JPS629680B2 - - Google Patents
Info
- Publication number
- JPS629680B2 JPS629680B2 JP9626078A JP9626078A JPS629680B2 JP S629680 B2 JPS629680 B2 JP S629680B2 JP 9626078 A JP9626078 A JP 9626078A JP 9626078 A JP9626078 A JP 9626078A JP S629680 B2 JPS629680 B2 JP S629680B2
- Authority
- JP
- Japan
- Prior art keywords
- temperature
- time
- coating
- anodized
- composition
- 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
- 238000000576 coating method Methods 0.000 claims description 27
- 239000011248 coating agent Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 22
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 230000007797 corrosion Effects 0.000 claims description 12
- 238000005260 corrosion Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 229910000838 Al alloy Inorganic materials 0.000 claims description 6
- 239000003431 cross linking reagent Substances 0.000 claims description 6
- 239000011253 protective coating Substances 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 5
- 239000008199 coating composition Substances 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 239000003112 inhibitor Substances 0.000 claims description 4
- BNCADMBVWNPPIZ-UHFFFAOYSA-N 2-n,2-n,4-n,4-n,6-n,6-n-hexakis(methoxymethyl)-1,3,5-triazine-2,4,6-triamine Chemical group COCN(COC)C1=NC(N(COC)COC)=NC(N(COC)COC)=N1 BNCADMBVWNPPIZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000005727 Friedel-Crafts reaction Methods 0.000 claims description 2
- 230000036571 hydration Effects 0.000 claims description 2
- 238000006703 hydration reaction Methods 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- 238000002791 soaking Methods 0.000 claims 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical class [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical class [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims 1
- 229920006243 acrylic copolymer Polymers 0.000 claims 1
- 229910052804 chromium Inorganic materials 0.000 claims 1
- 239000011651 chromium Substances 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 229910052750 molybdenum Inorganic materials 0.000 claims 1
- 239000011733 molybdenum Chemical class 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 229920000058 polyacrylate Polymers 0.000 claims 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical class [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims 1
- 229910052721 tungsten Chemical class 0.000 claims 1
- 239000010937 tungsten Chemical class 0.000 claims 1
- 239000000463 material Substances 0.000 description 26
- -1 ethylhexyl Chemical group 0.000 description 22
- 239000011347 resin Substances 0.000 description 14
- 229920005989 resin Polymers 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 238000007789 sealing Methods 0.000 description 9
- 239000004925 Acrylic resin Substances 0.000 description 7
- 229920000178 Acrylic resin Polymers 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- 239000004971 Cross linker Substances 0.000 description 4
- 229920000877 Melamine resin Polymers 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N 2-propanol Substances CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical class C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 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 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 238000002048 anodisation reaction Methods 0.000 description 2
- 238000007743 anodising Methods 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 229960002887 deanol Drugs 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 239000012972 dimethylethanolamine Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 150000007974 melamines Chemical class 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N protonated dimethyl amine Natural products CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- NVKTUNLPFJHLCG-UHFFFAOYSA-N strontium chromate Chemical compound [Sr+2].[O-][Cr]([O-])(=O)=O NVKTUNLPFJHLCG-UHFFFAOYSA-N 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- NDKWCCLKSWNDBG-UHFFFAOYSA-N zinc;dioxido(dioxo)chromium Chemical compound [Zn+2].[O-][Cr]([O-])(=O)=O NDKWCCLKSWNDBG-UHFFFAOYSA-N 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- NCXUNZWLEYGQAH-UHFFFAOYSA-N 1-(dimethylamino)propan-2-ol Chemical compound CC(O)CN(C)C NCXUNZWLEYGQAH-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
- XKMDZVINHIFHLY-UHFFFAOYSA-N 1-ethenyl-3,5-dimethylbenzene Chemical compound CC1=CC(C)=CC(C=C)=C1 XKMDZVINHIFHLY-UHFFFAOYSA-N 0.000 description 1
- XNIOWJUQPMKCIJ-UHFFFAOYSA-N 2-(benzylamino)ethanol Chemical compound OCCNCC1=CC=CC=C1 XNIOWJUQPMKCIJ-UHFFFAOYSA-N 0.000 description 1
- 229940058020 2-amino-2-methyl-1-propanol Drugs 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 1
