JP6750964B2 - Method for manufacturing aluminum alloy material - Google Patents
Method for manufacturing aluminum alloy material Download PDFInfo
- Publication number
- JP6750964B2 JP6750964B2 JP2016094924A JP2016094924A JP6750964B2 JP 6750964 B2 JP6750964 B2 JP 6750964B2 JP 2016094924 A JP2016094924 A JP 2016094924A JP 2016094924 A JP2016094924 A JP 2016094924A JP 6750964 B2 JP6750964 B2 JP 6750964B2
- Authority
- JP
- Japan
- Prior art keywords
- aluminum alloy
- alloy material
- oxide film
- surface treatment
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229910000838 Al alloy Inorganic materials 0.000 title claims description 153
- 239000000956 alloy Substances 0.000 title claims description 140
- 238000004519 manufacturing process Methods 0.000 title claims description 44
- 238000000034 method Methods 0.000 title description 50
- 238000004381 surface treatment Methods 0.000 claims description 117
- 239000000463 material Substances 0.000 claims description 76
- -1 alkyl silicate Chemical compound 0.000 claims description 62
- 229910000077 silane Inorganic materials 0.000 claims description 41
- 238000005530 etching Methods 0.000 claims description 32
- 238000005554 pickling Methods 0.000 claims description 22
- 239000000758 substrate Substances 0.000 claims description 22
- 229910045601 alloy Inorganic materials 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 229910052802 copper Inorganic materials 0.000 claims description 12
- 230000001105 regulatory effect Effects 0.000 claims description 8
- 125000005369 trialkoxysilyl group Chemical group 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 5
- 229910018134 Al-Mg Inorganic materials 0.000 claims description 3
- 229910018467 Al—Mg Inorganic materials 0.000 claims description 3
- 229910018464 Al—Mg—Si Inorganic materials 0.000 claims description 3
- 229910018571 Al—Zn—Mg Inorganic materials 0.000 claims description 3
- 229910017818 Cu—Mg Inorganic materials 0.000 claims description 3
- 239000004840 adhesive resin Substances 0.000 description 99
- 229920006223 adhesive resin Polymers 0.000 description 99
- 239000002585 base Substances 0.000 description 62
- 239000007788 liquid Substances 0.000 description 40
- 239000011777 magnesium Substances 0.000 description 38
- 238000010438 heat treatment Methods 0.000 description 37
- 239000010949 copper Substances 0.000 description 34
- 239000000853 adhesive Substances 0.000 description 31
- 230000001070 adhesive effect Effects 0.000 description 31
- 238000000576 coating method Methods 0.000 description 28
- 239000011248 coating agent Substances 0.000 description 27
- 239000003921 oil Substances 0.000 description 18
- 229920005989 resin Polymers 0.000 description 17
- 239000011347 resin Substances 0.000 description 17
- 230000007797 corrosion Effects 0.000 description 15
- 238000005260 corrosion Methods 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 230000007423 decrease Effects 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- 229910052782 aluminium Inorganic materials 0.000 description 12
- 125000004429 atom Chemical group 0.000 description 12
- 239000003513 alkali Substances 0.000 description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 11
- 229910052749 magnesium Inorganic materials 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 239000012670 alkaline solution Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 230000006866 deterioration Effects 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 9
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 9
- 238000000137 annealing Methods 0.000 description 9
- 238000004140 cleaning Methods 0.000 description 9
- 238000012986 modification Methods 0.000 description 9
- 230000004048 modification Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 239000006087 Silane Coupling Agent Substances 0.000 description 8
- 239000011151 fibre-reinforced plastic Substances 0.000 description 8
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 6
- 230000032683 aging Effects 0.000 description 6
- 238000005238 degreasing Methods 0.000 description 6
- 238000001336 glow discharge atomic emission spectroscopy Methods 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229910003849 O-Si Inorganic materials 0.000 description 5
- 229910003872 O—Si Inorganic materials 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000005097 cold rolling Methods 0.000 description 5
- 239000003822 epoxy resin Substances 0.000 description 5
- 238000005304 joining Methods 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229920000647 polyepoxide Polymers 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 230000035882 stress Effects 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- OBMBUODDCOAJQP-UHFFFAOYSA-N 2-chloro-4-phenylquinoline Chemical compound C=12C=CC=CC2=NC(Cl)=CC=1C1=CC=CC=C1 OBMBUODDCOAJQP-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LVGKNOAMLMIIKO-UHFFFAOYSA-N Elaidinsaeure-aethylester Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC LVGKNOAMLMIIKO-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 description 2
- 239000004954 Polyphthalamide Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000004918 carbon fiber reinforced polymer Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- LVGKNOAMLMIIKO-QXMHVHEDSA-N ethyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC LVGKNOAMLMIIKO-QXMHVHEDSA-N 0.000 description 2
- 229940093471 ethyl oleate Drugs 0.000 description 2
- 239000011152 fibreglass Substances 0.000 description 2
- 238000005098 hot rolling Methods 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000010721 machine oil Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 description 2
- 229920006375 polyphtalamide Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 2
- 229910000165 zinc phosphate Inorganic materials 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- QMMJWQMCMRUYTG-UHFFFAOYSA-N 1,2,4,5-tetrachloro-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=C(Cl)C(Cl)=CC(Cl)=C1Cl QMMJWQMCMRUYTG-UHFFFAOYSA-N 0.000 description 1
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 1
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229910018131 Al-Mn Inorganic materials 0.000 description 1
- 229910018125 Al-Si Inorganic materials 0.000 description 1
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 1
- 229910018461 Al—Mn Inorganic materials 0.000 description 1
- 229910018520 Al—Si Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000003483 aging Methods 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000009749 continuous casting Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000009503 electrostatic coating Methods 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000010137 moulding (plastic) Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920002577 polybenzoxazole Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000002990 reinforced plastic Substances 0.000 description 1
- 239000010731 rolling oil Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 125000003808 silyl group Chemical class [H][Si]([H])([H])[*] 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000001587 sorbitan monostearate Substances 0.000 description 1
- 229940035048 sorbitan monostearate Drugs 0.000 description 1
- 235000011076 sorbitan monostearate Nutrition 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- ZUEKXCXHTXJYAR-UHFFFAOYSA-N tetrapropan-2-yl silicate Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)OC(C)C ZUEKXCXHTXJYAR-UHFFFAOYSA-N 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
- B32B3/10—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a discontinuous layer, i.e. formed of separate pieces of material
- B32B3/14—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a discontinuous layer, i.e. formed of separate pieces of material characterised by a face layer formed of separate pieces of material which are juxtaposed side-by-side
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J201/00—Adhesives based on unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/78—Pretreatment of the material to be coated
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
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- Engineering & Computer Science (AREA)
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- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Chemical Treatment Of Metals (AREA)
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Description
本発明は、アルミニウム合金材の製造方法、アルミニウム合金材、及びアルミニウム合金材を用いた接合体に関する。 The present invention relates to a method for manufacturing an aluminum alloy material, an aluminum alloy material, and a bonded body using the aluminum alloy material.
自動車、船舶及び航空機などの輸送機に用いられる部材の軽量化の観点から、炭素繊維やアルミ合金、鉄鋼材料といった、強度、材質、質量等の異なる異種材料を接合する技術の開発が注目されている。特に、接着樹脂（樹脂接着剤）は、電食による材料の腐食がなく、多様な材料を腐食せずに接合可能なことから、近年積極的に研究されている。しかしながら、高湿環境下では、金属と接着樹脂の界面に水分が浸入し、金属表面の腐食・劣化が起こり、金属と接着樹脂の界面で容易に剥離するため、接着強度が著しく低下してしまう。そのため、金属と接着樹脂の界面を腐食から保護し、湿潤環境下でも接着強度を低下させないような前処理が、接着耐久性を左右する重要な因子となる。 From the viewpoint of reducing the weight of members used in transportation machines such as automobiles, ships, and aircraft, attention has been paid to the development of technology for joining dissimilar materials such as carbon fiber, aluminum alloys, and steel materials having different strengths, materials, and masses. There is. In particular, an adhesive resin (resin adhesive) has been actively studied in recent years because it does not corrode materials due to electrolytic corrosion and can bond various materials without corroding. However, in a high-humidity environment, water penetrates into the interface between the metal and the adhesive resin, causing corrosion and deterioration of the metal surface and easily peeling off at the interface between the metal and the adhesive resin, resulting in a significant decrease in adhesive strength. .. Therefore, pretreatment that protects the interface between the metal and the adhesive resin from corrosion and does not reduce the adhesive strength even in a wet environment is an important factor that determines the adhesive durability.
ここで、接着用前処理としては、防食の観点から、金属表面の耐食性や塗料密着性を向上させるための表面処理が知られている。 Here, as the pretreatment for adhesion, a surface treatment for improving the corrosion resistance of the metal surface and the paint adhesion is known from the viewpoint of corrosion protection.
例えば、特許文献１には、テトラエチルオルソシリケート等のテトラアルキルシリケートと、シリカゾル等の水和酸化物ゾルを含む水性組成物でアルミニウム等の金属を処理することにより、その上に形成される接着剤などの塗膜の初期密着性や密着性の長期安定性を向上させる手法が記載されている。 For example, in Patent Document 1, an adhesive formed on a metal such as aluminum by treating a metal such as aluminum with an aqueous composition containing a tetraalkyl silicate such as tetraethyl orthosilicate and a hydrated oxide sol such as silica sol. And other methods for improving the initial adhesion and long-term stability of the adhesion of the coating film.
また、特許文献２には、少なくとも２個の３置換シリル基を有する少なくとも１種類の多官能性シランのみから本質的になる第一の処理溶液で金属基板を処理した後、少なくとも１種類のオルガノ官能性シランを含む第二の処理溶液を含む第二の被覆を施すことにより、金属の耐食性を向上させる手法が記載されている。 Further, in Patent Document 2, after treating a metal substrate with a first treatment solution consisting essentially of at least one multifunctional silane having at least two tri-substituted silyl groups, at least one organo Techniques for improving the corrosion resistance of metals by applying a second coating containing a second treatment solution containing a functional silane are described.
また、特許文献３には、アミノシランと多シリル官能シランを含む溶液により金属基材を処理することにより、金属の耐食性を向上させる手法が記載されている。 Further, Patent Document 3 describes a method of improving the corrosion resistance of a metal by treating a metal base material with a solution containing aminosilane and polysilyl functional silane.
また、特許文献４には、亜鉛メッキ鋼板の表面をケイ酸化合物を含む水溶液でリンスした後、シランカップリング剤で処理することで耐食性を向上させる方法が記載されている。 Further, Patent Document 4 describes a method of improving corrosion resistance by rinsing the surface of a galvanized steel sheet with an aqueous solution containing a silicic acid compound and then treating the surface with a silane coupling agent.
また、特許文献５には、ケイ酸エステル、アルミニウム無機塩及びポリエチレングリコールを含有し、シランカップリング剤をさらに含有させた溶液を、亜鉛系めっき鋼板上に塗布、乾燥して皮膜を形成させることで、塗料密着性及び耐白錆性を向上させる手法が記載されている。 Further, in Patent Document 5, a solution containing a silicate ester, an aluminum inorganic salt and polyethylene glycol and further containing a silane coupling agent is applied on a zinc-based plated steel sheet and dried to form a film. Describes a method for improving paint adhesion and white rust resistance.
また、特許文献６には、ナトリウム水ガラス等の水ガラスと、アミノシラン等のシランを含む水溶液により、アルミニウムやアルミニウム合金等の金属材料の表面を処理することで、塗料密着性を向上させる手法が記載されている。 Further, Patent Document 6 discloses a method for improving coating adhesion by treating the surface of a metal material such as aluminum or an aluminum alloy with an aqueous solution containing water glass such as sodium water glass and silane such as aminosilane. Have been described.
また、特許文献７には、無機珪酸塩、有機官能性シラン及び２以上のトリアルコキシシリル基を含む架橋剤を含有するアルカリ溶液で金属シートを処理することにより、耐食性及び塗料付着性を向上させる手法が記載されている。 Further, in Patent Document 7, by treating a metal sheet with an alkaline solution containing an inorganic silicate, an organofunctional silane and a crosslinking agent containing two or more trialkoxysilyl groups, corrosion resistance and paint adhesion are improved. The method is described.
しかしながら、特許文献１に記載の手法では、長期の湿潤劣化試験により接着強度が著しく減少してしまうため、接着耐久性は十分なものとはいえない。 However, in the method described in Patent Document 1, the adhesive strength is remarkably reduced by the long-term wet deterioration test, and therefore the adhesive durability cannot be said to be sufficient.
また、特許文献２及び特許文献３に記載の手法では、生成するシラン皮膜の接着耐久性は十分でなく、高温乾燥または長時間の処理を必要とするなどプロセスへの実用性にも問題がある。 Further, in the methods described in Patent Documents 2 and 3, the adhesion durability of the produced silane coating is not sufficient, and there is a problem in the practicality of the process such as high temperature drying or long-time treatment. ..
また、特許文献４〜特許文献７に記載の手法は、あくまで金属表面の防食や塗料の密着性の改善を目的とするものである。したがって、形成される皮膜は肉厚となるが、肉厚な皮膜では皮膜自身の機械強度が低く、張力や応力に対して脆くなり、高い接着強度を得ることができない。 Further, the methods described in Patent Documents 4 to 7 are intended only for the purpose of preventing corrosion on the metal surface and improving the adhesiveness of the paint. Therefore, the formed film becomes thick, but a thick film has a low mechanical strength of the film itself, becomes brittle against tension and stress, and high adhesive strength cannot be obtained.
また、表面処理後のアルミニウム合金材は、加工性向上のため表面処理後に塗油を行い、その後成形し、接着を行う。ここで、表面処理皮膜と接着剤の間に潤滑油や圧延油などの機械油が含まれると、接着剤の密着性が大きく低下し、高い接着強度を得ることができないことから、表面に圧延油等の機械油が付着しても接着耐久性が低下しないアルミニウム合金材の開発が求められている。 In addition, the aluminum alloy material after the surface treatment is applied with oil after the surface treatment for improving the workability, and then molded and adhered. Here, if mechanical oil such as lubricating oil or rolling oil is contained between the surface treatment film and the adhesive, the adhesiveness of the adhesive will be significantly reduced and high adhesive strength cannot be obtained. There is a demand for the development of an aluminum alloy material that does not deteriorate the adhesion durability even when mechanical oil such as oil adheres.
