装飾的外観の評価実施例１４ １ケ月後： 変化なし ２ケ月後： 光沢なし、一部の小さい領域がビロード状塗膜を有する（表面の約 ３０％が影響を受けている）３ケ月後： 光沢なし、多くの小さい領域がビロー ド状塗膜を有する（表面の約５０％が影響を受けている）４ケ月後： 光沢なし 、非常に多くの小さい領域がビロード状塗膜を有する（表面の約７０％が影響を 受けている）６ケ月後： 独立した小さな領域が青色光沢を有し、表面全体がビ ロード状塗膜を有する 実施例１５ １ケ月後： 変化なし ２ケ月後： 変化なし ３ケ月後； 光沢なし、独立した領域がビロード状塗膜を有する（表面の約１０ ％が影響を受けている）４ケ月後： 光沢なし、独立した領域がビロード状塗膜 を有する（表面の約１０％が影響を受けている）６ケ月後： 光沢なし、一部の 領域がビロード状塗膜を有する（表面の約２０％が影響を受けている） 実施例１６ １ケ月後： 変化なし ２ケ月後： 変化なし ３ケ月後 光沢なし、一部の領域がビロード状塗膜を有する（表面の約３０％が 影響を受けている。） ４ケ月後： 独立した領域が青色光沢を有し、一部の領域がビロード状塗膜を有 する（表面の約３０％が影響を受けている）６ケ月後： 独立した領域が青色光 沢を有し、多くの領域がビロード状塗膜を有する（表面の約７０％が影響を受け ている）比較例７ １ケ月後： 変化なし ２ケ月後、 光沢なし、独立した領域がビロード状塗膜を有する（表面の約１０ ％が影響を受けている）３ケ月後二 表面の約２／３が青色光沢を有し、非常に 多くの領域がビロード状塗膜を有する（表面の約１００％が影響を受けている） ４ケ月後二 表面の約２／３が青色光沢を有し、非常に多くの領域がビロード状 塗膜を有する（表面の約１００％が影響を受けている） ６ケ月後二 表面の約２／３が黄色光沢を有し、表面全体がビロード状塗膜を有 する 国際調査報告 国際調査報告Table 5 Evaluation example 14 of decorative appearance in outdoor weather resistance test of test sheet 1 month later: No change After 2 months: No gloss, some small areas have a velvety coating (about the surface 30% affected) After 3 months: No shine, many small areas are billowy After 4 months with do-like coating (approximately 50% of the surface affected): No gloss , very many small areas have a velvety coating (approximately 70% of the surface is affected) After 6 months: Separate small areas have blue luster, and the entire surface is blue. Has a road-like coating film Example 15 1 month later: No change 2 months later: No change After 3 months; no shine, isolated areas with velvety coating (approximately 10 % affected) After 4 months: No gloss, velvety coating in separate areas After 6 months with (approximately 10% of the surface affected): no shine, some Area has a velvety coating (approximately 20% of surface affected) Example 16 1 month later: No change 2 months later: No change After 3 months, no gloss, some areas have a velvety coating (approximately 30% of the surface affected. ) After 4 months: Separate areas have a blue luster and some areas have a velvety coating. After 6 months (approximately 30% of the surface is affected): Separate areas are exposed to blue light It has a velvety coating in many areas (approximately 70% of the surface is affected). Comparative Example 7 1 month later: No change After 2 months, no shine, isolated areas with velvety coating (approximately 10 % affected) After 3 months, about 2/3 of the surface has a blue luster and is very Many areas have a velvety coating (approximately 100% of the surface affected) After 4 months, about 2/3 of the surface has a blue luster and many areas are velvety. Has a coating (approximately 100% of the surface is affected) After 6 months, about 2/3 of the surface has a yellow luster and the entire surface has a velvety coating. do international search report international search report
Claims (19)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3900169.5 | 1989-01-05 | ||
| DE3900169A DE3900169A1 (en) | 1989-01-05 | 1989-01-05 | METHOD OF IMPREGNIZING ANODICALLY PRODUCED SURFACES OF ALUMINUM |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04502647A true JPH04502647A (en) | 1992-05-14 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2501034A Pending JPH04502647A (en) | 1989-01-05 | 1989-12-22 | How to impregnate aluminum surface formed with anode |
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| Country | Link |
|---|---|
| EP (1) | EP0452345A1 (en) |
| JP (1) | JPH04502647A (en) |
| KR (1) | KR910700362A (en) |
| AU (1) | AU4804090A (en) |
| DE (1) | DE3900169A1 (en) |
| WO (1) | WO1990007589A1 (en) |
| ZA (1) | ZA9058B (en) |
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| JP2012197482A (en) * | 2011-03-22 | 2012-10-18 | Lixil Corp | Functional aluminum material and electrolytic treatment method therefor |
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| DE10028772B4 (en) * | 2000-06-07 | 2005-03-17 | Technische Universität Dresden | Aluminum material with ultrahydrophobic surface, process for its preparation and use |
| DE102005032421B4 (en) * | 2005-07-12 | 2008-03-27 | Erbslöh Ag | Method for producing a decorative trim piece |
| DE102007044159A1 (en) | 2007-09-11 | 2009-03-12 | Leibniz-Institut Für Polymerforschung Dresden E.V. | Metal materials with hybrid-stabilized oxide layer, process for the preparation and their use |
| CN106191962A (en) * | 2016-08-30 | 2016-12-07 | 无锡库帕油品有限公司 | A kind of aluminum and Aluminum Alloy Room Temperature environmental protection sealer and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE3233411A1 (en) * | 1982-09-09 | 1984-03-15 | Henkel KGaA, 4000 Düsseldorf | METHOD FOR COMPRESSING ANODICALLY PRODUCED OXIDE LAYERS ON ALUMINUM OR ALUMINUM ALLOYS |
| GB8309571D0 (en) * | 1983-04-08 | 1983-05-11 | Albright & Wilson | Accelerated sealing of anodised aluminium |
-
1989
- 1989-01-05 DE DE3900169A patent/DE3900169A1/en not_active Withdrawn
- 1989-12-22 AU AU48040/90A patent/AU4804090A/en not_active Abandoned
- 1989-12-22 KR KR1019900701973A patent/KR910700362A/en not_active Application Discontinuation
- 1989-12-22 WO PCT/EP1989/001596 patent/WO1990007589A1/en not_active Application Discontinuation
- 1989-12-22 EP EP90900181A patent/EP0452345A1/en not_active Withdrawn
- 1989-12-22 JP JP2501034A patent/JPH04502647A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2012197482A (en) * | 2011-03-22 | 2012-10-18 | Lixil Corp | Functional aluminum material and electrolytic treatment method therefor |
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| Publication number | Publication date |
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| ZA9058B (en) | 1990-09-26 |
| AU4804090A (en) | 1990-08-01 |
| WO1990007589A1 (en) | 1990-07-12 |
| KR910700362A (en) | 1991-03-15 |
| EP0452345A1 (en) | 1991-10-23 |
| DE3900169A1 (en) | 1990-07-12 |
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