- YLAXZGYLWOGCBF-UHFFFAOYSA-N 2-dodecylbutanedioic acid Chemical compound CCCCCCCCCCCCC(C(O)=O)CC(O)=O YLAXZGYLWOGCBF-UHFFFAOYSA-N 0.000 description 1
- PYSGFFTXMUWEOT-UHFFFAOYSA-N 3-(dimethylamino)propan-1-ol Chemical compound CN(C)CCCO PYSGFFTXMUWEOT-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- BLFRQYKZFKYQLO-UHFFFAOYSA-N 4-aminobutan-1-ol Chemical compound NCCCCO BLFRQYKZFKYQLO-UHFFFAOYSA-N 0.000 description 1
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 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
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 125000006350 alkyl thio alkyl group Chemical group 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000004103 aminoalkyl group Chemical group 0.000 description 1
- 125000004202 aminomethyl group Chemical group [H]N([H])C([H])([H])* 0.000 description 1
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- KVBCYCWRDBDGBG-UHFFFAOYSA-N azane;dihydrofluoride Chemical compound [NH4+].F.[F-] KVBCYCWRDBDGBG-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 description 1
- ZAFAJHDHPYDVCN-UHFFFAOYSA-N butanoic acid;phosphoric acid Chemical compound OP(O)(O)=O.CCCC(O)=O ZAFAJHDHPYDVCN-UHFFFAOYSA-N 0.000 description 1
- BCFSVSISUGYRMF-UHFFFAOYSA-N calcium;dioxido(dioxo)chromium;dihydrate Chemical compound O.O.[Ca+2].[O-][Cr]([O-])(=O)=O BCFSVSISUGYRMF-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical class [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 125000002704 decyl group Chemical group [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])* 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000013527 degreasing agent Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- CMMUKUYEPRGBFB-UHFFFAOYSA-L dichromic acid Chemical class O[Cr](=O)(=O)O[Cr](O)(=O)=O CMMUKUYEPRGBFB-UHFFFAOYSA-L 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- AAQNGTNRWPXMPB-UHFFFAOYSA-N dipotassium;dioxido(dioxo)tungsten Chemical compound [K+].[K+].[O-][W]([O-])(=O)=O AAQNGTNRWPXMPB-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [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])* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 229960001867 guaiacol Drugs 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000005358 mercaptoalkyl group Chemical group 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- 125000004092 methylthiomethyl group Chemical group [H]C([H])([H])SC([H])([H])* 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical class O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- 125000002347 octyl 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])[H] 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000000466 oxiranyl group Chemical group 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000037452 priming Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011780 sodium chloride 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
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004634 thermosetting polymer Substances 0.000 description 1
- 150000004684 trihydrates Chemical class 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical class O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
- B05D7/16—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies using synthetic lacquers or varnishes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- 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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2202/00—Metallic substrate
- B05D2202/20—Metallic substrate based on light metals
- B05D2202/25—Metallic substrate based on light metals based on Al
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2350/00—Pretreatment of the substrate
- B05D2350/30—Change of the surface
- B05D2350/33—Roughening
- B05D2350/40—Roughening by adding a porous layer
Description
【発明の詳細な説明】
本発明は一般的には金属へ保護被覆を与えるた
めの方法に関するものであり、詳細には特に腐食
に対する保護について従来可能であつたよりも優
れた被覆がアルミニウムおよびアルミニウム合金
へ適用され、それによつて長寿命の最終製品が製
造されるような方法に関するものである。
アルミニウム基材に保護被覆、たとえばいわゆ
る“防食”塗装または下地塗装を適用する現行の
方法は、化学的表面処理方法に続く下地塗料の適
用に頼つている。例えばアルミニウム基材または
作業片を先ず陽極酸化し、次に封孔し、最後に下
地塗装がほどこされる多段階の別々に別れた工程
が必要である。換言すれば、層の積み重ねによつ
て最終的被覆をもたらし、それらの層の化学的／
機械的結合がその保護被覆の耐久性、したがつて
そのアルミニウム製品の使用寿命を左右する。こ
の積層被覆物を形成する全操作には可成りの時間
と労力がかかる。
本発明は、この技術における改良、およびその
目的のため、必要な封孔および下地塗装操作が同
時に行なわれる新規方法の提案、ならびにこのよ
うな同時操作を達成するための新規材料の調合に
関する。例えば、本発明の方法は完全操作のため
の時間と労力の実質的な節減を可能にする一方、
同時に塗料と酸化物フイルムとの合体結合によつ
てもたらされる、従来可能であつたよりも優れた
被覆を生成する。このことはその封孔操作中に酸
化物フイルムの小孔中へ可溶性樹脂を導入するこ
とによるためであると考えられる。それに引続い
て、その熱硬化性樹脂が硬化操作中に架橋されて
耐久性でかつ保護性の被覆を与える。
さらに詳細には、本明細書に提案される材料
は、その陽極被膜を１水和物（Al2O3・H2O）と
３水和物（Al2O3・3H2O）の形態へ封孔すると同
時に、それに水溶性有機樹脂を含浸させる。その
水溶性有機樹脂材料は、調節された時間／温度条
件で未封孔の陽極被膜へ適用された場合、厳しい
腐食環境に耐えうる樹脂含浸の封孔された陽極被
膜を提供する。そのような環境には、高度な湿分
および屡々塩分を含む大気にさらされる海岸地帯
の例があり、たとえば航空、海運、建築および自