そこで、本発明は、高温湿潤環境に曝されても、接着強度が低下し難く、接着耐久性に優れ、かつ生産性に優れたアルミニウム合金材を製造できるアルミニウム合金材の製造方法、アルミニウム合金材、及びアルミニウム合金材を用いた接合体を提供することを主目的とする。 Therefore, the present invention provides a method for producing an aluminum alloy material, which is capable of producing an aluminum alloy material which is resistant to a decrease in adhesive strength even when exposed to a high temperature wet environment, has excellent adhesive durability, and is excellent in productivity, and an aluminum alloy material. And to provide a joined body using an aluminum alloy material.
本発明者らは、前述した課題を解決するために鋭意検討した結果、表面に形成された酸化皮膜中のＭｇ量及びＣｕ量が特定の範囲に調整されたアルミニウム基材の酸化皮膜に、アルキルシリケートまたはそのオリゴマーと有機シラン化合物とを含む所定の水溶液を塗布することにより形成された皮膜は、基材との結合力が強く、耐食性を有し、薄くとも強度に優れ、かつ接着剤との接合性が良好であることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the amount of Mg and the amount of Cu in the oxide film formed on the surface of the aluminum-based oxide film adjusted to a specific range are A film formed by applying a predetermined aqueous solution containing a silicate or an oligomer thereof and an organic silane compound has a strong bonding force with a base material, has corrosion resistance, and is excellent in strength even if thin, and with an adhesive. The inventors have found that the bondability is good and have completed the present invention.
即ち、本発明に係るアルミニウム合金材の製造方法は、アルミニウム合金基材の表面の少なくとも一部に、Ｍｇを０．１原子％以上３０原子％未満含有し、Ｃｕが０．６原子％未満に規制された酸化皮膜を形成する酸化皮膜形成工程と、前記酸化皮膜の少なくとも一部に、０．００５質量％以上１質量％未満のアルキルシリケートまたはそのオリゴマーと、０．００５質量％以上１質量％未満の有機シラン化合物とを含み、ｐＨが２以上７以下である水溶液を塗布することを含む表面処理皮膜形成工程とを備えることを特徴とする。 That is, in the method for producing an aluminum alloy material according to the present invention, at least a part of the surface of the aluminum alloy substrate contains Mg in an amount of 0.1 atomic% or more and less than 30 atomic% and Cu in an amount of less than 0.6 atomic %. An oxide film forming step of forming a regulated oxide film, and 0.005% by mass or more and less than 1% by mass of an alkyl silicate or an oligomer thereof in at least a part of the oxide film and 0.005% by mass or more and 1% by mass. And a surface treatment film forming step including applying an aqueous solution having a pH of 2 or more and 7 or less.
ここで、前記皮膜中のＭｇ量、及びＣｕ量は、高周波グロー放電発光分光分析法（ＧＤ−ＯＥＳ：Glow Discharge-Optical Emission Spectroscopy）により測定した値である。 Here, the amount of Mg and the amount of Cu in the said film|membrane are the values measured by the high frequency glow discharge optical emission spectroscopy (GD-OES:Glow Discharge-Optical Emission Spectroscopy).
また、本発明のアルミニウム合金材の製造方法においては、前記有機シラン化合物が分子内に加水分解可能なトリアルコキシシリル基を複数有するシラン化合物、その加水分解物またはその重合体を含むことが好ましい。 In the method for producing an aluminum alloy material of the present invention, it is preferable that the organic silane compound contains a silane compound having a plurality of hydrolyzable trialkoxysilyl groups in the molecule, a hydrolyzate thereof, or a polymer thereof.
また、本発明のアルミニウム合金材の製造方法においては、前記酸化皮膜形成工程がエッチング処理段階を含み、前記エッチング処理段階におけるエッチング量が１．９ｇ／ｍ２以下であってもよい。 Further, in the method for manufacturing an aluminum alloy material of the present invention, the oxide film forming step may include an etching treatment step, and an etching amount in the etching treatment step may be 1.9 g/m 2 or less.
また、本発明のアルミニウム合金材の製造方法においては、前記エッチング処理段階の最後の段階が酸洗であることが好ましい。 Further, in the method for producing an aluminum alloy material of the present invention, it is preferable that the last step of the etching treatment step is pickling.
前記アルミニウム合金基材は、例えば、Ａｌ−Ｍｇ系合金、Ａｌ−Ｃｕ−Ｍｇ系合金、Ａｌ−Ｍｇ−Ｓｉ系合金又はＡｌ−Ｚｎ−Ｍｇ系合金で形成することができる。 The aluminum alloy base material can be formed of, for example, an Al-Mg-based alloy, an Al-Cu-Mg-based alloy, an Al-Mg-Si-based alloy, or an Al-Zn-Mg-based alloy.
また、本発明は、前記アルミニウム合金材の製造方法により得られたアルミニウム合金材をも包含する。 The present invention also includes an aluminum alloy material obtained by the method for producing an aluminum alloy material.
また、本発明の接合体は、前記アルミニウム合金材と他の部材とを接着樹脂を介して接合したものである。 Further, the joined body of the present invention is obtained by joining the aluminum alloy material and another member through an adhesive resin.
本発明によれば、高温湿潤環境に曝されても、接着強度が低下し難く、接着耐久性に優れたアルミニウム合金材を実現することができる。また、本発明によれば、酸化皮膜を形成したアルミニウム合金基材に対して、アルキルシリケートまたはそのオリゴマーと有機シラン化合物とを含む水溶液を用いて、シリケート処理及び有機シラン処理を同時に行うことで、簡略化された工程でアルミニウム合金材（表面処理アルミニウム合金材ともいう）の製造が可能となり、設備投資費や製造コストを低減することができる。 According to the present invention, it is possible to realize an aluminum alloy material in which the adhesive strength does not easily decrease even when exposed to a high temperature and wet environment and the adhesive durability is excellent. Further, according to the present invention, with respect to the aluminum alloy base material on which the oxide film is formed, using an aqueous solution containing an alkyl silicate or an oligomer thereof and an organic silane compound, by performing the silicate treatment and the organic silane treatment at the same time, An aluminum alloy material (also referred to as a surface-treated aluminum alloy material) can be manufactured in a simplified process, and capital investment and manufacturing cost can be reduced.
以下、本発明を実施するための形態について、詳細に説明する。なお、本発明は、以下に説明する実施形態に限定されるものではない。 Hereinafter, modes for carrying out the present invention will be described in detail. The present invention is not limited to the embodiments described below.
（第１の実施形態）
まず、本実施形態のアルミニウム合金材の製造方法及び当該製造方法により得られるアルミニウム合金材について説明する。本実施形態に係るアルミニウム合金材の製造方法は、アルミニウム合金基材の表面の少なくとも一部に、Ｍｇを０．１原子％以上３０原子％未満含有し、Ｃｕが０．６原子％未満に規制された酸化皮膜を形成する酸化皮膜形成工程と、前記酸化皮膜の少なくとも一部に、０．００５質量％以上１質量％未満のアルキルシリケートまたはそのオリゴマーと、０．００５質量％以上１質量％未満の有機シラン化合物とを含み、ｐＨが２以上７以下である水溶液を塗布することを含む表面処理皮膜形成工程とを備えるものである。
図１は本実施形態のアルミニウム合金材１０の製造方法を示すフローチャート図である。図１に示すように、本実施形態のアルミニウム合金材１０を製造する際は、基材作製工程Ｓ１、酸化皮膜形成工程Ｓ２、及び表面処理皮膜形成工程Ｓ３を行う。以下、各工程について説明する。
(First embodiment)
First, the manufacturing method of the aluminum alloy material of the present embodiment and the aluminum alloy material obtained by the manufacturing method will be described. In the method for manufacturing an aluminum alloy material according to the present embodiment, Mg is contained in at least a part of the surface of the aluminum alloy base material in an amount of 0.1 atomic% or more and less than 30 atomic %, and Cu is regulated to less than 0.6 atomic %. An oxide film forming step of forming a formed oxide film, and 0.005% by mass or more and less than 1% by mass of an alkyl silicate or an oligomer thereof in at least a part of the oxide film and 0.005% by mass or more and less than 1% by mass. And a surface treatment film forming step, which comprises applying an aqueous solution containing the organic silane compound of 2 above and having a pH of 2 or more and 7 or less.
FIG. 1 is a flowchart showing a method for manufacturing the aluminum alloy material 10 of this embodiment. As shown in FIG. 1, when manufacturing the aluminum alloy material 10 of the present embodiment, a base material manufacturing step S1, an oxide film forming step S2, and a surface treatment film forming step S3 are performed. Each step will be described below.
＜ステップＳ１：基材作製工程＞
基材の形状は特に限定されるものではなく、アルミニウム合金材を用いて作製する部材の形状等に応じて、板状の他、鋳造材、鍛造材、押し出し材（例えば、中空棒状等）等としてとりうる任意の形状であってもよい。基材作製工程Ｓ１では、例として板状の基材（基板）を作製する場合には、例えば下記の手順で、基板を作製する。先ず、所定の組成を有するアルミニウム合金を、連続鋳造により溶解し、鋳造して鋳塊を作製する（溶解鋳造工程）。次に、作製した鋳塊に均質化熱処理を施す（均質化熱処理工程）。その後、均質化熱処理された鋳塊に、熱間圧延を施して熱延板を作製する（熱間圧延工程）。そして、この熱延板に３００〜５８０℃で荒焼鈍又は中間焼鈍を行い、最終冷間圧延率５％以上の冷間圧延を少なくとも１回施して、所定の板厚の冷延板（基板）を得る（冷間圧延工程）。
<Step S1: Base material manufacturing process>
The shape of the base material is not particularly limited, and depending on the shape and the like of the member manufactured using the aluminum alloy material, in addition to the plate shape, a cast material, a forged material, an extruded material (for example, a hollow rod shape), etc. It may have any shape that can be taken as. In the base material manufacturing step S1, for example, when a plate-shaped base material (substrate) is manufactured, the substrate is manufactured by the following procedure, for example. First, an aluminum alloy having a predetermined composition is melted by continuous casting and cast to produce an ingot (melt casting step). Next, the produced ingot is subjected to homogenizing heat treatment (homogenizing heat treatment step). Then, the homogenized heat-treated ingot is hot-rolled to produce a hot-rolled sheet (hot-rolling step). Then, this hot-rolled sheet is subjected to rough annealing or intermediate annealing at 300 to 580° C., and subjected to cold rolling at a final cold rolling rate of 5% or more at least once to obtain a cold-rolled sheet (substrate) having a predetermined sheet thickness. Is obtained (cold rolling step).
冷間圧延工程では、荒焼鈍又は中間焼鈍の温度を３００℃以上とすることが好ましく、これにより、成形性向上の効果がより発揮される。また、荒焼鈍又は中間焼鈍の温度は、５８０℃以下とすることが好ましく、これにより、バーニングの発生による成形性の低下を抑制しやすくなる。一方、最終冷間圧延率は、５％以上とすることが好ましく、これにより、成形性向上の効果がより発揮される。なお、均質化熱処理及び熱間圧延の条件は、特に限定されるものではなく、熱延板を通常得る場合の条件で行うことができる。また、中間焼鈍は行わなくてもよい。 In the cold rolling step, it is preferable that the temperature of the rough annealing or the intermediate annealing is 300° C. or higher, and thereby the effect of improving the formability is more exerted. Further, the temperature of the rough annealing or the intermediate annealing is preferably set to 580° C. or lower, which makes it easy to suppress the deterioration of the formability due to the occurrence of burning. On the other hand, the final cold rolling rate is preferably set to 5% or more, whereby the effect of improving formability is more exerted. The conditions for the homogenizing heat treatment and hot rolling are not particularly limited, and the conditions for obtaining a hot rolled sheet can be used. Moreover, the intermediate annealing may not be performed.
［基材］
基材（アルミニウム合金基材）は、アルミニウム合金からなる。基材を形成するアルミニウム合金の種類は、特に限定されるものではなく、加工される部材の用途に応じて、ＪＩＳに規定される又はＪＩＳに近似する種々の非熱処理型若しくは熱処理型のアルミニウム合金から適宜選択して使用することができる。ここで、非熱処理型アルミニウム合金としては、純アルミニウム（１０００系）、Ａｌ−Ｍｎ系合金（３０００系）、Ａｌ−Ｓｉ系合金（４０００系）及びＡｌ−Ｍｇ系合金（５０００系）がある。また、熱処理型アルミニウム合金としては、Ａｌ−Ｃｕ−Ｍｇ系合金（２０００系）、Ａｌ−Ｍｇ−Ｓｉ系合金（６０００系）及びＡｌ−Ｚｎ−Ｍｇ系合金（７０００系）がある。
[Base material]
The base material (aluminum alloy base material) is made of an aluminum alloy. The type of aluminum alloy forming the base material is not particularly limited, and various non-heat treatment type or heat treatment type aluminum alloys defined by JIS or similar to JIS are selected according to the use of the member to be processed. Can be appropriately selected and used. Here, as the non-heat treatment type aluminum alloy, there are pure aluminum (1000 series), Al-Mn series alloy (3000 series), Al-Si series alloy (4000 series) and Al-Mg series alloy (5000 series). Further, as the heat treatment type aluminum alloy, there are an Al—Cu—Mg type alloy (2000 type), an Al—Mg—Si type alloy (6000 type) and an Al—Zn—Mg type alloy (7000 type).
例えば、本実施形態のアルミニウム合金材を自動車用部材に用いる場合は、強度の観点から、基材は０．２％耐力が１００ＭＰａ以上であることが好ましい。このような特性を満足する基材を形成可能なアルミニウム合金としては、２０００系、５０００系、６０００系及び７０００系などのように、マグネシウムを比較的多く含有するものがあり、これらの合金は必要に応じて調質してもよい。また、各種アルミニウム合金の中でも、時効硬化能に優れ、合金元素量が比較的少なくスクラップのリサイクル性や成形性にも優れていることから、６０００系アルミニウム合金を用いることが好ましい。 For example, when the aluminum alloy material of the present embodiment is used as a member for automobiles, the 0.2% proof stress of the base material is preferably 100 MPa or more from the viewpoint of strength. Aluminum alloys capable of forming a base material satisfying such characteristics include those containing a relatively large amount of magnesium, such as 2000 series, 5000 series, 6000 series and 7000 series, and these alloys are required. It may be tempered according to. In addition, among various aluminum alloys, it is preferable to use the 6000 series aluminum alloy because it has excellent age hardening ability, has a relatively small amount of alloying elements, and has excellent scrap recyclability and formability.
＜ステップＳ２：酸化皮膜形成工程＞
酸化皮膜形成工程（ステップＳ２）では、ステップＳ１の基材作製工程で作製された基材の表面の少なくとも一部（すなわち、一部又は全部）に、Ｍｇを０．１原子％以上３０原子％未満含有し、Ｃｕが０．６原子％未満に規制された酸化皮膜を形成する。本実施形態において、酸化皮膜形成工程（ステップＳ２）は、具体的には、例えば、基材３を加熱処理して酸化皮膜１を形成する加熱処理段階と、当該加熱処理段階後のエッチング処理段階とを備える。
<Step S2: oxide film forming step>
In the oxide film forming step (step S2), at least a part (that is, a part or all) of the surface of the base material manufactured in the base material manufacturing step of step S1 contains Mg in an amount of 0.1 atomic% or more and 30 atomic% or more. To form an oxide film containing less than 0.6 atom% of Cu. In the present embodiment, specifically, the oxide film forming step (step S2) includes, for example, a heat treatment step of heat-treating the base material 3 to form the oxide film 1, and an etching treatment step after the heat treatment step. With.
図２に、基材３の表面に酸化皮膜１が形成された、表面処理皮膜形成工程前のアルミニウム合金材を示す。なお、図２に示される表面処理皮膜形成工程前のアルミニウム合金材では、基材３の一方の表面の全部に酸化皮膜１が形成されているが、本実施形態はこれに限定されるものではない。例えば、基材３の表面の一部のみに酸化皮膜１が形成されていてもよい。また、基材３の両面に酸化皮膜１が形成されていてもよい。 FIG. 2 shows an aluminum alloy material in which the oxide film 1 is formed on the surface of the base material 3 and before the surface treatment film forming step. In the aluminum alloy material before the surface treatment film forming step shown in FIG. 2, the oxide film 1 is formed on the entire one surface of the substrate 3, but the present embodiment is not limited to this. Absent. For example, the oxide film 1 may be formed only on a part of the surface of the base material 3. Further, the oxide film 1 may be formed on both surfaces of the base material 3.
加熱処理段階における加熱処理としては、基材３を、例えば４００〜５８０℃の温度に加熱して、基材３の表面に酸化皮膜１を形成する。また、加熱処理は、アルミニウム合金材１０の強度を調整する効果もある。なお、ここで行う加熱処理は、基材３が熱処理型アルミニウム合金で形成されている場合には溶体化処理であり、基材３が非熱処理型アルミニウム合金で形成されている場合には、焼鈍（最終焼鈍）における加熱処理である。 As the heat treatment in the heat treatment stage, the base material 3 is heated to a temperature of 400 to 580° C., for example, to form the oxide film 1 on the surface of the base material 3. The heat treatment also has the effect of adjusting the strength of the aluminum alloy material 10. The heat treatment performed here is a solution treatment when the base material 3 is formed of a heat treatment type aluminum alloy, and an annealing is performed when the base material 3 is formed of a non-heat treatment type aluminum alloy. It is a heat treatment in (final annealing).
この加熱処理は、強度向上の観点から、加熱速度１００℃／分以上の急速加熱とすることが好ましい。また、加熱温度を４００℃以上に設定して急速加熱することで、アルミニウム合金材１０の強度や、そのアルミニウム合金材１０の塗装後加熱（ベーキング）した後の強度を、より高めることができる。一方、加熱温度を５８０℃以下に設定して急速加熱することにより、バーニングの発生による成形性の低下を抑制することができる。更に、強度を向上させる観点からは、加熱処理における保持時間は３〜３０秒とすることが好ましい。このように基材３を、加熱温度４００〜５８０℃で加熱すると、基材３の表面に、例えば、膜厚が１〜３０ｎｍの酸化皮膜１が形成される。なお、加熱処理の前には、必要に応じてアルカリ脱脂等を行ってもよい。 From the viewpoint of improving strength, this heat treatment is preferably rapid heating at a heating rate of 100° C./min or more. Further, by setting the heating temperature to 400° C. or higher and performing rapid heating, the strength of the aluminum alloy material 10 and the strength of the aluminum alloy material 10 after heating (baking) after coating can be further increased. On the other hand, by setting the heating temperature to 580° C. or lower and performing rapid heating, it is possible to suppress deterioration of formability due to occurrence of burning. Further, from the viewpoint of improving the strength, the holding time in the heat treatment is preferably 3 to 30 seconds. Thus, when the base material 3 is heated at a heating temperature of 400 to 580° C., the oxide film 1 having a film thickness of 1 to 30 nm is formed on the surface of the base material 3, for example. Before the heat treatment, alkali degreasing or the like may be performed if necessary.
加熱処理後のエッチング処理段階においては、アルミニウム合金基材３の表面の一部又は全部に対して、酸性溶液による処理（酸洗）及びアルカリ溶液による処理（アルカリ洗浄、アルカリ脱脂）のうちの少なくとも１つを行う。酸洗の際に用いる薬液（酸洗剤）は、特に限定されるものではないが、例えば、硫酸、硝酸及びフッ酸から選ばれる群からなる１種以上を含む溶液を用いることができる。また、酸洗剤には、脱脂性を高めるために界面活性剤を含有させてもよい。また、酸洗の条件は、基材３の合金組成や酸化皮膜１の厚み等を考慮して適宜設定することができ、特に限定されないが、たとえば、ｐＨが４以下(好ましくは２以下)、処理温度１０〜８０℃、処理時間１〜１２０秒の条件を適用することができる。 In the etching treatment step after the heat treatment, at least part of the surface of the aluminum alloy substrate 3 is treated with an acidic solution (pickling) or an alkaline solution (alkali cleaning, degreasing). Do one. The chemical solution (acid detergent) used for pickling is not particularly limited, but for example, a solution containing at least one selected from the group consisting of sulfuric acid, nitric acid, and hydrofluoric acid can be used. Further, the acid detergent may contain a surfactant in order to enhance degreasing property. The conditions of pickling can be appropriately set in consideration of the alloy composition of the base material 3, the thickness of the oxide film 1 and the like, and are not particularly limited, but for example, the pH is 4 or less (preferably 2 or less), Conditions of a treatment temperature of 10 to 80° C. and a treatment time of 1 to 120 seconds can be applied.
また、アルカリ洗浄（アルカリ脱脂）の際に用いる薬液も、特に限定されるものではないが、例えば、水酸化ナトリウム及び水酸化カリウムから選ばれる群からなる１種以上を含む溶液を用いることができる。また、アルカリ溶液による処理の条件は、基材３の合金組成や酸化皮膜１の厚み等を考慮して適宜設定することができ、特に限定されないが、例えば、ｐＨが１０以上、処理温度１０〜８０℃、処理時間１〜１２０秒の条件を適用することができる。 Further, the chemical solution used in the alkali cleaning (alkali degreasing) is not particularly limited, but for example, a solution containing at least one selected from the group selected from sodium hydroxide and potassium hydroxide can be used. .. The condition of the treatment with the alkaline solution can be appropriately set in consideration of the alloy composition of the base material 3, the thickness of the oxide film 1 and the like, and is not particularly limited, but for example, the pH is 10 or more, the treatment temperature is 10 to 10. The conditions of 80° C. and treatment time of 1 to 120 seconds can be applied.
なお、アルカリ洗浄を行う場合においては、アルカリ洗浄よりも後に、酸洗を行うことが好ましい。また、アルカリ洗浄なしで、酸洗だけを行ってもよい。すなわち、エッチング処理段階においては、最後の段階が酸洗であることが好ましい。この理由は以下のとおりである。すなわち、アルカリ洗浄では、基材表面のＭｇを除去することが難しく、基材表面のＭｇの存在によりエッチング量を増やす必要がある。しかしながら、エッチング量が増えるとＣｕの濃化の原因となることから、酸洗でＭｇを除去する必要があるためである。 In the case of carrying out the alkali cleaning, it is preferable to carry out the pickling after the alkali cleaning. Alternatively, only pickling may be performed without alkali cleaning. That is, in the etching process stage, the last stage is preferably pickling. The reason for this is as follows. That is, it is difficult to remove Mg on the surface of the base material by alkali cleaning, and it is necessary to increase the etching amount due to the presence of Mg on the surface of the base material. However, it is necessary to remove Mg by pickling, because an increase in the amount of etching causes a concentration of Cu.
また、各薬液での洗浄後にはリンスを行うことが好ましい。リンスの方法は特に限定されないが、例えば、スプレー、浸漬等が挙げられる。また、リンスに用いられる洗浄液としては、例えば、工業水、純水、イオン交換水等が挙げられる。 In addition, it is preferable to perform rinsing after cleaning with each chemical. The rinsing method is not particularly limited, and examples thereof include spraying and dipping. Examples of the cleaning liquid used for rinsing include industrial water, pure water, ion-exchanged water and the like.
以上のようなエッチング処理段階を実施することにより、酸化皮膜１中のＭｇ量を０．１原子％以上３０原子％未満に調整し、かつ、Ｃｕ量を０．６原子％未満に規制する。ここで、酸化皮膜中のＭｇ量及びＣｕ量は、酸洗やアルカリ洗浄における各種条件（処理時間、処理温度、及び、薬液の濃度及びｐＨ等）を適宜制御することによって調整ないし規制することができる。 By carrying out the above etching treatment step, the amount of Mg in the oxide film 1 is adjusted to 0.1 atom% or more and less than 30 atom %, and the amount of Cu is regulated to less than 0.6 atom %. Here, the amount of Mg and the amount of Cu in the oxide film can be adjusted or regulated by appropriately controlling various conditions (treatment time, treatment temperature, concentration and pH of the chemical solution, etc.) in pickling and alkaline washing. it can.
また、エッチング処理段階におけるエッチング量は、１．９ｇ／ｍ２以下であることが好ましい。エッチング量１．９ｇ／ｍ２を超えると、基材３の表面において銅の濃化が生じ、劣化環境である高温湿潤環境において、接着樹脂の劣化の原因となるおそれがある。また、当該エッチング量は、より好ましくは１．５ｇ／ｍ２以下であり、さらに好ましくは１．３ｇ／ｍ２以下である。なお、当該エッチング量の下限は、特に限定されるものではないが、例えば、０．００５ｇ／ｍ２である。 In addition, the etching amount in the etching treatment stage is preferably 1.9 g/m 2 or less. When the etching amount exceeds 1.9 g/m 2 , copper is concentrated on the surface of the base material 3, which may cause deterioration of the adhesive resin in a high temperature wet environment which is a deterioration environment. Further, the etching amount is more preferably 1.5 g/m 2 or less, and further preferably 1.3 g/m 2 or less. The lower limit of the etching amount is not particularly limited, but is 0.005 g/m 2 , for example.
ここで、本明細書中におけるエッチング量（単位：ｇ／ｍ２）は、酸化皮膜形成工程前後の基材の重量の減少量（単位：ｇ）を測定し、これを基材の表面積（単位：ｍ２）で割ることにより算出される値である。 Here, the etching amount (unit: g/m 2 ) in the present specification is obtained by measuring the reduction amount (unit: g) of the weight of the base material before and after the oxide film forming step, : M 2 ) It is a value calculated by dividing.
［酸化皮膜１］
本酸化皮膜形成工程によれば、基材３の表面の少なくとも一部に、Ｍｇを０．１原子％以上３０原子％未満含有し、Ｃｕが０．６原子％未満に規制された酸化皮膜１が形成される。以下、酸化皮膜１に含まれる各成分量の好適な範囲について説明する。
[Oxide film 1]
According to the present oxide film forming step, the oxide film 1 containing Mg in an amount of 0.1 atom% or more and less than 30 atom% and Cu regulated to less than 0.6 atom% on at least a part of the surface of the base material 3. Is formed. Hereinafter, a suitable range of the amount of each component contained in the oxide film 1 will be described.
＜Ｍｇ含有量＞
アルミニウム合金材の基材を構成するアルミニウム合金には、通常、合金成分としてマグネシウムが含まれており、このような基材３の表面にアルミニウムとマグネシウムの複合酸化物である酸化皮膜１を形成すると、表面にマグネシウム酸化皮膜が濃化した状態で存在することとなる。よって、この状態では、後述する次のステップＳ３である表面処理皮膜形成工程を経ようとも、マグネシウム酸化皮膜層が厚すぎることから、後述する表面処理皮膜２に多くのマグネシウムが含まれることとなり、このように形成した表面処理皮膜２では、皮膜自体の強度が得られず、初期の接着性が低下する。
<Mg content>
The aluminum alloy constituting the base material of the aluminum alloy material usually contains magnesium as an alloy component, and when the oxide film 1 which is a composite oxide of aluminum and magnesium is formed on the surface of the base material 3 as described above. Thus, the magnesium oxide film is present on the surface in a concentrated state. Therefore, in this state, the magnesium oxide film layer is too thick even if the surface treatment film forming step of the next step S3 to be described later is performed, so that the surface treatment film 2 to be described later contains a large amount of magnesium, In the surface-treated film 2 thus formed, the strength of the film itself cannot be obtained, and the initial adhesiveness is lowered.
また、水分、酸素及び塩化物イオンなどが浸透してくる高温湿潤環境においては、接着樹脂層との界面の水和や基材の腐食の原因となり、アルミニウム合金材の接着耐久性を低下させる。具体的には、後述する表面処理皮膜形成前の酸化皮膜１中のＭｇ含有量が３０原子％以上になると、表面処理皮膜形成後のアルミニウム合金材の初期の接着性や接着耐久性が低下する傾向がある。そこで、本実施形態のアルミニウム合金材１０の製造方法では、表面処理皮膜形成前の酸化皮膜１におけるＭｇ含有量を３０原子％未満に規制する。これにより、初期の接着性や接着耐久性を向上することができる。表面処理皮膜形成前の酸化皮膜１のＭｇ含有量は、初期の接着性や接着耐久性の向上の観点から、２５原子％未満が好ましく、２０原子％未満がより好ましく、さらに好ましくは１０原子％未満である。 Further, in a high temperature wet environment where water, oxygen, chloride ions, etc. permeate, it causes hydration of the interface with the adhesive resin layer and corrosion of the base material, and reduces the adhesion durability of the aluminum alloy material. Specifically, when the Mg content in the oxide film 1 before forming the surface treatment film described later is 30 atomic% or more, the initial adhesiveness and adhesion durability of the aluminum alloy material after forming the surface treatment film decrease. Tend. Therefore, in the method for manufacturing the aluminum alloy material 10 of the present embodiment, the Mg content in the oxide film 1 before forming the surface treatment film is restricted to less than 30 atomic %. Thereby, the initial adhesiveness and adhesive durability can be improved. The Mg content of the oxide film 1 before the formation of the surface treatment film is preferably less than 25 atom %, more preferably less than 20 atom %, and further preferably 10 atom% from the viewpoint of improving the initial adhesiveness and adhesive durability. Is less than.