動車工業で出会うような環境がある。
本発明の好ましい樹脂塗料材料は水溶性アクリ
ル樹脂から構成されるポリマーであり、そのアク
リル樹脂は種々のアクリル含有材料、たとえばア
クリロニトリル、メタクリロニトリル、アクリル
アミド、メタクリルアミド、メタクリル酸、アク
リル酸、メタクリル酸エステルおよびアクリル酸
エステルのような材料から構成されていてもよ
い。最も好ましくは、その樹脂塗料材料は次の一
般式を有するものから選択される重合または共重
合されたモノマーから構成される：
CH2＝CH(A)−Ｃ（Ｏ）−Ｏ−Ｒ
上式中Ａは水素、メチルまたはエチルであり；
Ｒは水素、１〜20個好ましくは２〜８個の炭素原
子のアルキル、１〜20個の好ましくは２〜８個、
さらに好ましくは２〜５個の炭素原子の水酸基置
換アルキル、１〜20個好ましくは２〜８個の炭素
原子の１級または２級アミノ置換アルキルで、そ
のアミノ基の置換分が１〜６個の炭素原子のアル
キルまたはヒドロキシアルキル基であるもの、１
〜20個好ましくは２〜８個の炭素原子のメルカプ
ト置換アルキル、20個まで好ましくは８個までの
炭素原子のアルキルチオアルキレン、およびオキ
シラン環を有する８個までの炭素原子の基で最も
好ましくはグリシジルのように３個の炭素原子の
ものでよい。
上記に規定したモノマーのうち最も好ましいも
のはアクリルおよびメタクリル系のものである。
酸の好適な例はアクリル酸およびメタクリル酸
である。アルキルエステルの好適な例は、アルキ
ル基がメチル、エチル、プロピル、イソプロピ
ル、ブチル、３級ブチル、ペンチル、ヘキシル、
エチルヘキシル、オクチル、デシル、ドデシル等
であるアクリルまたはメタクリル酸のエステルで
あり；水酸基置換アルキルの好適な例はヒドロキ
シルエチル、ヒドロキシプロピル、ヒドロキシブ
チル、ヒドロキシルペンチル、ヒドロキシヘキシ
ル、ヒドロキシルオクチル、ヒドロキシデシル、
ヒドロキシルドデシル、等であり；アミノアルキ
ルの好適な例はアミノメチル、アミノエチル、オ
ミノプロピル、アミノブチル、アミノペンチル、
アミノヘキシル、アミノオクチル、アミノデシ
ル、アミノドデシルで、そのアミノ基が１級また
は２級アミノであり、そのアミノ基の置換基が１
〜６個好ましくは１〜４個の炭素原子のアルキル
基であるものであり；メルカプトアルキルの好適
な例はメチルメルカプト、エチルメルカプト、プ
ロピルメルカプト、ブチルメルカプト、ペンチル
メルカプト、ヘキシルメルカプト、オクチルメル
カプト、デシルメルカプト、ドデシルメルカプ
ト、等であり；同様にアルコキシアルキルおよび
アルキルチオアルキル基はメトキシメチル、エト
キシメチル、エトキシエチル、メチルチオメチ
ル、エチルチオエチル等である。
その重合樹脂はホモポリマーであつてもよい
が、その最終塗料材料に改良された耐食性、割れ
にくさ、接着性、光沢性、たわみ性、耐久性、硬
度、流れ性および耐溶剤性といつたような種々の
性質を与えるように、モノマー混合物を利用する
のが最も望ましい。
ポリマーは、乳化または溶液重合で有機溶剤中
でアゾ触媒を用いて行なうような既知の重合法に
よつて製造することができる。
好ましい重合性モノマー混合物は、主要量すな
わち約75〜約99重量％のアクリルまたはメタクリ
ル酸エステル（前述の式中のＲがアルキルであ
る）および少量、すなわち合計で100重量％にな
るように約１〜約25重量％の酸（Ｒが水素であ
る）を含有するものである。
さらに、エチレン系不飽和基を有するその他の
共重合性モノマー、たとえば酢酸ビニル、塩化ビ
ニル等の如き脂肪族ビニル、またはスチレン、ビ
ニルスチレン、３・５−ジメチルスチレン、パラ
−ｔ−ブチルスチレン、α−メチルスチレン等の
如き芳香族ビニルが、0.1〜約15重量％の少量、
前述したモノマー混合物中へ添加されてもよい。
塗料材料は好ましくは塩基性のPH、さらに好ま
しくは８〜９のPHを有し、好ましくは水可溶化剤
を含有し、その量は重合体材料によつて変化させ
ることができる。好ましくは、水可溶化剤は樹脂
の約１部から20部或は40部までの範囲の量で使用
される。アミン、アンモニアまたはアルカリ金属
の如き任意の可溶化剤を使用してもよいことは認
められるべきであり、その処理温度が高いために
高沸点のものが使用される。最も好ましくは、そ
の水可溶化剤は窒素含有物質で、たとえばジエチ
ルエタノールアミンのようなアルコール系アミ
ン；２アミノ−２メチル−１プロパノール；ジエ
タノールアミン、トリエタノールアミン、ジメチ
ルプロパノールアミン、ジメチルイソプロパノー
ルアミン、ジメチルブタノールアミン、Ｎ−ベン
ジルエタノールアミン、２−〔２−（ジメチルアミ
ン）エトキシ〕エタノール；１−〔２−（ジメチル
アミン）エトキシル〕−２−プロパノール等であ
る。
塗料材料はまた架橋に有効な量の浴安定窒素含
有架橋剤、たとえば尿素型、メラミン型、ベンゾ
グアナミンを含有していてもよく、好ましくはメ
ラミン型を含有する。種々のメラミン類が使用す
ることができるが、最も好ましいのは置換メラミ
ン類、たとえばポリメチロールメラミンのポリア
ルキルエーテルで、それぞれのアルキル基が１〜
４個の炭素原子を含むもので、最も好ましいのは
ヘキサメトキシメチルメラミンである。
良好な架橋剤の選択の基準は、塗料材料がもた
らされる高温度で安定性を有すること、およびそ
の材料に添加される耐食性顔料に対して合理的に
安定であること、およびアクリル樹脂塗料材料に
良好な架橋性を与えることができることである。
使用される架橋剤の量は、その架橋剤中の官能
基の数が、アルキル樹脂中に存在する官能基の数
に実質的に等しくなるように、樹脂中に存在する
カルボン酸基の数に匹敵する。
低い架橋温度にするために、アクリル樹脂塗料
材料へ熱硬化触媒を添加することが望ましい。好
ましい触媒はフリーデル−クラフツ酸触媒であ
り、窒素含有架橋剤に基いて約１〜約15％の量で
添加される。これらの触媒は樹脂と架橋剤との間
の縮合反応を誘起する。使用してもよい好適な酸
触媒は、パラトルエンスルホン酸、ドデシルコハ
ク酸、ｎ−ブチル酸ホスフエート、燐酸等であ
る。
不安定性をもたらすことがある樹脂の加水分解
またはその他の反応を抑制する遊離ラジカル抑制
剤を添加することが望ましいことも見出されてい
る。これらの抑制剤は塗料材料（アクリル樹脂お
よび架橋剤を一緒にしたもの）の約１〜約10重量
％の量で添加してよい。好適な抑制剤はグアイア
コール、ハイドロキノン等である。
さらに、その塗料組成物は最終塗膜に実質的に
改良された耐食性を与える種々の材料を含有して
もよい。これらの材料は周期表の−Ｂ族の水溶
性金属塩である。好適な耐食性材料はクロム酸
塩、重クロム酸塩、モリブデン酸塩、タングステ
ン酸塩等であり、たとえばクロム酸ストロンチウ
ム、クロム酸カルシウム、クロム酸亜鉛、クロム
酸カリ、クロム酸ナトリウム、重クロム酸ナトリ
ウム、タングステン酸カリ、モリブデン酸ナトリ
ウム、珪クロム酸鉛およびクロム酸と重クロム酸
のアンモニウム塩である。さらに、前述したモリ
ブデン酸およびタングステン酸の錯塩、および上
述の水可溶化用アミン類、たとえばジメチルエタ
ノールアミンが使用されてもよい。
アクリル樹脂は、低分子樹脂、すなわち約
10000より小さく、さらに好ましくは約5000より
も小さい分子量（数平均）を有し、かつ150より
小さく、好ましくは100よりも小さい酸価を有す
るものであることがまた好ましい。
好ましい配合物は次の成分から成るものであ
る。
配合Ａ成分
重量部
アクリル酸エチル（71.4％）、アクリル酸
（12.9％）およびメタクリル酸メチル
（15.7％）の重合物のアクリル樹脂を、
アセトン、イソプロパノール溶剤中に入
れたもの（70重量％） …………1.25
ヘキサメトキシメチルメラミン …………１
水可溶化剤（ジメチルエタノールアミン）
…………1.1
クロム酸ストロンチウム …………2.5
パラトルエンスルホン酸（水中25％）
…………0.24
水 …………9.5
充填剤、顔料、染料、着色料、レベリング剤等
の如き他の成分をその塗料材料へ添加してもよい
ことは認められるべきである。これらの成分は、
被覆された製品が使用されるべき用途にしたがつ
て添加することができる。
未封孔の陽極被膜を同時に封孔および含浸する
工程は、新らしく陽極酸化された未封孔状態のア
ルミニウム基材表面を、前述の材料の１つが入つ
た処理容器中に浸漬することによつて行なわれ
る。ここで提案されている新規な水溶性樹脂材料
は、１％未満から70％を超えるまでの濃度範囲で
有用である。その浴は76.6℃〜93.3℃（170〜210
〓）、にゲル化または樹脂の沈でんまたは分離を
起すこと無く無期限に維持することができる。PH
を塩基性PH、好ましくは約7.5〜約9.0、さらに好
ましくは約8.2に調整することによつて、優れた
安定性を維持するPH調整を簡単に行うことができ
る。時間と温度は、温度が高くなる程時間は短か
くなる関係を有する。陽極被膜は酸化物の水和に
よつて未封孔の状態から封孔された状態へ変化
し、次の反応にしたがつて金属酸化物１水和物お
よび金属酸化物３水和物の構造的特性を有する。
(1) Al2O3＋H2O→2AlO（OH）
→Al2O3・H2O
(2) 2AlO（OH）＋2H2O
→Al2O3・3H2O
陽極被膜の封孔／含浸に続いて、その陽極酸化
された金属は、水中ですすぎ洗いされ、次に硬化
目的のために好ましくは93.3℃〜260℃（200〜
500〓）に調節された乾燥炉中に置く。この工程
は１〜60分位の時間を必要とし、時間と温度は逆
の関係を有する。硬化が航空機工業向けの部材の
ためのものである場合には、通常148.8℃（300
〓）より高い温度は使用されない。ときとして、
その部材を硬化操作に先立つて乾燥させ、それに
よつて同時封孔／含浸段階後のすすぎ洗い段階を
省略することが望ましい場合がある。
上記はアルミニウム基材の調整および陽極酸化
の普通の段階にしたがつた代表的処理手順を述べ
たものである。陽極酸化のためのこのような調製
には(イ)脱脂、(ロ)アルカリ洗浄、および(ハ)操作(イ)
、
(ロ)および(ハ)のそれぞれのあとの中間水すすぎ洗い
による脱酸を含んでいる。陽極酸化は電解液、お
よびクロム酸、硫酸および変性硫酸型の、それに
限定されるわけではないが、陽極被膜を発達させ
るに必要な工程変数を使用して行い、続いてその
直後に水ですすぎ洗いする。アルミニウムおよび
アルミニウム合金の洗浄および仕上げの論議につ
いては、参考のためにここに記載する、
American Society for Metals出版のMetals
Handbook、第８版（1964年）、第２巻611−634
ページを参照されたい。
アルミニウムおよびアルミニウム合金部材、特
に7075−T6に対して、本発明にしたがつて腐食
抑制塗膜を適用する特定的実施例を以下に記載す
る。
実施例 １
(1) 前記部材をトリクロルエチレンまたは１−１
−１トリクロルエタン材料を使用して気相脱脂
し、次にその脱脂器中に乾燥するまで放置し
た。
(2) その脱脂した部材を20〜25重量％の活性アル
カリ度、約37.5ｇ／の濃度を有しかつ約76.6
℃（約170〓）に維持されている、PH11.8〜13
の抑制アルカリ洗浄剤中で約18分間洗浄した。
(3) 次にその部材を外気温度の水〔約20℃（約70
〓）〕で約90秒間すすぎ洗いした。
(4) その部材を66゜ボーメ硫酸127.3〜172.3ｇ／
（17〜23オンス／ガロン）（重量）、重クロム
酸ナトリウム22.5〜37.5ｇ／（３〜５オン
ス／ガロン）（重量）、および２フツ化アンモニ
ウム4.5〜6.0ｇ／（0.6〜0.8オンス／ガロ
ン）（重量）から成り、かつ室温〔約20℃（約
70〓）〕に維持されたアルミニウム酸化物除去
剤中で約８分間酸化物を除去した。
(5) 次にその部材を外気温の水で約２分間すすぎ
洗いした。
(6) 次にその部材を約30分間、15％66゜ボーメ硫
酸中で６〜24ボルト（DC）で12.9〜16.1アン
ペア／ｄm2（12〜15アンペア／平方フイート）
でかつ約20℃（約70〓）に維持して陽極酸化し
た。
(7) その陽極酸化した部材を外気温の水で約２分
間すすぎ洗いした。
(8) 次にその部材を、水２部対“配合Ａ”１部に
希釈しかつ79.4±2.8℃（175±５〓）に維持し
た水溶性有機樹脂塗料材料、「配合Ａ」中に約
１時間浸漬した。
(9) その部材が同時に封孔および下地塗装される
この浴に続いて、その部材を外気温で60±５分
間空気乾燥した。
(10) 最後にその部材を乾燥空気炉中で15分間146
±2.8℃で硬化させた。
実施例 ２
塗装されるべき部材を実施例１における(1)から
(7)までの段階にしたがつて調製した。
(8) 次にその部材を、実施例１に記載した樹脂−
含有水溶性組成物を82.2±2.8℃（180±５〓）
に維持した浴によつて約30分間封孔および下地
塗装した。
(9) この浴に続いて、その部材を実施例１の段階
９および10におけると同じように空気乾燥およ
び硬化させたが、しかしながらその硬化はこの
場合には123.8±2.8℃（255±５〓）で約30分
間行なわれた。
実施例 ３
本実施例においては塗装されるべき部材を実施
例１と同じ段階(1)から(5)までに従つて調製した。
(6) 次にその部材を、クロム酸29.9〜52.4ｇ／
（４〜７オンス／ガロン）（重量）中で、約48ボ
ルト（DC）、1.07アンペア／ｄm2（１アンペ
ア／平方フイート）（最小）で、約37.7℃（100
〓）に維持した操作で約48分間陽極酸化した。
次にその部材を実施例１と同じ段階(7)から(10)ま
での段階に従つて処理した。
実施例 ４
本実施例においては塗装されるベき部材を実施
例３と同じ段階(1)から(6)までの段階に従つて調製
した。
外気温の水で約２分間すすぎ洗いしたのちに、
その部材を実施例２と同じ段階(8)から(10)までの段
階に従つて処理した。
実施例２の試験片について、6.5〜7.2のPH範囲
内で、35℃で操作された塩分５％の霧中で環境塩
噴霧試験を実施した。これらの試験片を9000時間
曝したのち、腐食による浸蝕のきざしは認められ
なかつた。試験した他の実施例のものでもそれに
匹敵する結果が得られた。
これらのすべての試験から、特定範囲の高温度
での封孔によつて、腐食による浸蝕に対する最大
の保護が達成されることが結論された。
上記のそれぞれの場合における塗装されたアル
ミニウム部材は、封孔および有機室下地塗装の別
別の工程から従来得られたよりも優れた、アルミ
ニウムおよびアルミニウム合金に対する腐食保護
が上記の方法によつて与えられることを示してい
た。このことは従来の如く連続した別々の工程と
して陽極酸化され、封孔し、そしてクロム酸亜鉛
およびエポキシ下地塗装された成分と、本明細書
に記載したように処理された成分とを、両者とも
に同じ腐食環境へ同じ長時間もたらすことによる
比較試験によつて決定された。塩分５％噴霧に
3900時間曝したのち試験部材を検査すると、先行
技術のすべての部材は腐食欠陥を示したが、一方
本明細書に記載の処理による部材はいずれも腐食
のきざしを示さなかつた。
さらに、陽極被膜の封孔および下地塗装の同時
操作を行なう費用は、封孔および下地塗装を別々
の操作で行なう費用よりも相当に小さいことが見
出された。このことは主として下地塗料塗装操作
中に必要な手作業労働を入れる必要が無いことに
よつている。本発明の方法はアルミニウムおよび
アルミニウム合金に対して有用であり、この場合
それらの合金はアルミニウムおよび周期表の他の
元素から構成されている。それについては参照の
ためここに記載するMetals Handbook、第８版
（1961年）、（American Society for Metals出
版）917ページを参照されたい。
DETAILED DESCRIPTION OF THE INVENTION The present invention relates generally to a method for providing protective coatings to metals, and more particularly to methods for providing protective coatings on aluminum and aluminum alloys, which provide superior coatings for protection against corrosion than previously possible. The present invention relates to a method that can be applied to a product, thereby producing a long-life end product. Current methods of applying protective coatings to aluminum substrates, such as so-called "anticorrosive" paints or basecoats, rely on chemical surface treatment methods followed by the application of a basecoat. For example, a multi-step, separate process is required in which the aluminum substrate or workpiece is first anodized, then sealed, and finally a base coat applied. In other words, the stacking of layers results in the final coating, and the chemical/
Mechanical bonding determines the durability of the protective coating and thus the service life of the aluminum product. The entire operation of forming this laminated coating requires considerable time and effort. The present invention relates to improvements in this technology and to that end the proposal of a new method in which the necessary sealing and priming operations are carried out simultaneously, as well as the formulation of new materials to accomplish such simultaneous operations. For example, the method of the invention allows substantial savings in time and effort for complete operation, while
At the same time, the combined bonding of paint and oxide film produces a better coating than was previously possible. This is thought to be due to the introduction of soluble resin into the small pores of the oxide film during the pore sealing operation. Subsequently, the thermoset resin is crosslinked during a curing operation to provide a durable and protective coating. More specifically, the material proposed herein has its anodic coating in the form of monohydrate (Al 2 O 3 .H 2 O) and trihydrate (Al 2 O 3 .3H 2 O). At the same time, it is impregnated with a water-soluble organic resin. The water-soluble organic resin material provides a resin-impregnated sealed anodic coating that can withstand harsh corrosive environments when applied to an unsealed anodic coating under controlled time/temperature conditions. Examples of such environments are coastal areas exposed to highly humid and often saline atmospheres, such as those encountered in aviation, shipping, construction, and the automobile industry. Preferred resin coating materials of the present invention are polymers composed of water-soluble acrylic resins, which acrylic resins are composed of various acrylic-containing materials, such as acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, methacrylic acid, acrylic acid, methacrylic acid It may be composed of materials such as esters and acrylates. Most preferably, the resin coating material is composed of polymerized or copolymerized monomers selected from those having the following general formula: CH2 =CH(A)-C(O)-O-R in which A is hydrogen, methyl or ethyl;