一方、本実施形態のアルミニウム合金材１０の製造方法では、表面処理皮膜形成前の酸化皮膜１のＭｇ含有量の下限値は、経済性の観点から０．１原子％以上とする。なお、ここでいう表面処理皮膜形成前の酸化皮膜１中のＭｇ含有量は、高周波グロー放電発光分光分析法（ＧＤ−ＯＥＳ）により測定することができる。 On the other hand, in the method for manufacturing the aluminum alloy material 10 of the present embodiment, the lower limit value of the Mg content of the oxide film 1 before forming the surface treatment film is 0.1 atom% or more from the viewpoint of economy. The Mg content in the oxide film 1 before the formation of the surface treatment film can be measured by a high frequency glow discharge optical emission spectroscopy (GD-OES).
＜Ｃｕ含有量＞
酸化皮膜１を形成する際に基材３に対して脱脂工程や酸洗工程などにより過剰なエッチングを行うと、基材３に含まれるＣｕが表面に濃化し、酸化皮膜１のＣｕ含有量が増加する。酸化皮膜１の表面にＣｕが存在すると、後述する次のステップＳ３である表面処理皮膜形成工程において形成される表面処理皮膜２にＣｕが過剰に含まれることとなり、接着耐久性の低下原因となる。
<Cu content>
When the base material 3 is excessively etched by a degreasing process, a pickling process, or the like when forming the oxide film 1, Cu contained in the base material 3 is concentrated on the surface, and the Cu content of the oxide film 1 is increased. To increase. If Cu is present on the surface of the oxide film 1, Cu will be excessively contained in the surface treatment film 2 formed in the surface treatment film forming step, which is the next step S3, which will be described later, which causes a decrease in adhesion durability. ..
そこで、本実施形態のアルミニウム合金材１０の製造方法では、表面処理皮膜形成前の酸化皮膜１中のＣｕ含有量を０．６原子％未満に規制する。なお、表面処理皮膜形成前の酸化皮膜１におけるＣｕ含有量は、０．５原子％未満であることがより好ましい。 Therefore, in the method for manufacturing the aluminum alloy material 10 of the present embodiment, the Cu content in the oxide film 1 before forming the surface treatment film is regulated to less than 0.6 atomic %. The Cu content in the oxide film 1 before forming the surface treatment film is more preferably less than 0.5 atom %.
＜膜厚＞
表面処理皮膜形成前の酸化皮膜１の膜厚は、１〜３０ｎｍであることが好ましい。表面処理皮膜形成前の酸化皮膜１の膜厚が１ｎｍ未満の場合、表面処理皮膜形成工程で使用される表面処理液が反応する酸化皮膜１が薄く、表面処理液が過剰となり、未反応の表面処理液が基材上に残り、これが接着耐久性の低下の原因となるおそれがある。また、表面処理液が過剰でない場合でも、表面処理皮膜形成前の酸化皮膜１の膜厚を１ｎｍ未満に制御するには、過度の酸洗浄などが必要となるため、生産性が劣り、実用性が低下しやすい。また、アルカリ脱脂や酸による過剰なエッチングは基材３に含有されるＣｕが表面濃化する原因となり、接着耐久性の低下の原因となるため、エッチング量は１．９ｇ／ｍ２以下にすることが好ましい。
<Film thickness>
The thickness of the oxide film 1 before forming the surface treatment film is preferably 1 to 30 nm. When the film thickness of the oxide film 1 before forming the surface treatment film is less than 1 nm, the surface treatment liquid used in the surface treatment film formation process reacts with a thin oxide film 1 and the surface treatment liquid becomes excessive, resulting in an unreacted surface. The treatment liquid may remain on the base material, which may cause deterioration in adhesion durability. Further, even if the surface treatment liquid is not excessive, in order to control the film thickness of the oxide film 1 before forming the surface treatment film to be less than 1 nm, excessive acid cleaning or the like is required, resulting in poor productivity and practicability. Is easy to decrease. In addition, since alkali degreasing or excessive etching with acid causes the surface of Cu contained in the base material 3 to be concentrated, which causes a decrease in adhesion durability, the etching amount is set to 1.9 g/m 2 or less. It is preferable.
一方、表面処理皮膜形成前の酸化皮膜１の膜厚が３０ｎｍを超えると、表面処理皮膜形成工程で使用される表面処理液が反応する酸化皮膜１に対して不足し、酸化皮膜１との反応が不十分となり、これが接着耐久性の低下の原因となるおそれがある。また、膜厚が３０ｎｍを超える酸化皮膜１には多くのマグネシウムが含まれており、皮膜自体の強度が低下し、初期の接着性が悪くなるおそれがある。なお、表面処理皮膜形成前の酸化皮膜１の膜厚は、化成性及び生産性などの観点から、２ｎｍ以上２０ｎｍ未満であることがより好ましい。 On the other hand, when the film thickness of the oxide film 1 before forming the surface treatment film exceeds 30 nm, the surface treatment liquid used in the surface treatment film forming step becomes insufficient with respect to the reactive oxide film 1 and reacts with the oxide film 1. Is insufficient, which may cause deterioration of adhesion durability. Further, the oxide film 1 having a film thickness of more than 30 nm contains a large amount of magnesium, so that the strength of the film itself may be lowered and the initial adhesiveness may be deteriorated. The thickness of the oxide film 1 before forming the surface treatment film is more preferably 2 nm or more and less than 20 nm from the viewpoint of chemical conversion and productivity.
＜ステップＳ３：表面処理皮膜形成工程＞
表面処理皮膜形成工程（ステップＳ３）は、ステップ２で形成された酸化皮膜１の少なくとも一部に、０．００５質量％以上１質量％未満のアルキルシリケートまたはそのオリゴマーと、０．００５質量％以上１質量％未満の有機シラン化合物とを含み、ｐＨが２以上７以下である水溶液（表面処理液）を塗布することを含む。前記酸化皮膜形成工程（ステップＳ２）で形成された酸化皮膜１に当該表面処理液を塗布して表面処理することにより、酸化皮膜１と表面処理液が反応し、少なくともアルミニウム（Ａｌ）、ケイ素（Ｓｉ）、酸素（Ｏ）、及び、有機シラン化合物を含む表面処理皮膜２が基材３の表面上に形成される。ただし、酸化皮膜１が均一な表面処理皮膜２になるわけではなく、酸化皮膜１はＡｌとＯを主として含み、かつＳｉを含む（Ａｌ−Ｏ−Ｓｉ結合を含む）皮膜に改質され、その上に、ＳｉとＯ（シロキサン結合）を主として含み、かつＡｌを含む（Ａｌ−Ｏ−Ｓｉ結合を含む）皮膜が形成されて、最表面側から基材側に向けてＳｉ濃度が低下し、また、Ａｌ濃度が増加する構造を有する皮膜となる。すなわち、Ａｌ−Ｏ−Ｓｉ結合のＡｌとＳｉの比が断面方向で異なっており、表面処理皮膜２とアルミニウム合金基材３との結合はＡｌリッチなＡｌ−Ｏ−Ｓｉ結合であり、アルミニウム合金基材とこの皮膜との間の強度は酸化皮膜１と同様の強度を保つことができ、また、表面処理材（表面処理後のアルミニウム合金材）の表面はＳｉリッチなＡｌ−Ｏ−Ｓｉ結合を有する。また、有機シラン化合物と接着樹脂の化学結合を形成することも可能であり、これによってより良好な耐食性となり、接着樹脂との結合も強化される。また、この皮膜２自体は非常に薄く、アルキルシリケートまたはそのオリゴマーと有機シラン化合物の皮膜厚み方向の分布状態は異なるが、少なくとも混じった構造となっており、更に極薄であり、皮膜２自体の強度も高い。この様に、アルキルシリケートまたはそのオリゴマー及び有機シラン化合物のいずれをも含む表面処理液を用いて表面処理を行うことで、上記の表面処理皮膜２が形成され、有機シラン化合物のみを用いて表面処理するよりも接着耐久性が向上した合金材を得ることができる。
<Step S3: Surface treatment film forming step>
In the surface treatment film forming step (step S3), at least a part of the oxide film 1 formed in step 2 contains 0.005% by mass or more and less than 1% by mass of alkyl silicate or its oligomer, and 0.005% by mass or more. Application of an aqueous solution (surface treatment liquid) containing an organic silane compound in an amount of less than 1% by mass and having a pH of 2 or more and 7 or less. By applying the surface treatment liquid to the oxide film 1 formed in the oxide film formation step (step S2) and performing the surface treatment, the oxide film 1 and the surface treatment liquid react, and at least aluminum (Al), silicon ( The surface treatment film 2 containing Si), oxygen (O), and an organic silane compound is formed on the surface of the base material 3. However, the oxide film 1 does not become a uniform surface-treated film 2, but the oxide film 1 is modified to a film mainly containing Al and O and also containing Si (including an Al-O-Si bond). A film mainly containing Si and O (siloxane bond) and containing Al (including Al-O-Si bond) is formed on the upper surface, and the Si concentration decreases from the outermost surface side toward the substrate side. Further, the film has a structure in which the Al concentration increases. That is, the ratio of Al to Si in the Al-O-Si bond is different in the cross-sectional direction, and the bond between the surface treatment film 2 and the aluminum alloy base material 3 is an Al-rich Al-O-Si bond. The strength between the base material and this film can maintain the same strength as the oxide film 1, and the surface of the surface-treated material (aluminum alloy material after surface treatment) has a Si-rich Al-O-Si bond. Have. It is also possible to form a chemical bond between the organosilane compound and the adhesive resin, which leads to better corrosion resistance and strengthens the bond with the adhesive resin. Further, the film 2 itself is extremely thin, and although the distribution state of the alkyl silicate or its oligomer and the organic silane compound in the film thickness direction is different, it has a structure in which at least they are mixed, and it is extremely thin. The strength is also high. Thus, the surface treatment film 2 is formed by performing the surface treatment using the surface treatment liquid containing both the alkyl silicate or the oligomer thereof and the organic silane compound, and the surface treatment is performed using only the organic silane compound. It is possible to obtain an alloy material having improved adhesion durability.
図３に、基材３の表面上に表面処理皮膜２が形成された本実施形態のアルミニウム合金材を示す。なお、図３に示されるアルミニウム合金材では、基材３の一方の表面の全部に表面処理皮膜２が形成されているが、本実施形態はこれに限定されるものではない。例えば、基材３の表面の一部のみに表面処理皮膜２が形成されていてもよい。また、基材３の両面に表面処理皮膜２が形成されていてもよい。 FIG. 3 shows the aluminum alloy material of the present embodiment in which the surface treatment film 2 is formed on the surface of the base material 3. In the aluminum alloy material shown in FIG. 3, the surface treatment film 2 is formed on the entire one surface of the base material 3, but the present embodiment is not limited to this. For example, the surface treatment film 2 may be formed only on a part of the surface of the base material 3. Further, the surface treatment film 2 may be formed on both surfaces of the base material 3.
以下、表面処理皮膜を形成するために用いる表面処理液について説明する。
当該表面処理液のｐＨは２以上７以下である。表面処理液のｐＨが２よりも低いとアルミニウム合金が溶解しすぎ均一な皮膜が得られない。そのため、皮膜強度が低下し、応力がかかった際に有機シラン化合物処理層の内部で破壊が生じてしまう。一方、表面処理液のｐＨが７よりも高いとアルキルシリケートまたはそのオリゴマーが沈殿するため、アルミニウムとケイ素が反応することができなくなる。したがって、表面処理液のｐＨは２以上７以下の範囲とする必要がある。表面処理液のｐＨは、金属酸化被膜との反応性を考慮すると、好ましくは３以上である。表面処理液のｐＨは、ＴＥＯＳの安定性の観点からは、好ましくは６以下である。なお、表面処理液のｐＨは、例えば塩酸や硫酸、硝酸、酢酸などの酸を添加すること等により適宜調整することができる。
The surface treatment liquid used to form the surface treatment film will be described below.
The surface treatment liquid has a pH of 2 or more and 7 or less. If the pH of the surface treatment liquid is lower than 2, the aluminum alloy is too dissolved to obtain a uniform film. Therefore, the film strength is reduced, and when stress is applied, the organic silane compound-treated layer is broken inside. On the other hand, when the pH of the surface treatment liquid is higher than 7, the alkyl silicate or its oligomer is precipitated, so that aluminum and silicon cannot react with each other. Therefore, the pH of the surface treatment liquid needs to be in the range of 2 or more and 7 or less. The pH of the surface treatment liquid is preferably 3 or more in consideration of the reactivity with the metal oxide film. The pH of the surface treatment liquid is preferably 6 or less from the viewpoint of the stability of TEOS. The pH of the surface treatment solution can be appropriately adjusted by adding an acid such as hydrochloric acid, sulfuric acid, nitric acid or acetic acid.
表面処理液中のアルキルシリケートまたはそのオリゴマーの濃度は、０．００５質量％以上１質量％未満である。表面処理液中のアルキルシリケートまたはそのオリゴマーの濃度が１質量％以上であると、生成する皮膜が厚くなり、強度が低下する。一方、表面処理液中のアルキルシリケートまたはそのオリゴマーの濃度が０．００５質量％未満であると、アルキルシリケートまたはそのオリゴマーの濃度が低すぎるため、アルミニウムとケイ素が十分に反応することができなくなり、十分な接着耐久性が得られなくなる。表面処理液中のアルキルシリケートまたはそのオリゴマーの濃度は、好ましくは０．０１質量％以上であり、より好ましくは０．０２質量％以上である。また、表面処理液中のケイ酸塩の濃度は、好ましくは０．５質量％未満であり、より好ましくは０．２質量％未満である。 The concentration of the alkyl silicate or its oligomer in the surface treatment liquid is 0.005% by mass or more and less than 1% by mass. When the concentration of the alkyl silicate or its oligomer in the surface treatment liquid is 1% by mass or more, the formed film becomes thick and the strength decreases. On the other hand, when the concentration of the alkyl silicate or its oligomer in the surface treatment liquid is less than 0.005% by mass, the concentration of the alkyl silicate or its oligomer is too low, so that aluminum and silicon cannot react sufficiently, Sufficient adhesion durability cannot be obtained. The concentration of the alkyl silicate or its oligomer in the surface treatment liquid is preferably 0.01% by mass or more, more preferably 0.02% by mass or more. The concentration of silicate in the surface treatment liquid is preferably less than 0.5% by mass, more preferably less than 0.2% by mass.
また、表面処理液中の有機シラン化合物の濃度は、０．００５質量％以上１質量％未満である。表面処理液中の有機シラン化合物の濃度が１質量％以上であると、生成する表面処理皮膜が厚くなり、強度が低下してしまう。一方、表面処理液中の有機シラン化合物の濃度が０．００５質量％未満であると、有機シラン化合物の濃度が低すぎるため、有機シラン化合物を含む表面処理皮膜を十分に形成することができなくなり、十分な接着耐久性が得られなくなる。表面処理液中の有機シラン化合物の濃度は、好ましくは０．０１質量％以上であり、より好ましくは０．０２質量％以上である。また、表面処理液中の有機シラン化合物の濃度は、好ましくは０．５質量％未満であり、より好ましくは０．２質量％未満である。 The concentration of the organic silane compound in the surface treatment liquid is 0.005% by mass or more and less than 1% by mass. When the concentration of the organic silane compound in the surface treatment liquid is 1% by mass or more, the surface treatment film produced becomes thick and the strength is reduced. On the other hand, when the concentration of the organic silane compound in the surface treatment liquid is less than 0.005% by mass, the concentration of the organic silane compound is too low, so that the surface treatment film containing the organic silane compound cannot be sufficiently formed. , Sufficient adhesion durability cannot be obtained. The concentration of the organic silane compound in the surface treatment liquid is preferably 0.01% by mass or more, more preferably 0.02% by mass or more. The concentration of the organic silane compound in the surface treatment liquid is preferably less than 0.5% by mass, more preferably less than 0.2% by mass.
本発明において、表面処理液に含まれるアルキルシリケートまたはそのオリゴマーの種類は特に限定されないが、反応後に皮膜の腐食や接着樹脂の劣化の原因となるような副生成物を生じないテトラアルキルシリケートまたはそのオリゴマーが好ましい。この観点からは、テトラメチルオルソシリケート、テトラエチルオルソシリケート、テトライソプロピルオルソシリケート等のテトラアルキルシリケートまたはそのオリゴマーが好ましく、中でも、経済性や安全性の観点からは、テトラエチルオルソシリケートまたはそのオリゴマーが好ましい。なお、重合物には、オリゴマーなどが含まれる。ここで、アルキルシリケートまたはそのオリゴマーとしては、１種のみを単独で用いてもよく、２種以上を組み合わせて用いてもよい。 In the present invention, the type of the alkyl silicate or the oligomer thereof contained in the surface treatment liquid is not particularly limited, but a tetraalkyl silicate or its which does not produce a by-product that causes corrosion of the coating or deterioration of the adhesive resin after the reaction. Oligomers are preferred. From this viewpoint, tetraalkyl silicates such as tetramethyl orthosilicate, tetraethyl orthosilicate, and tetraisopropyl orthosilicate or oligomers thereof are preferable, and among them, tetraethyl orthosilicate or oligomers thereof are preferable from the viewpoint of economy and safety. The polymer includes oligomers and the like. Here, as the alkyl silicate or the oligomer thereof, only one kind may be used alone, or two or more kinds may be used in combination.
本発明において、表面処理液に含まれる有機シラン化合物の種類は特に限定されないが、有機シラン化合物は加水分解可能なトリアルコキシシリル基を分子内に複数有するシラン化合物、その加水分解物またはその重合体を含んでいてもよい。分子内に加水分解可能なトリアルコキシシリル基を複数有するシラン化合物は、緻密なシロキサン結合を形成するだけでなく、金属酸化物との反応性が高く、化学的に安定な皮膜を形成するため、皮膜の湿潤耐久性を更に高めることができる。また、有機シラン処理皮膜は加工油、プレス油等の機械油や接着剤のような有機化合物との相互溶解性が高く、皮膜に加工油、プレス油等の機械油が付着していてもその影響を緩和できるため、塗油による接着耐久性の低下を防ぐ役割も担う。上記シラン化合物の種類は特に限定されないが、経済性の観点からは、加水分解可能なトリアルコキシシリル基を分子内に２つ有するシラン化合物（ビスシラン化合物）が好ましく、例えば、ビストリアルコキシシリルエタン、ビストリアルコキシシリルベンゼン、ビストリアルコキシシリルヘキサン、ビストリアルコキシシリルプロピルアミン、ビストリアルコキシシリルプロピルテトラスルフィドなどを用いることができる。とりわけ、汎用性、経済性の観点から、ビストリエトキシシリルエタン（ＢＴＳＥ）が好ましい。ここで、有機シラン化合物としては、１種のみを単独で用いてもよく、２種以上を組み合わせて用いてもよい。 In the present invention, the type of the organic silane compound contained in the surface treatment liquid is not particularly limited, but the organic silane compound is a silane compound having a plurality of hydrolyzable trialkoxysilyl groups in the molecule, its hydrolyzate or its polymer. May be included. A silane compound having a plurality of hydrolyzable trialkoxysilyl groups in the molecule not only forms a dense siloxane bond, but also has high reactivity with a metal oxide and forms a chemically stable film. The wet durability of the film can be further enhanced. Further, the organic silane-treated film has high mutual solubility with machine oils such as processing oil and press oil and organic compounds such as adhesives, and even if machine oil such as processing oil and press oil adheres to the film, Since the effect can be mitigated, it also plays a role in preventing the decrease in adhesion durability due to oiling. The type of the silane compound is not particularly limited, but from the economical viewpoint, a silane compound (bissilane compound) having two hydrolyzable trialkoxysilyl groups in the molecule is preferable, and examples thereof include bistrialkoxysilylethane and bistrialkenyl. Alkoxysilylbenzene, bistrialkoxysilylhexane, bistrialkoxysilylpropylamine, bistrialkoxysilylpropyl tetrasulfide and the like can be used. Above all, bistriethoxysilylethane (BTSE) is preferable from the viewpoint of versatility and economy. Here, as the organic silane compound, only one kind may be used alone, or two or more kinds may be used in combination.
また、有機シラン化合物は、有機樹脂成分と化学結合しうる反応性官能基を有するシランカップリング剤、その加水分解物またはその重合体を含んでいてもよい。例えば、アミノ基、エポキシ基、メタクリル基、ビニル基及びメルカプト基などの反応性官能基をもつシランカップリング剤を単独で使用、もしくはシラン化合物と併用することで、皮膜と樹脂との間に化学結合を形成させ、接着耐久性を更に高めることができる。なおシランカップリング剤の官能基は、前述したものに限定されるものではなく、各種官能基を有するシランカップリング剤を、使用する接着樹脂に応じて適宜選択して使用することができる。シランカップリング剤の好適な具体例としては、例えば、３−アミノプロピルトリメトキシシラン、３−アミノプロピルトリエトキシシラン、３−（Ｎ−アミノエチル）−アミノプロピルトリメトキシシラン、３−（Ｎ−アミノエチル）−アミノプロピルトリエトキシシラン、３−メルカプトプロピルトリメトキシシラン、３−メルカプトプロピルトリエトキシシラン、３−グリシドキシプロピルトリメトキシシラン、３−グリシドキシプロピルトリエトキシシラン、３−メタクリロキシプロピルトリメトキシシラン、３−メタクリロキシプロピルトリエトキシシラン等が挙げられる。ここで、シランカップリング剤としては、１種のみを単独で用いてもよく、２種以上を組み合わせて用いてもよい。 Further, the organosilane compound may contain a silane coupling agent having a reactive functional group capable of chemically bonding with the organic resin component, a hydrolyzate thereof, or a polymer thereof. For example, by using a silane coupling agent having a reactive functional group such as an amino group, an epoxy group, a methacryl group, a vinyl group and a mercapto group alone or in combination with a silane compound, a chemical reaction between the film and the resin A bond can be formed to further enhance the adhesion durability. The functional groups of the silane coupling agent are not limited to those described above, and silane coupling agents having various functional groups can be appropriately selected and used according to the adhesive resin used. Specific preferred examples of the silane coupling agent include, for example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(N-aminoethyl)-aminopropyltrimethoxysilane, and 3-(N- Aminoethyl)-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-methacryloxy Examples thereof include propyltrimethoxysilane and 3-methacryloxypropyltriethoxysilane. Here, as the silane coupling agent, only one kind may be used alone, or two or more kinds may be used in combination.
なお、表面処理液は、上記アルキルシリケートまたはそのオリゴマーや有機シラン化合物以外にも、所望により、安定剤、補助剤等の１つ以上をさらに含んでいてもよい。例えば、安定剤として、ギ酸、酢酸等の炭素数１〜４のカルボン酸や、メタノール、エタノール等の炭素数１〜４のアルコール等の有機化合物等を含んでいてもよい。 In addition to the alkyl silicate or its oligomer or the organic silane compound, the surface treatment liquid may further contain one or more stabilizers, auxiliaries and the like, if desired. For example, as a stabilizer, a carboxylic acid having 1 to 4 carbon atoms such as formic acid and acetic acid, an organic compound such as alcohol having 1 to 4 carbon atoms such as methanol and ethanol, and the like may be contained.
表面処理液の塗布方法としては、浸漬処理、スプレー、ロールコート、バーコート、静電塗布等が挙げられる。また、表面処理後にはリンスは無い方が良いが、場合によっては純水等で行ってもよい。 Examples of the method of applying the surface treatment liquid include dipping treatment, spraying, roll coating, bar coating, electrostatic coating and the like. Further, it is preferable that no rinsing is performed after the surface treatment, but in some cases, rinsing may be performed with pure water or the like.
上記表面処理液の塗布後には、必要に応じて、加熱により表面処理液を乾燥させる。加熱温度は、好ましくは７０℃以上、より好ましくは８０℃以上、更に好ましくは９０℃以上である。また、加熱温度が高すぎると、アルミニウム合金の特性に影響を及ぼすため、当該加熱温度は、好ましくは２２０℃以下、より好ましくは２００℃以下、更に好ましくは１９０℃以下である。また、乾燥時間は、加熱温度にもよるが、好ましくは２秒以上であり、より好ましくは５秒以上であり、さらに好ましくは１０秒以上である。また、当該乾燥時間は、好ましくは２０分以下、より好ましくは５分以下、さらに好ましくは２分以下である。 After applying the surface treatment liquid, the surface treatment liquid is dried by heating, if necessary. The heating temperature is preferably 70° C. or higher, more preferably 80° C. or higher, even more preferably 90° C. or higher. Further, if the heating temperature is too high, it affects the properties of the aluminum alloy, so the heating temperature is preferably 220° C. or lower, more preferably 200° C. or lower, and further preferably 190° C. or lower. The drying time depends on the heating temperature, but is preferably 2 seconds or more, more preferably 5 seconds or more, and further preferably 10 seconds or more. The drying time is preferably 20 minutes or less, more preferably 5 minutes or less, and further preferably 2 minutes or less.
表面処理液の塗布量は、十分な接着耐久性の向上効果を得る観点から、乾燥後の皮膜量が０．５ｍｇ／ｍ２以上２０ｍｇ／ｍ２以下となるように調整することが好ましい。また、より好ましくは、乾燥後の皮膜量が１ｍｇ／ｍ２以上１５ｍｇ／ｍ２以下となるように調整する。表面処理液の塗布量が少なすぎると、アルキルシリケートまたはそのオリゴマーあるいは有機シラン化合物の量が少なくなりすぎ、良好な接着耐久性を得られない場合がある。また、表面処理液の塗布量が多くなりすぎると、形成される表面処理皮膜が厚くなりすぎて表面処理皮膜内で剥離がおこり、接着耐久性が損なわれる場合がある。また、例えば自動車の組み立て工程後の塗装工程の前処理工程として行われるリン酸亜鉛処理において十分なリン酸亜鉛の付着が得られず、十分な耐食性が得られない。 The coating amount of the surface treatment liquid is preferably adjusted so that the coating amount after drying is 0.5 mg/m 2 or more and 20 mg/m 2 or less from the viewpoint of obtaining a sufficient effect of improving the adhesion durability. Further, more preferably, the amount of the film after drying is adjusted to 1 mg/m 2 or more and 15 mg/m 2 or less. If the coating amount of the surface treatment liquid is too small, the amount of the alkyl silicate or its oligomer or the organic silane compound will be too small, and good adhesion durability may not be obtained. Further, if the coating amount of the surface treatment liquid is too large, the formed surface treatment film becomes too thick and peeling may occur in the surface treatment film, which may deteriorate the adhesion durability. Further, for example, in the zinc phosphate treatment performed as a pretreatment step of a coating step after an automobile assembly step, sufficient zinc phosphate adhesion cannot be obtained and sufficient corrosion resistance cannot be obtained.
＜その他の工程＞
本実施形態のアルミニウム合金材１０の製造方法では、前述した各工程に悪影響を与えない範囲において、各工程の間又は前後に、他の工程を含めてもよい。例えば、表面処理皮膜形成工程Ｓ３後に、予備時効処理を施す予備時効処理工程を設けてもよい。この予備時効処理は、７２時間以内に４０〜１２０℃で、８〜３６時間の低温加熱することにより行うことが好ましい。この条件で予備時効処理することにより、成形性及びベーキング後の強度向上を図ることができる。その他に、例えばアルミニウム合金材１０の表面の異物を除去する異物除去工程や、各工程で発生した不良品を除去する不良品除去工程などを行ってもよい。
<Other processes>
In the manufacturing method of the aluminum alloy material 10 of the present embodiment, other steps may be included between or before and after each step as long as the above steps are not adversely affected. For example, a preliminary aging treatment step of performing a preliminary aging treatment may be provided after the surface treatment film forming step S3. This preliminary aging treatment is preferably performed by heating at a low temperature of 40 to 120° C. for 8 to 36 hours within 72 hours. By performing the pre-aging treatment under this condition, the formability and the strength after baking can be improved. In addition, for example, a foreign matter removing step of removing foreign matter on the surface of the aluminum alloy material 10 or a defective article removing step of removing defective articles generated in each step may be performed.