R is hydrogen, alkyl of 1 to 20, preferably 2 to 8 carbon atoms, 1 to 20, preferably 2 to 8;
More preferably hydroxyl-substituted alkyl of 2 to 5 carbon atoms, primary or secondary amino-substituted alkyl of 1 to 20 carbon atoms, preferably 2 to 8 carbon atoms, and the amino group has 1 to 6 substitutions. is an alkyl or hydroxyalkyl group of carbon atoms, 1
mercapto-substituted alkyl of up to 20 preferably 2 to 8 carbon atoms, alkylthioalkylene of up to 20 preferably up to 8 carbon atoms, and groups of up to 8 carbon atoms with an oxirane ring, most preferably glycidyl It can be one with 3 carbon atoms, such as . Among the monomers defined above, the most preferred are acrylic and methacrylic. Suitable examples of acids are acrylic acid and methacrylic acid. Preferred examples of alkyl esters include methyl, ethyl, propyl, isopropyl, butyl, tertiary butyl, pentyl, hexyl,
esters of acrylic or methacrylic acid such as ethylhexyl, octyl, decyl, dodecyl; preferred examples of hydroxy-substituted alkyl are hydroxylethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, hydroxyhexyl, hydroxyoctyl, hydroxydecyl,
hydroxydodecyl, etc.; preferred examples of aminoalkyl are aminomethyl, aminoethyl, ominopropyl, aminobutyl, aminopentyl,
aminohexyl, aminooctyl, aminodecyl, aminododecyl, the amino group is primary or secondary amino, and the substituent of the amino group is 1
~6 alkyl groups, preferably 1 to 4 carbon atoms; preferred examples of mercaptoalkyl are methyl mercapto, ethyl mercapto, propyl mercapto, butyl mercapto, pentyl mercapto, hexyl mercapto, octyl mercapto, decyl Mercapto, dodecylmercapto, etc.; likewise alkoxyalkyl and alkylthioalkyl groups are methoxymethyl, ethoxymethyl, ethoxyethyl, methylthiomethyl, ethylthioethyl, and the like. The polymeric resin, which may be a homopolymer, provides the final coating material with improved corrosion resistance, crack resistance, adhesion, gloss, flexibility, durability, hardness, flowability and solvent resistance. Most preferably, mixtures of monomers are utilized to provide a variety of properties such as: The polymers can be prepared by known polymerization methods such as emulsion or solution polymerization in organic solvents using azo catalysts. Preferred polymerizable monomer mixtures include a major amount, about 75 to about 99 weight percent, of an acrylic or methacrylic ester (wherein R in the above formula is alkyl) and a minor amount, about 1 to about 100 percent by weight. ~25% by weight acid (R is hydrogen). Furthermore, other copolymerizable monomers having ethylenically unsaturated groups, such as aliphatic vinyls such as vinyl acetate, vinyl chloride, etc., or styrene, vinylstyrene, 3,5-dimethylstyrene, para-t-butylstyrene, α - small amounts of vinyl aromatics, such as methylstyrene, from 0.1 to about 15% by weight;
It may also be added to the monomer mixtures described above. The coating material preferably has a basic PH, more preferably a PH of 8 to 9, and preferably contains a water solubilizer, the amount of which can vary depending on the polymeric material. Preferably, the water solubilizer is used in an amount ranging from about 1 part to 20 or 40 parts of resin. It should be appreciated that any solubilizing agent may be used, such as amines, ammonia or alkali metals, and those with high boiling points are used because of the high processing temperatures. Most preferably, the water solubilizer is a nitrogen-containing substance, such as an alcoholic amine such as diethylethanolamine; 2-amino-2methyl-1-propanol; diethanolamine, triethanolamine, dimethylpropanolamine, dimethylisopropanolamine, dimethyl These include butanolamine, N-benzylethanolamine, 2-[2-(dimethylamine)ethoxy]ethanol; 1-[2-(dimethylamine)ethoxyl]-2-propanol. The coating material may also contain a crosslinking effective amount of a bath-stable nitrogen-containing crosslinker, such as the urea type, melamine type, benzoguanamine, preferably the melamine type. Although a variety of melamines can be used, most preferred are substituted melamines, such as polyalkyl ethers of polymethylolmelamine, in which each alkyl group is