そして、製造されたアルミニウム合金材１０は、接合体の作製前又は自動車用部材への加工前に、その表面にプレス油等の機械油が塗布される。プレス油は、エステル成分を含有するものが主に使用される。アルミニウム合金材１０にプレス油を塗布する方法や条件は、特に限定されるものではなく、通常のプレス油を塗布する方法や条件が広く適用でき、例えば、エステル成分としてオレイン酸エチルを含有するプレス油に、アルミニウム合金材１０を浸漬すればよい。なお、エステル成分もオレイン酸エチルに限定されるものではなく、ステアリン酸ブチルやソルビタンモノステアレートなど、様々なものを利用することができる。 Then, the manufactured aluminum alloy material 10 is coated with a mechanical oil such as a press oil on the surface thereof before the production of the joined body or the processing into the automobile member. As the press oil, one containing an ester component is mainly used. The method and conditions for applying the press oil to the aluminum alloy material 10 are not particularly limited, and the method and conditions for applying a normal press oil can be widely applied. For example, a press containing ethyl oleate as an ester component. The aluminum alloy material 10 may be immersed in oil. The ester component is not limited to ethyl oleate, and various compounds such as butyl stearate and sorbitan monostearate can be used.
ここで、本実施形態のアルミニウム合金材１０は、最表面に機械油の溶解性に富む皮膜２を備えているため、機械油が塗布された後でも、その上に接着樹脂を良好に接合することができる。 Here, since the aluminum alloy material 10 of the present embodiment is provided with the coating 2 having a high solubility of mechanical oil on the outermost surface, the adhesive resin is satisfactorily bonded onto the coating even after the mechanical oil is applied. be able to.
以上詳述したように、本実施形態のアルミニウム合金材１０の製造方法によれば、酸化皮膜を形成したアルミニウム合金基材に対して、アルキルシリケートまたはそのオリゴマーと有機シラン化合物とを含む水溶液を用いて、シリケート処理及び有機シラン処理を同時に行うことで、簡略化された工程でアルミニウム合金材の製造が可能となり、設備投資費や製造コストを低減することができる。また、本実施形態のアルミニウム合金材１０は、表面処理皮膜形成工程前の酸化皮膜１中のＭｇ量を特定範囲に調整しているため、基材３の溶出を抑制でき、またそれに伴う基材３の表面のマグネシウム酸化物による脆弱性を抑制して、接着樹脂の劣化を抑制できる。さらに、表面処理皮膜形成工程前の酸化皮膜１中のＣｕ量を特定量未満に規制しているため、酸化皮膜１に表面処理を施すことにより形成される表面処理皮膜２と接着樹脂の接着耐久性が向上する。その結果、本実施形態のアルミニウム合金材１０は、高温湿潤環境に曝されても、界面剥離が抑制され、長期間に亘って接着強度の低下を抑制できる。また、有機シラン化合物のみを用いて表面処理するよりも接着耐久性を向上させることができる。 As described above in detail, according to the method for manufacturing the aluminum alloy material 10 of the present embodiment, an aqueous solution containing an alkyl silicate or its oligomer and an organic silane compound is used for an aluminum alloy base material having an oxide film formed thereon. By simultaneously performing the silicate treatment and the organic silane treatment, the aluminum alloy material can be manufactured in a simplified process, and the capital investment cost and the manufacturing cost can be reduced. Further, since the aluminum alloy material 10 of the present embodiment adjusts the amount of Mg in the oxide film 1 before the surface treatment film forming step to a specific range, the elution of the base material 3 can be suppressed, and the base material accompanying it can be suppressed. It is possible to suppress the brittleness of the surface of No. 3 due to the magnesium oxide and suppress the deterioration of the adhesive resin. Further, since the amount of Cu in the oxide film 1 before the surface treatment film forming step is regulated to be less than a specific amount, the adhesion durability of the surface treatment film 2 and the adhesive resin formed by subjecting the oxide film 1 to the surface treatment. The property is improved. As a result, the aluminum alloy material 10 of the present embodiment suppresses interfacial peeling even when exposed to a high temperature wet environment, and can suppress a decrease in adhesive strength over a long period of time. Further, the adhesion durability can be improved as compared with the case where the surface treatment is performed using only the organic silane compound.
（第１の実施形態の変形例）
次に、本発明の第１の実施形態の変形例に係る接着樹脂層付きアルミニウム合金材について説明する。図４は本変形例の接着樹脂層付きアルミニウム合金材の構成を模式的に示す断面図である。なお、図４においては、図３に示すアルミニウム合金材１０の構成要素と同じものには同じ符号を付し、その詳細な説明は省略する。図４に示すように、本変形例の接着樹脂層付きアルミニウム合金材１１は、前述した第１の実施形態のアルミニウム合金材における表面処理皮膜２を覆うように、接着樹脂からなる接着樹脂層４が形成されている。
(Modification of the first embodiment)
Next, an aluminum alloy material with an adhesive resin layer according to a modified example of the first embodiment of the present invention will be described. FIG. 4 is a cross-sectional view schematically showing the structure of the aluminum alloy material with the adhesive resin layer according to this modification. In FIG. 4, the same components as those of the aluminum alloy material 10 shown in FIG. 3 are designated by the same reference numerals, and detailed description thereof will be omitted. As shown in FIG. 4, the aluminum alloy material 11 with an adhesive resin layer according to the present modification covers the surface treatment film 2 of the aluminum alloy material according to the first embodiment described above, and the adhesive resin layer 4 made of an adhesive resin. Are formed.
［接着樹脂層４］
接着樹脂層４は、接着樹脂などからなり、本変形例の接着樹脂層付きアルミニウム合金材１１は、この接着樹脂層４を介して他の部材と接合される。なお、他の部材には、接着樹脂層付きアルミニウム合金材１１と同様に表面処理皮膜が形成されている別のアルミニウム合金材、酸化皮膜及び表面処理皮膜が形成されていないアルミニウム合金材、樹脂成形体等が包含される。
[Adhesive resin layer 4]
The adhesive resin layer 4 is made of an adhesive resin or the like, and the aluminum alloy material 11 with an adhesive resin layer of the present modification is joined to other members via the adhesive resin layer 4. As for the other members, similar to the aluminum alloy material 11 with the adhesive resin layer, another aluminum alloy material on which a surface treatment film is formed, an aluminum alloy material on which an oxide film and a surface treatment film are not formed, a resin molding The body and the like are included.
接着樹脂層４を構成する接着樹脂は、特に限定されるものではなく、エポキシ系樹脂、ウレタン系樹脂、ニトリル系樹脂、ナイロン系樹脂、アクリル系樹脂など、従来からアルミニウム合金材を接合する際に用いられてきた接着樹脂を用いることができる。 The adhesive resin that constitutes the adhesive resin layer 4 is not particularly limited, and is conventionally used when joining an aluminum alloy material such as an epoxy resin, a urethane resin, a nitrile resin, a nylon resin, or an acrylic resin. Adhesive resins that have been used can be used.
接着樹脂層４の厚さも、特に限定されるものではないが、１０〜５００μｍが好ましく、５０〜４００μｍがより好ましい。接着樹脂層４の厚さが１０μｍ未満の場合には、接着樹脂層付きアルミニウム合金材１１と、他の接着樹脂層を備えていないアルミニウム合金材とを接着樹脂層４を介して接合する場合に、高い接着耐久性が得られないことがある。一方、接着樹脂層４の厚さが５００μｍを超える場合には、接着強度が小さくなる場合がある。 The thickness of the adhesive resin layer 4 is also not particularly limited, but is preferably 10 to 500 μm, more preferably 50 to 400 μm. When the thickness of the adhesive resin layer 4 is less than 10 μm, when the aluminum alloy material 11 with an adhesive resin layer and an aluminum alloy material not provided with another adhesive resin layer are bonded via the adhesive resin layer 4. , High adhesion durability may not be obtained. On the other hand, when the thickness of the adhesive resin layer 4 exceeds 500 μm, the adhesive strength may be reduced.
［製造方法］
次に、本変形例の接着樹脂層付きアルミニウム合金材１１の製造方法について説明する。図５は本変形例の接着樹脂層付きアルミニウム合金材１１の製造方法を示すフローチャート図である。図５に示すように、本変形例の接着樹脂層付きアルミニウム合金材１１を製造する際は、前述したステップＳ１〜Ｓ３に加えて、接着樹脂層形成工程Ｓ４を行う。
[Production method]
Next, a method for manufacturing the aluminum alloy material 11 with the adhesive resin layer of this modification will be described. FIG. 5 is a flowchart showing a method for manufacturing the aluminum alloy material 11 with the adhesive resin layer according to this modification. As shown in FIG. 5, when manufacturing the aluminum alloy material 11 with an adhesive resin layer of the present modification, an adhesive resin layer forming step S4 is performed in addition to steps S1 to S3 described above.
［ステップＳ４：接着樹脂層形成工程］
接着樹脂層形成工程Ｓ４では、表面処理皮膜２を覆うように、接着剤などからなる接着樹脂層４を形成する。接着樹脂層４の形成方法は、特に限定されるものではないが、例えば、接着樹脂が固体である場合には、熱を加えて圧着したり、これを溶剤に溶解させて溶液とした後に、また、接着樹脂が液状である場合にはそのまま、表面処理皮膜２の表面に噴霧したり塗布する方法が挙げられる。
[Step S4: Adhesive Resin Layer Forming Step]
In the adhesive resin layer forming step S4, the adhesive resin layer 4 made of an adhesive or the like is formed so as to cover the surface treatment film 2. The method for forming the adhesive resin layer 4 is not particularly limited. For example, when the adhesive resin is a solid, heat is applied for pressure bonding, or this is dissolved in a solvent to form a solution, Further, when the adhesive resin is in a liquid state, a method of spraying or coating the surface of the surface treatment film 2 as it is can be mentioned.
また、本変形例の接着樹脂層付きアルミニウム合金材１１においても、前述した第１の実施形態と同様に、酸化皮膜形成工程Ｓ２、表面処理皮膜形成工程Ｓ３及び／又は接着樹脂層形成工程Ｓ４の後に、予備時効処理を施す予備時効処理工程を設けてもよい。 Further, also in the aluminum alloy material 11 with an adhesive resin layer of the present modified example, the oxide film forming step S2, the surface treatment film forming step S3 and/or the adhesive resin layer forming step S4 are performed as in the first embodiment described above. After that, a preliminary aging treatment step for performing the preliminary aging treatment may be provided.
本変形例の接着樹脂層付きアルミニウム合金材においては、接着樹脂層をあらかじめ備えるため、接合体や自動車用部材を作製する際に、アルミニウム合金材の表面に接着樹脂を塗布するなどの作業を省略することができる。なお、本変形例の接着樹脂層付きアルミニウム合金材における上記以外の構成及び効果は、前述した第１の実施形態と同様である。 Since the aluminum alloy material with the adhesive resin layer of this modification is provided with the adhesive resin layer in advance, when the bonded body or the automobile member is manufactured, the work such as applying the adhesive resin to the surface of the aluminum alloy material is omitted. can do. The configurations and effects of the aluminum alloy material with the adhesive resin layer of the present modification other than the above are the same as those of the first embodiment described above.
（第２の実施形態）
次に、本発明の第２の実施形態に係る接合体について説明する。本実施形態の接合体は、前述した第１の実施形態のアルミニウム合金材又はその変形例の接着樹脂層付きアルミニウム合金材を用いたものである。図６〜９Ｂは本実施形態の接合体の構成例を模式的に示す断面図である。なお、図６〜９Ｂにおいては、図３及び４に示すアルミニウム合金材１０、接着樹脂層付きアルミニウム合金材１１の構成要素と同じものには同じ符号を付し、その詳細な説明は省略する。
(Second embodiment)
Next, a joined body according to the second embodiment of the present invention will be described. The joined body of the present embodiment uses the above-described aluminum alloy material of the first embodiment or the modified aluminum alloy material with an adhesive resin layer. 6 to 9B are cross-sectional views schematically showing a configuration example of the joined body of the present embodiment. 6 to 9B, the same components as those of the aluminum alloy material 10 and the adhesive resin layer-coated aluminum alloy material 11 shown in FIGS. 3 and 4 are denoted by the same reference numerals, and detailed description thereof will be omitted.
［接合体の構成］
本実施形態の接合体は、例えば、図６に示す接合体２０のように、図３に示す２枚のアルミニウム合金材１０を、表面処理皮膜２が形成されている面同士が対向するように配置し、接着樹脂５を介して接合した構成とすることができる。即ち、接合体２０では、接着樹脂５は、一面が一方のアルミニウム合金材１０の表面処理皮膜２側に接合され、その他面が他方のアルミニウム合金材１０の表面処理皮膜２側に接合されている。
[Structure of bonded body]
In the joined body of the present embodiment, for example, like the joined body 20 shown in FIG. 6, the two aluminum alloy materials 10 shown in FIG. 3 are arranged so that the surfaces on which the surface treatment film 2 is formed face each other. It may be arranged and joined via the adhesive resin 5. That is, in the bonded body 20, one surface of the adhesive resin 5 is bonded to the surface treatment film 2 side of the one aluminum alloy material 10 and the other surface is bonded to the surface treatment film 2 side of the other aluminum alloy material 10. ..
ここで、本実施形態の接合体における接着樹脂５は、前述した接着樹脂層４を構成する接着樹脂と同様のものを使用することができる。具体的には、接着樹脂５は、エポキシ系樹脂、ウレタン系樹脂、ニトリル系樹脂、ナイロン系樹脂、アクリル系樹脂などを使用することができる。また、接着樹脂５の厚さは、特に限定されるものではないが、接着強度向上の観点から、１０〜５００μｍが好ましく、より好ましくは５０〜４００μｍである。 Here, as the adhesive resin 5 in the joined body of the present embodiment, the same adhesive resin as the above-mentioned adhesive resin forming the adhesive resin layer 4 can be used. Specifically, the adhesive resin 5 may be an epoxy resin, a urethane resin, a nitrile resin, a nylon resin, an acrylic resin, or the like. The thickness of the adhesive resin 5 is not particularly limited, but is preferably 10 to 500 μm, more preferably 50 to 400 μm from the viewpoint of improving the adhesive strength.
接合体２０では、前述したように、接着樹脂５の両面が、第１の実施形態のアルミニウム合金材１０の表面処理皮膜２であるため、自動車用部材に用いた際、高温湿潤環境に曝されても、接着樹脂５と表面処理皮膜２との界面の接着強度が低下しにくく、接着耐久性が向上する。また、本実施形態の接合体２０では、接着樹脂５の種類に影響されず、従来からアルミニウム合金材の接合に用いられている接着樹脂全般において界面での接着耐久性が向上する。 As described above, in the joined body 20, since both surfaces of the adhesive resin 5 are the surface-treated coating 2 of the aluminum alloy material 10 of the first embodiment, when the adhesive body 5 is used as an automobile member, it is exposed to a high temperature and humid environment. However, the adhesive strength at the interface between the adhesive resin 5 and the surface-treated film 2 is less likely to decrease, and the adhesive durability is improved. In addition, in the bonded body 20 of the present embodiment, the bonding durability at the interface is improved regardless of the type of the adhesive resin 5 in all adhesive resins conventionally used for bonding aluminum alloy materials.