Containing 4 carbon atoms, the most preferred is hexamethoxymethylmelamine. Criteria for the selection of a good crosslinking agent are that it be stable at the high temperatures to which the coating material will be subjected, and that it be reasonably stable to the corrosion-resistant pigments added to the material, and that it be suitable for acrylic resin coating materials. It is possible to provide good crosslinking properties. The amount of crosslinking agent used depends on the number of carboxylic acid groups present in the resin such that the number of functional groups in the crosslinking agent is substantially equal to the number of functional groups present in the alkyl resin. Comparable. It is desirable to add a thermosetting catalyst to the acrylic resin coating material in order to achieve a low crosslinking temperature. A preferred catalyst is a Friedel-Crafts acid catalyst, which is added in an amount of about 1 to about 15% based on the nitrogen-containing crosslinker. These catalysts induce a condensation reaction between the resin and the crosslinker. Suitable acid catalysts that may be used are para-toluenesulfonic acid, dodecylsuccinic acid, n-butyric acid phosphate, phosphoric acid, and the like. It has also been found desirable to add free radical inhibitors to inhibit hydrolysis or other reactions of the resin that can lead to instability. These inhibitors may be added in amounts of about 1 to about 10% by weight of the coating material (acrylic resin and crosslinker combined). Suitable inhibitors are guaiacol, hydroquinone, and the like. Additionally, the coating composition may contain various materials that provide substantially improved corrosion resistance to the final coating. These materials are water-soluble metal salts of group -B of the periodic table. Suitable corrosion-resistant materials are chromates, dichromates, molybdates, tungstates, etc., such as strontium chromate, calcium chromate, zinc chromate, potassium chromate, sodium chromate, sodium dichromate. , potassium tungstate, sodium molybdate, lead silicate, and ammonium salts of chromic acid and dichromic acid. Furthermore, the aforementioned complex salts of molybdic acid and tungstic acid, and the aforementioned water-solubilizing amines, such as dimethylethanolamine, may be used. Acrylic resin is a low molecular weight resin, i.e. approximately
It is also preferred to have a molecular weight (number average) of less than 10,000, more preferably less than about 5,000, and an acid number of less than 150, preferably less than 100. A preferred formulation consists of the following ingredients: Composition A Component Weight Parts : An acrylic resin made from a polymer of ethyl acrylate (71.4%), acrylic acid (12.9%) and methyl methacrylate (15.7%).
In acetone, isopropanol solvent (70% by weight) …………1.25 Hexamethoxymethylmelamine …………1 Water solubilizer (dimethylethanolamine)
…………1.1 Strontium chromate …………2.5 Paratoluenesulfonic acid (25% in water)
…0.24 Water …9.5 It should be recognized that other ingredients such as fillers, pigments, dyes, colorants, leveling agents etc. may be added to the coating material. These ingredients are
It can be added according to the application for which the coated product is to be used. The process of simultaneously sealing and impregnating an unsealed anodic coating is accomplished by immersing a freshly anodized unsealed aluminum substrate surface into a treatment vessel containing one of the aforementioned materials. It is carried out with The new water-soluble resin materials proposed herein are useful at concentrations ranging from less than 1% to more than 70%. The bath is 76.6℃~93.3℃ (170~210℃
〓), can be maintained indefinitely without gelation or precipitation or separation of the resin. PH
By adjusting the pH to a basic pH, preferably about 7.5 to about 9.0, more preferably about 8.2, the pH can be easily adjusted to maintain excellent stability. Time and temperature have a relationship such that the higher the temperature, the shorter the time. The anodic coating changes from an unsealed state to a sealed state due to hydration of the oxide, and as a result of the next reaction, the structure of metal oxide monohydrate and metal oxide trihydrate changes. It has certain characteristics. (1) Al 2 O 3 +H 2 O→2AlO(OH) →Al 2 O 3・H 2 O (2) 2AlO(OH)＋2H 2 O →Al 2 O 3・3H 2 O Sealing/impregnation of anode coating Following, the anodized metal is rinsed in water and then heated preferably at 93.3°C to 260°C (200°C to 200°C) for curing purposes.
Place it in a drying oven adjusted to 500 〓). This step requires a time of about 1 to 60 minutes, and time and temperature have an inverse relationship. If the curing is for parts for the aircraft industry, the temperature is usually 148.8°C (300°C).
〓) Higher temperatures are not used. Sometimes,
It may be desirable to dry the component prior to the curing operation, thereby eliminating the rinsing step after the simultaneous sealing/impregnation step. The above describes a typical processing procedure that follows the usual steps of preparing and anodizing an aluminum substrate. Such preparation for anodizing involves (a) degreasing, (b) alkaline cleaning, and (c) manipulation.
,
Includes deacidification by intermediate water rinsing after each of (b) and (c). Anodization is performed using an electrolyte and process variables necessary to develop an anodic coating, including but not limited to chromic acid, sulfuric acid, and modified sulfuric acid types, followed immediately by a water rinse. Wash. For discussion of cleaning and finishing aluminum and aluminum alloys, please refer to the following for reference:
Metals published by the American Society for Metals
Handbook, 8th edition (1964), Volume 2, 611-634
Please refer to the page. Specific examples of applying corrosion inhibiting coatings in accordance with the present invention to aluminum and aluminum alloy components, particularly 7075-T6, are described below. Example 1 (1) The above member was treated with trichlorethylene or 1-1
-1 trichloroethane material was used for vapor phase degreasing and then left in the degreaser until dry. (2) The degreased material has an active alkalinity of 20 to 25% by weight, a concentration of about 37.5 g/
Maintained at ℃ (approximately 170〓), PH11.8~13
for approximately 18 minutes in a suppressive alkaline detergent. (3) Next, soak the component in water at outside temperature [approx. 20°C (approx. 70°C)]
〓)〕 for about 90 seconds. (4) 66° Baume sulfuric acid 127.3~172.3g/
(17-23 oz/gal) (wt), sodium dichromate 22.5-37.5 g/(3-5 oz/gal) (wt), and ammonium difluoride 4.5-6.0 g/(0.6-0.8 oz/gal) ) (weight), and at room temperature [approximately 20℃ (approximately
The oxide was removed for approximately 8 minutes in an aluminum oxide remover maintained at 70°C. (5) The part was then rinsed with water at ambient temperature for approximately 2 minutes. (6) The part is then heated at 6 to 24 volts (DC) in 15% 66° Baume sulfuric acid for approximately 30 minutes at 12.9 to 16.1 amps/dm 2 (12 to 15 amps/sq ft).
The temperature was maintained at approximately 20°C (approximately 70°C) during anodization. (7) Rinse the anodized part with water at ambient temperature for approximately 2 minutes. (8) The material was then diluted in 2 parts water to 1 part ``Formulation A'' and maintained at 79.4±2.8°C (175±5〓). Soaked for 1 hour. (9) Following this bath in which the part was simultaneously sealed and primed, the part was air dried for 60±5 minutes at ambient temperature. (10) Finally, place the part in a dry air oven for 15 minutes.
Cured at ±2.8°C. Example 2 The parts to be painted are from (1) in Example 1.
It was prepared according to the steps up to (7). (8) Next, the member was made of the resin described in Example 1.
Containing water-soluble composition at 82.2±2.8℃ (180±5〓)
The holes were sealed and a base coat was applied for about 30 minutes in a bath maintained at a constant temperature. (9) Following this bath, the part was air dried and cured as in steps 9 and 10 of Example 1, except that the cure was now 123.8±2.8°C (255±5°C). ) and lasted approximately 30 minutes. Example 3 In this example, the parts to be painted were prepared following the same steps (1) to (5) as in Example 1. (6) Next, the material was mixed with 29.9 to 52.4 g of chromic acid/
(4 to 7 ounces/gallon) (by weight) at approximately 48 volts (DC), 1.07 amps/ dm2 (1 amp/sq. ft.) (minimum), and approximately 37.7 degrees Celsius (100
Anodic oxidation was performed for approximately 48 minutes with operation maintained at 〓). The part was then processed according to the same steps (7) to (10) as in Example 1. Example 4 In this example, the parts to be painted were prepared according to the same steps (1) to (6) as in Example 3. After rinsing with water at outside temperature for about 2 minutes,
The part was processed according to the same steps (8) to (10) as in Example 2. Environmental salt spray tests were conducted on the specimens of Example 2 in a 5% salinity fog operated at 35° C. within the PH range of 6.5 to 7.2. After exposing these specimens for 9000 hours, no signs of erosion due to corrosion were observed. Comparable results were obtained with other examples tested. From all these tests it was concluded that maximum protection against corrosion attack was achieved by sealing at a certain range of high temperatures. The painted aluminum parts in each of the above cases are provided with better corrosion protection against aluminum and aluminum alloys by the method described above than was conventionally obtained from the separate steps of sealing and organic undercoating. It showed that. This means that components that are conventionally anodized, sealed, and zinc chromate and epoxy primed as successive separate steps and components that have been treated as described herein. Determined by comparative tests by exposure to the same corrosive environment for the same extended period of time. For spraying 5% salt
Upon inspection of the test members after 3900 hours of exposure, all prior art members showed corrosion defects, whereas none of the members treated herein showed any signs of corrosion. Furthermore, it has been found that the cost of performing the anodic coating sealing and basecoating operations simultaneously is significantly less than the cost of performing the sealing and basecoating operations in separate operations. This is primarily due to the lack of manual labor required during the basecoating operation. The method of the invention is useful for aluminum and aluminum alloys, where those alloys are composed of aluminum and other elements of the periodic table. See the Metals Handbook , 8th edition (1961), (published by the American Society for Metals), page 917, which is hereby incorporated by reference.