また、図７Ａに示す接合体２１ａ又は図７Ｂに示す接合体２１ｂのように、図３に示すアルミニウム合金材１０の表面処理皮膜２が形成されている面に、接着樹脂５を介して、酸化皮膜及び表面処理皮膜が形成されていない他のアルミニウム合金材６又は樹脂成形体７を接合した構成とすることもできる。 Further, like the bonded body 21a shown in FIG. 7A or the bonded body 21b shown in FIG. 7B, the surface of the aluminum alloy material 10 shown in FIG. 3 on which the surface treatment film 2 is formed is oxidized via the adhesive resin 5. It is also possible to adopt a configuration in which another aluminum alloy material 6 or resin molded body 7 on which the coating and the surface treatment coating are not formed is joined.
ここで、酸化皮膜及び表面処理皮膜が形成されていない他のアルミニウム合金材６には、前述した基材３と同様のものを使用することができ、具体的には、ＪＩＳに規定される又はＪＩＳに近似する種々の非熱処理型若しくは熱処理型アルミニウム合金からなるものを使用することができる。 Here, as the other aluminum alloy material 6 on which the oxide film and the surface treatment film are not formed, the same material as the above-mentioned base material 3 can be used, and specifically, it is specified in JIS or It is possible to use various non-heat treatment type or heat treatment type aluminum alloys close to JIS.
また、樹脂成形体７としては、例えば、ガラス繊維強化プラスチック（ＧＦＲＰ）、炭素繊維強化プラスチック（ＣＦＲＰ）、ボロン繊維強化プラスチック（ＢＦＲＰ）、アラミド繊維強化プラスチック（ＡＦＲＰ，ＫＦＲＰ）、ポリエチレン繊維強化プラスチック（ＤＦＲＰ）及びザイロン強化プラスチック（ＺＦＲＰ）などの各種繊維強化プラスチックにより形成した繊維強化プラスチック成形体を用いることができる。これらの繊維強化プラスチック成形体を用いることにより、一定の強度を維持しつつ、接合体を軽量化することが可能となる。 Examples of the resin molded body 7 include glass fiber reinforced plastic (GFRP), carbon fiber reinforced plastic (CFRP), boron fiber reinforced plastic (BFRP), aramid fiber reinforced plastic (AFRP, KFRP), polyethylene fiber reinforced plastic ( Fiber reinforced plastic moldings formed of various fiber reinforced plastics such as DFRP) and Zylon reinforced plastic (ZFRP) can be used. By using these fiber-reinforced plastic molded products, it becomes possible to reduce the weight of the bonded product while maintaining a constant strength.
なお、樹脂成形体７は、前述した繊維強化プラスチック以外に、ポリプロピレン（ＰＰ）、アクリル−ブタジエン−スチレン共重合体（ＡＢＳ）樹脂、ポリウレタン（ＰＵ）、ポリエチレン（ＰＥ）、ポリ塩化ビニル（ＰＶＣ）、ナイロン６、ナイロン６，６、ポリスチレン（ＰＳ）、ポリエチレンテレフタレート（ＰＥＴ）、ポリアミド（ＰＡ）、ポリフェニレンスルフィド（ＰＰＳ）、ポリブチレンテレフタレート（ＰＢＴ）、ポリフタルアミド（ＰＰＡ）などの繊維強化されていない樹脂を使用することもできる。 In addition to the fiber reinforced plastics described above, the resin molded body 7 includes polypropylene (PP), acrylic-butadiene-styrene copolymer (ABS) resin, polyurethane (PU), polyethylene (PE), polyvinyl chloride (PVC). Fiber reinforced with nylon, nylon 6, nylon 6,6, polystyrene (PS), polyethylene terephthalate (PET), polyamide (PA), polyphenylene sulfide (PPS), polybutylene terephthalate (PBT), polyphthalamide (PPA), etc. It is also possible to use no resin.
図７Ａ及び図７Ｂに示す接合体２１ａ，２１ｂでは、接着樹脂５の片面が表面処理皮膜２側に接合されているため、前述した接合体２０と同様に、自動車用部材に用いた際、高温湿潤環境に曝されても、接着樹脂の種類に影響されず、界面での接着耐久性が向上する。また、図７Ｂに示す接合体２１ｂは、アルミニウム合金材１０と樹脂成形体７とを接合しているため、アルミニウム合金材同士の接合体に比べて軽量であり、この接合体２１ｂを用いることにより自動車の更なる軽量化を実現することができる。なお、図７Ａ及び図７Ｂに示す接合体２１ａ，２１ｂにおける上記以外の構成及び効果は、図６に示す接合体２０と同様である。 In the bonded bodies 21a and 21b shown in FIGS. 7A and 7B, one surface of the adhesive resin 5 is bonded to the surface treatment film 2 side, and therefore, when used as a vehicle member, as in the bonded body 20 described above, a high temperature is obtained. Even when exposed to a wet environment, the adhesive durability at the interface is improved without being affected by the type of adhesive resin. Further, since the joined body 21b shown in FIG. 7B joins the aluminum alloy material 10 and the resin molded body 7, it is lighter in weight than the joined body of aluminum alloy materials, and by using this joined body 21b. Further weight reduction of the automobile can be realized. The configurations and effects of the bonded bodies 21a and 21b shown in FIGS. 7A and 7B other than the above are the same as those of the bonded body 20 shown in FIG.
更に、図８に示す接合体２２のように、図４に示す接着樹脂層４を備えた接着樹脂層付きアルミニウム合金材１１と、図３に示す接着樹脂層４を備えていないアルミニウム合金材１０とを接合した構成とすることもできる。具体的には、接着樹脂層付きアルミニウム合金材１１の接着樹脂層４側に、アルミニウム合金材１０の表面処理皮膜２が接合されたものである。その結果、アルミニウム合金材１０の皮膜２と接着樹脂層付きアルミニウム合金材１１の皮膜２は、それぞれ接着樹脂層付きアルミニウム合金材１１の接着樹脂層４を介して、互いに対向するように配置された構成となっている。 Further, like the joined body 22 shown in FIG. 8, the aluminum alloy material 11 with the adhesive resin layer 4 shown in FIG. 4 and the aluminum alloy material 10 without the adhesive resin layer 4 shown in FIG. It is also possible to adopt a configuration in which and are joined. Specifically, the surface treatment film 2 of the aluminum alloy material 10 is joined to the adhesive resin layer 4 side of the aluminum alloy material 11 with the adhesive resin layer. As a result, the coating 2 of the aluminum alloy material 10 and the coating 2 of the aluminum alloy material 11 with the adhesive resin layer were arranged so as to face each other via the adhesive resin layer 4 of the aluminum alloy material 11 with the adhesive resin layer. It is composed.
接合体２２では、接着樹脂層４の両面が表面処理皮膜２側に接合されているため、前述した接合体２０と同様に、接合体２２を自動車用部材に用いた際に、高温湿潤環境に曝されても、接着樹脂の種類に影響されず、界面での接着耐久性が向上する。なお、図８に示す接合体２２における上記以外の構成及び効果は、図６に示す接合体２０と同様である。 In the joined body 22, since both surfaces of the adhesive resin layer 4 are joined to the surface treatment film 2 side, when the joined body 22 is used for an automobile member, it is exposed to a high temperature and humid environment, as in the joined body 20 described above. Even if exposed, the adhesion durability at the interface is improved without being affected by the type of adhesive resin. The structure and effects of the bonded body 22 shown in FIG. 8 other than the above are the same as those of the bonded body 20 shown in FIG.
更に、図９Ａに示す接合体２３ａ又は図９Ｂに示す接合体２３ｂのように、図４に示す接着樹脂層４を備えた接着樹脂層付きアルミニウム合金材１１の接着樹脂層４側に、表面処理皮膜が形成されていない他のアルミニウム合金材６又は繊維強化プラスチック成形体などの樹脂成形体７を接合した構成とすることもできる。これら接合体２３ａ，２３ｂでは、接着樹脂層４の片面が表面処理皮膜２側に接合されているため、前述した接合体２０と同様に、接合体２３を自動車用部材に用いる際、高温湿潤環境に曝されても、接着樹脂の種類に影響されず、界面での接着耐久性が向上する。 Further, as in the joined body 23a shown in FIG. 9A or the joined body 23b shown in FIG. 9B, a surface treatment is performed on the adhesive resin layer 4 side of the aluminum alloy material 11 with an adhesive resin layer having the adhesive resin layer 4 shown in FIG. It is also possible to adopt a configuration in which another aluminum alloy material 6 on which no film is formed or a resin molded body 7 such as a fiber reinforced plastic molded body is joined. In these bonded bodies 23a and 23b, one surface of the adhesive resin layer 4 is bonded to the surface treatment film 2 side. Therefore, similar to the bonded body 20 described above, when the bonded body 23 is used as an automobile member, a high temperature wet environment is used. Even if exposed to, the adhesive durability at the interface is improved without being affected by the type of adhesive resin.
また、図９Ｂに示す接合体２３ｂは、接着樹脂層付きアルミニウム合金材１１と樹脂成形体７とを接合しているため、アルミニウム合金材同士の接合体に比べて軽量であり、軽量化が求められている自動車や車両の部材に好適である。なお、図９Ａ及び図９Ｂに示す接合体２３ａ，２３ｂにおける上記以外の構成及び効果は、図６に示す接合体２０と同様である。 Further, since the joined body 23b shown in FIG. 9B joins the adhesive resin layer-attached aluminum alloy material 11 and the resin molded body 7, it is lighter in weight than the joined body of aluminum alloy materials, and a reduction in weight is required. It is suitable for existing automobiles and vehicle members. The configurations and effects of the bonded bodies 23a and 23b shown in FIGS. 9A and 9B other than the above are the same as those of the bonded body 20 shown in FIG.
［接合体の製造方法］
前述した接合体２０〜２３の製造方法、特に接合方法は、従来公知の接合方法を用いることができる。そして、接着樹脂５をアルミニウム合金材に形成する方法は、特に限定されるものではないが、例えば、予め接着樹脂５によって作製した接着シートを用いてもよいし、接着樹脂５を表面処理皮膜２の表面に噴霧または塗布することによって形成してもよい。なお、接合体２０〜２３は、アルミニウム合金材１０や接着樹脂層付きアルミニウム合金材１１と同様に、自動車用部材への加工前に、その表面にプレス油を塗布してもよい。
[Method for manufacturing bonded body]
As a method of manufacturing the above-described joined bodies 20 to 23, particularly a joining method, a conventionally known joining method can be used. The method for forming the adhesive resin 5 on the aluminum alloy material is not particularly limited, but for example, an adhesive sheet prepared in advance with the adhesive resin 5 may be used, or the adhesive resin 5 may be used for the surface treatment film 2. It may be formed by spraying or applying on the surface of. As with the aluminum alloy material 10 and the aluminum alloy material 11 with an adhesive resin layer, the bonded bodies 20 to 23 may be coated with a press oil on the surface thereof before being processed into a vehicle member.
また、図示しないが、本実施形態の接合体に、両面に表面処理皮膜２が形成されたアルミニウム合金材を用いた場合、接着樹脂５又は接着樹脂層４を介して、これらのアルミニウム合金材又は皮膜２が形成されていない他のアルミニウム合金材６又は樹脂成形体７を、さらに接合することが可能となる。 Although not shown, when an aluminum alloy material having the surface-treated coatings 2 formed on both surfaces is used for the joined body of the present embodiment, these aluminum alloy materials or the adhesive resin layer 4 are used. It is possible to further bond the other aluminum alloy material 6 or the resin molded body 7 on which the film 2 is not formed.
（第３の実施形態）
次に、本発明の第３の実施形態に係る自動車用部材について説明する。本実施形態の自動車用部材は、前述した第２の実施形態の接合体を用いたものであり、例えば、自動車用パネルなどである。
(Third Embodiment)
Next, an automobile member according to a third embodiment of the present invention will be described. The automobile member of the present embodiment uses the joined body of the second embodiment described above, and is, for example, an automobile panel or the like.
また、本実施形態の自動車用部材の製造方法は、特に限定されるものではないが、従来公知の製造方法を適用することができる。例えば、図６〜９Ｂに示す接合体２０〜２３ｂに切断加工やプレス加工などを施して所定形状の自動車用部材を製造する。 The method for manufacturing the automobile member of the present embodiment is not particularly limited, but a conventionally known manufacturing method can be applied. For example, the joined bodies 20 to 23b shown in FIGS. 6 to 9B are subjected to cutting, pressing or the like to manufacture a vehicle member having a predetermined shape.
本実施形態の自動車用部材は、前述した第２の実施形態の接合体から製造されるため、高温湿潤環境に曝されても、接着樹脂又は接着樹脂層と、酸化皮膜の水和の影響をほとんど受けることなく、アルミニウム合金基材の溶出も抑制できる。その結果、本実施形態の自動車用部材では、高温湿潤環境に曝された場合の界面剥離を抑制し、接着強度の低下を抑制することが可能となる。 Since the automobile member of the present embodiment is manufactured from the bonded body of the above-described second embodiment, even if it is exposed to a high temperature humid environment, the influence of the hydration of the adhesive resin or the adhesive resin layer and the oxide film can be prevented. The elution of the aluminum alloy base material can be suppressed with almost no reception. As a result, in the automobile member of the present embodiment, it is possible to suppress interfacial peeling when exposed to a high temperature and humid environment and to suppress a decrease in adhesive strength.
以下、本発明の実施例及び比較例を挙げて、本発明の効果について具体的に説明する。本実施例においては、以下に示す方法及び条件で、アルミニウム合金材を作製し、その接着耐久性などを評価した。 Hereinafter, the effects of the present invention will be specifically described with reference to Examples and Comparative Examples of the present invention. In this example, an aluminum alloy material was produced by the method and conditions shown below, and its adhesion durability and the like were evaluated.
（基材作製工程及び酸化皮膜形成工程）
基材の作製及び酸化皮膜の形成は以下のようにして行った。
(Substrate manufacturing process and oxide film forming process)
The base material was prepared and the oxide film was formed as follows.