Claims (1)
保護被覆する方法において、 上記被覆すべき部材を陽極酸化し、 この陽極酸化した部材に、水溶性アクリル重合
体又は共重合体と窒素系架橋剤とを含む水性被覆
組成物を、76.6℃〜93.3℃の範囲の温度で60〜30
分間で施し、この時間と温度は温度が高くなる程
時間は短くなる関係にあり、それによつて上記組
成物で陽極酸化部材を水和により封孔し、同時に
陽極酸化部材を下塗りして、後の硬化処理で架橋
することができる表面被覆を与え、次いで 封孔、下塗りした部材を93.3℃〜260℃の範囲
の温度で、60〜１分間で硬化し、この時間と温度
は温度が高くなる程時間は短くなる関係にある ことを特徴とする、上記保護被覆方法。 ２ 被覆組成物の適用を、部材を組成物中に79.4
℃の温度を保ちながら１時間浸漬することによつ
て行う、特許請求の範囲第１項に記載の方法。 ３ 被覆組成物の適用を、部材を組成物中に82.2
℃の温度を保ちながら30分間浸漬することによつ
て行う、特許請求の範囲第１項に記載の方法。 ４ 架橋剤がヘキサメトキシメチルメラミンであ
る、特許請求の範囲第３項に記載の方法。 ５ 架橋剤が、各アルキル基が１〜４個の炭素原
子を含むポリメチロールメラミンのポリアルキル
エーテルである、特許請求の範囲第１項に記載の
方法。 ６ 被覆組成物に対しフリーデルクラフツ触媒
を、93.3℃〜260℃の温度に60〜１分間曝したと
き完全に硬化するのに充分な量で加え、その条件
で硬化を行い、然もその時間と温度は温度が高く
なる程時間は短かくなる関係にある、特許請求の
範囲第１項に記載の方法。 ７ 被覆組成物が、クロム、モリブデンおよびタ
ングステンの水溶性金属塩を含む腐食抑制剤を含
む、特許請求の範囲第１項に記載の方法。[Claims] 1. A method for protectively coating aluminum and aluminum alloy members, wherein the member to be coated is anodized, and the anodized member is coated with a water-soluble acrylic polymer or copolymer and a nitrogen-based crosslinking agent. and at a temperature ranging from 76.6°C to 93.3°C.
This time and temperature are in a relationship that the higher the temperature, the shorter the time.Therefore, the anodized member is sealed with the above composition by hydration, and at the same time, the anodized member is undercoated. A curing process provides a surface coating that can be crosslinked, and then the sealed and primed parts are cured for 60 to 1 minute at temperatures ranging from 93.3°C to 260°C, with the time and temperature increasing at higher temperatures. The above-mentioned protective coating method is characterized in that the heating time is shortened. 2 Application of the coating composition to the component in the composition 79.4
The method according to claim 1, which is carried out by soaking for 1 hour while maintaining a temperature of .degree. 3 Applying the coating composition to the component in the composition 82.2
The method according to claim 1, which is carried out by soaking for 30 minutes while maintaining a temperature of .degree. 4. The method according to claim 3, wherein the crosslinking agent is hexamethoxymethylmelamine. 5. The method of claim 1, wherein the crosslinking agent is a polyalkyl ether of polymethylolmelamine in which each alkyl group contains 1 to 4 carbon atoms. 6 Add a Friedel-Crafts catalyst to the coating composition in an amount sufficient to cause complete curing when exposed to temperatures between 93.3°C and 260°C for 60 to 1 minute, and cure under these conditions, but for that period of time. 2. The method according to claim 1, wherein the relationship between and and temperature is such that the higher the temperature, the shorter the time. 7. The method of claim 1, wherein the coating composition comprises a corrosion inhibitor comprising water-soluble metal salts of chromium, molybdenum and tungsten.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US82333177A | 1977-08-10 | 1977-08-10 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5429852A JPS5429852A (en) | 1979-03-06 |
| JPS629680B2 true JPS629680B2 (en) | 1987-03-02 |
Family
ID=25238460
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9626078A Granted JPS5429852A (en) | 1977-08-10 | 1978-08-09 | Method of protectively coating aluminum and aluminum alloy members |
Country Status (10)
| Country | Link |
|---|---|
| JP (1) | JPS5429852A (en) |
| AU (1) | AU521356B2 (en) |
| CA (1) | CA1111368A (en) |
| DE (1) | DE2830857A1 (en) |
| FR (1) | FR2400070A1 (en) |
| GB (1) | GB1604317A (en) |
| IE (1) | IE47111B1 (en) |
| IT (1) | IT1098376B (en) |
| NL (1) | NL7807842A (en) |
| SE (1) | SE7808528L (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2054410B (en) * | 1979-06-30 | 1983-09-14 | Toyo Seikan Kaisha Ltd | Weld seam-coated cans and their production |
| DE3040729A1 (en) * | 1979-10-31 | 1981-05-14 | Nippon Paint Co., Ltd., Osaka | AQUEOUS PAINT AND ITS USE |
| GB2271729A (en) * | 1992-10-20 | 1994-04-27 | Lo Chung Ching | Aluminum frame of a door or window |
| US6410197B1 (en) | 1998-09-18 | 2002-06-25 | Lexmark International, Inc. | Methods for treating aluminum substrates and products thereof |
| JP4025967B2 (en) * | 2001-11-30 | 2007-12-26 | 株式会社カサタニ | Composition and method for anodizing magnesium alloy |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50119733A (en) * | 1974-03-07 | 1975-09-19 |
-
1978
- 1978-05-31 GB GB25675/78A patent/GB1604317A/en not_active Expired
- 1978-06-30 AU AU37666/78A patent/AU521356B2/en not_active Expired
- 1978-07-03 IE IE1332/78A patent/IE47111B1/en unknown
- 1978-07-13 DE DE19782830857 patent/DE2830857A1/en not_active Withdrawn
- 1978-07-24 NL NL787807842A patent/NL7807842A/en not_active Application Discontinuation
- 1978-07-27 CA CA308,273A patent/CA1111368A/en not_active Expired
- 1978-08-08 IT IT2660778A patent/IT1098376B/en active
- 1978-08-09 SE SE7808528A patent/SE7808528L/en unknown
- 1978-08-09 JP JP9626078A patent/JPS5429852A/en active Granted
- 1978-08-10 FR FR7823618A patent/FR2400070A1/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50119733A (en) * | 1974-03-07 | 1975-09-19 |
Also Published As
| Publication number | Publication date |
|---|---|
| NL7807842A (en) | 1979-02-13 |
| JPS5429852A (en) | 1979-03-06 |
| SE7808528L (en) | 1979-02-11 |
| IT7826607A0 (en) | 1978-08-08 |
| DE2830857A1 (en) | 1979-02-22 |
| AU3766678A (en) | 1980-01-03 |
| GB1604317A (en) | 1981-12-09 |
| FR2400070B3 (en) | 1981-04-10 |
| IE47111B1 (en) | 1983-12-28 |
| IT1098376B (en) | 1985-09-07 |
| IE781332L (en) | 1979-02-10 |
| FR2400070A1 (en) | 1979-03-09 |
| AU521356B2 (en) | 1982-04-01 |
| CA1111368A (en) | 1981-10-27 |
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