＜実施例１＞
ＪＩＳ６０１６（Ｍｇ：０．５４質量％、Ｓｉ：１．１１質量％、Ｃｕ：０．１４質量％）の６０００系アルミニウム合金を用いて、前述した方法により板厚１ｍｍのアルミニウム合金冷延板を作製した。そして、この冷延板を長さ１００ｍｍ、幅２５ｍｍに切断して基材とした。次に、実体到達温度５５０℃まで加熱処理し、冷却した。
つづいて、アルカリ溶液による処理として、基材にｐＨ１３に調整した水酸化カリウム溶液を用いて、温度５０℃、処理時間１０秒間の条件で浸漬処理を行い、その後水洗を行った。
次に、酸洗として、ｐＨ１に調整した硫酸とフッ酸を含む水溶液を用いて、温度５０℃、処理時間１０秒の条件で浸漬処理を行い、その後水洗した。この操作により表１に記載のエッチング量、及びＭｇ量とＣｕ量の酸化皮膜を基材に形成した。
<Example 1>
Using the JIS6016 (Mg: 0.54 mass%, Si: 1.11 mass%, Cu: 0.14 mass%) 6000 series aluminum alloy, a 1 mm thick aluminum alloy cold-rolled sheet was produced by the method described above. did. Then, this cold rolled plate was cut into a length of 100 mm and a width of 25 mm to obtain a base material. Next, heat treatment was performed up to the actual temperature reached of 550° C., and cooling was performed.
Subsequently, as a treatment with an alkaline solution, a potassium hydroxide solution adjusted to pH 13 was used as a substrate, an immersion treatment was performed under the conditions of a temperature of 50° C. and a treatment time of 10 seconds, followed by washing with water.
Next, as pickling, an aqueous solution containing sulfuric acid and hydrofluoric acid adjusted to pH 1 was used for immersion treatment under conditions of a temperature of 50° C. and a treatment time of 10 seconds, followed by washing with water. By this operation, the oxide film having the etching amount, the Mg amount and the Cu amount shown in Table 1 was formed on the substrate.
＜実施例２＞
酸洗の処理時間を６０秒とした以外は、実施例１同様の処理を行い、表１に記載のエッチング量、及びＭｇ量とＣｕ量の酸化皮膜を基材に形成した。
<Example 2>
The same treatment as in Example 1 was performed, except that the pickling treatment time was 60 seconds, to form an oxide film having the etching amounts and the Mg and Cu amounts shown in Table 1 on the substrate.
＜実施例３＞
酸洗の処理時間を１２０秒とした以外は、実施例１同様の処理を行い、表１に記載のエッチング量、及びＭｇ量とＣｕ量の酸化皮膜を基材に形成した。
<Example 3>
The same treatment as in Example 1 was performed, except that the pickling treatment time was 120 seconds, to form an oxide film having the etching amount and the Mg amount and the Cu amount shown in Table 1 on the substrate.
＜実施例４＞
アルカリ溶液による処理の処理時間を１１０秒とし、酸洗の処理時間を１１０秒とした以外は、実施例１同様の処理を行い、表１に記載のエッチング量、及びＭｇ量とＣｕ量の酸化皮膜を基材に形成した。
<Example 4>
Except that the treatment time of the treatment with the alkaline solution was 110 seconds and the treatment time of the pickling was 110 seconds, the same treatment as in Example 1 was performed, and the etching amounts and the amounts of Mg and Cu shown in Table 1 were oxidized. A film was formed on the substrate.
＜実施例５＞
アルカリ溶液による処理の処理時間を９０秒とし、酸洗条件として、ｐＨ１に調整した硫酸を含む水溶液を用いて、温度６０℃、処理時間１００秒とした以外は、実施例１同様の処理を行い、表１に記載のエッチング量、及びＭｇ量とＣｕ量の酸化皮膜を基材に形成した。
<Example 5>
The same treatment as in Example 1 was performed except that the treatment time with the alkaline solution was 90 seconds, and the pickling condition was an aqueous solution containing sulfuric acid adjusted to pH 1, the temperature was 60° C., and the treatment time was 100 seconds. An oxide film having the etching amount and the Mg amount and the Cu amount shown in Table 1 was formed on the substrate.
＜実施例６＞
アルカリ溶液による処理を行わず、酸洗条件として、ｐＨ１に調整した硝酸を含む水溶液を用いて、温度６０℃とした以外は、実施例１同様の処理を行い、表１に記載のエッチング量、及びＭｇ量とＣｕ量の酸化皮膜を基材に形成した。
<Example 6>
The same treatment as in Example 1 was performed, except that the treatment with an alkaline solution was not performed and the aqueous solution containing nitric acid adjusted to pH 1 was used as the pickling condition, and the temperature was 60° C. And an oxide film containing Mg and Cu was formed on the substrate.
＜実施例７＞
アルカリ溶液による処理を行わず、酸洗条件として、ｐＨ３にした以外は、実施例１同様の処理を行い、表１に記載のエッチング量、及びＭｇ量とＣｕ量の酸化皮膜を基材に形成した。
<Example 7>
The same treatment as in Example 1 was performed, except that the treatment with an alkali solution was not performed and the pH was set to 3 as the pickling condition, and an oxide film having the etching amount, the Mg amount and the Cu amount shown in Table 1 was formed on the substrate. did.
＜実施例８＞
アルカリ溶液による処理を行わず、酸洗条件として、ｐＨ３、処理時間２秒にした以外は、実施例１同様の処理を行い、表１に記載のエッチング量、及びＭｇ量とＣｕ量の酸化皮膜を基材に形成した。
<Example 8>
The same treatment as in Example 1 was performed, except that the treatment with an alkaline solution was not performed and the pH was 3 as the pickling condition, and the treatment time was 2 seconds. Was formed on the substrate.
＜比較例１＞
アルカリ溶液による処理の処理時間が１３０秒、酸洗条件として、ｐＨ１に調整した硫酸を含む水溶液を用いて、温度６０℃、処理時間２００秒とした以外は、実施例１同様の処理を行い、表１に記載のエッチング量、及びＭｇ量とＣｕ量の酸化皮膜を基材に形成した。
<Comparative Example 1>
The same treatment as in Example 1 was performed except that the treatment time with the alkaline solution was 130 seconds, and the pickling condition was an aqueous solution containing sulfuric acid adjusted to pH 1, the temperature was 60° C., and the treatment time was 200 seconds. An oxide film having the etching amount and the Mg amount and the Cu amount shown in Table 1 was formed on the substrate.
＜比較例２＞
アルカリ溶液による処理と酸洗、すなわちエッチングを行わなかった以外は、実施例１同様の処理を行い、表１に記載のＭｇ量とＣｕ量の酸化皮膜を基材に形成した。
<Comparative example 2>
The same treatment as in Example 1 was performed, except that the treatment with an alkaline solution and the pickling, that is, the etching was not performed, to form an oxide film having the amounts of Mg and Cu shown in Table 1 on the substrate.
（表面処理皮膜形成工程）
つづいて、各実施例１〜８及び比較例１〜２において、基材表面上の酸化皮膜に、０．１５質量％のテトラエチルオルソシリケート（ＴＥＯＳ）と、０．１質量％のビストリエトキシシリルエタン（ＢＴＳＥ）とを含み、かつ直径１ｎｍ以上のゾルを含まないｐＨが５に調整された水溶液（表面処理液）を、ディップまたはバーコータにより塗布して表面処理皮膜を形成し、各実施例及び比較例のアルミニウム合金材を作製した。なお、表面処理液の塗布後の乾燥は、１０５℃で、１分間行った。乾燥後の塗布量は、蛍光Ｘ線で、塗布前後の測定から、バーコーターで５ｍｇ／ｍ２程度、ディップで４ｍｇ／ｍ２程度であることを確認した。
(Surface treatment film forming process)
Subsequently, in each of Examples 1 to 8 and Comparative Examples 1 and 2, 0.15% by mass of tetraethyl orthosilicate (TEOS) and 0.1% by mass of bistriethoxysilylethane were added to the oxide film on the surface of the substrate. An aqueous solution (surface treatment solution) containing (BTSE) and having a diameter of 1 nm or more and containing no sol and having a pH adjusted to 5 is applied by a dip or a bar coater to form a surface treatment film. The aluminum alloy material of the example was produced. In addition, the drying after the application of the surface treatment liquid was performed at 105° C. for 1 minute. The coating amount after drying was confirmed to be about 5 mg/m 2 with a bar coater and about 4 mg/m 2 with a dip based on the measurement before and after coating with fluorescent X-ray.
＜比較例３＞
実施例５の同様の基材作製工程及び酸化皮膜形成工程を行い、基材表面上の酸化皮膜に、１．２質量％のテトラエチルオルソシリケート（ＴＥＯＳ）と、１．２質量％のビストリエトキシシリルエタン（ＢＴＳＥ）とを含み、かつ直径１ｎｍ以上のゾルを含まないｐＨが４に調整された水溶液（表面処理液）を、バーコータにより塗布して表面処理皮膜を形成し、各実施例及び比較例のアルミニウム合金材を作製した。なお、表面処理液の塗布後の乾燥は、１０５℃で、１分間行った。乾燥後の塗布量は、蛍光Ｘ線で、塗布前後の測定から、２９ｍｇ／ｍ２程度であることを確認した。
<Comparative example 3>
The same base material manufacturing step and oxide film forming step as in Example 5 were performed, and 1.2 mass% of tetraethyl orthosilicate (TEOS) and 1.2 mass% of bistriethoxysilyl were added to the oxide film on the surface of the base material. An aqueous solution (surface treatment liquid) containing ethane (BTSE) and having a diameter of 1 nm or more and containing no sol and having a pH adjusted to 4 was applied by a bar coater to form a surface treatment film. The aluminum alloy material of was produced. In addition, the drying after the application of the surface treatment liquid was performed at 105° C. for 1 minute. The coating amount after drying was confirmed to be about 29 mg/m 2 by fluorescent X-ray measurement before and after coating.
この様に作製した各実施例及び比較例に係るアルミニウム合金材の第２皮膜側の表面に、トルエンで希釈したプレス油を、乾燥後の塗布量が１ｇ／ｍ２となるように塗布した。 Pressing oil diluted with toluene was applied to the surface of the aluminum alloy material according to each of the examples and comparative examples thus prepared on the side of the second coating so that the coating amount after drying was 1 g/m 2 .
＜酸化皮膜成分の測定＞
酸化皮膜を形成後、表面処理皮膜を形成する前の各実施例及び比較例に係るアルミニウム合金基材の酸化皮膜について、高周波グロー放電発光分光分析法（ＧＤ−ＯＥＳ：ホリバ・ジョバンイボン社製型式ＪＹ−５０００ＲＦ）により膜厚方向にスパッタしながら測定し、アルミニウム（Ａｌ）、マグネシウム（Ｍｇ）、銅（Ｃｕ）、鉄（Ｆｅ）及びチタン（Ｔｉ）等の金属元素、及び酸素（Ｏ）、窒素（Ｎ）、炭素（Ｃ）、ケイ素（Ｓｉ）及び硫黄（Ｓ）等の元素について、各成分量の測定を行った。酸化皮膜中のマグネシウム（Ｍｇ）、銅（Ｃｕ）の最大濃度を、その皮膜中の皮膜濃度とした。ここで、これら各元素の濃度の算出において、特に酸素（Ｏ）及び炭素（Ｃ）は最表面やその近傍でコンタミの影響を受けやすい。以上のことから、各元素の濃度計算では、酸素（Ｏ）及び炭素（Ｃ）を除いて、濃度を算出した。
<Measurement of oxide film components>
After forming the oxide film and before forming the surface treatment film, the oxide film of the aluminum alloy base material according to each of the examples and comparative examples was subjected to high-frequency glow discharge emission spectrometry (GD-OES: manufactured by Horiba Jobin Yvon). JY-5000RF) while performing sputtering in the film thickness direction, and metal elements such as aluminum (Al), magnesium (Mg), copper (Cu), iron (Fe) and titanium (Ti), and oxygen (O), The amount of each component was measured for elements such as nitrogen (N), carbon (C), silicon (Si) and sulfur (S). The maximum concentration of magnesium (Mg) and copper (Cu) in the oxide film was defined as the film concentration in the film. Here, in the calculation of the concentrations of these elements, oxygen (O) and carbon (C) are particularly susceptible to contamination on the outermost surface and in the vicinity thereof. From the above, in the calculation of the concentration of each element, the concentration was calculated excluding oxygen (O) and carbon (C).
＜エッチング量＞
エッチング量（単位：ｇ／ｃｍ２）は、酸化皮膜形成工程前後の基材の重量の減少量（単位：ｇ）を測定し、これを基材の表面積（単位：ｍ２）で割ることにより算出した。
<Etching amount>
The etching amount (unit: g/cm 2 ) is obtained by measuring the reduction amount (unit: g) of the weight of the base material before and after the oxide film formation step and dividing this by the surface area (unit: m 2 ) of the base material. Calculated.
＜凝集破壊率（接着耐久性）＞
図１０Ａ及び図１０Ｂは凝集破壊率の測定方法を模式的に示す図であり、図１０Ａは側面図であり、図１０Ｂは平面図である。図１０Ａ及び図１０Ｂに示すように、構成が同じ２枚の供試材３１ａ，３１ｂ（２５ｍｍ幅）の端部を、熱硬化型エポキシ樹脂系接着樹脂によりラップ長１０ｍｍ（接着面積：２５ｍｍ×１０ｍｍ）となるように重ね合わせ貼り付けた。
ここで用いた接着樹脂３５は熱硬化型エポキシ樹脂系接着剤（ビスフェノールＡ型エポキシ樹脂量４０〜５０質量％）である。また、接着樹脂３５の厚さが２５０μｍとなるように微量のガラスビーズ（粒径２５０μｍ）を接着樹脂３５に添加して調節した。
重ね合わせてから３０分間、室温で乾燥させて、その後、１７０℃で２０分間加熱し、熱硬化処理を実施した。その後、室温で２４時間静置して接着試験体を作製した。
<Cohesive failure rate (adhesion durability)>
10A and 10B are diagrams schematically showing the method for measuring the cohesive failure rate, FIG. 10A is a side view, and FIG. 10B is a plan view. As shown in FIGS. 10A and 10B, the end portions of two test materials 31a and 31b (25 mm width) having the same configuration are wrapped with a thermosetting epoxy resin adhesive resin in a wrap length of 10 mm (bonding area: 25 mm×10 mm). ) Was pasted and pasted.
The adhesive resin 35 used here is a thermosetting epoxy resin adhesive (bisphenol A type epoxy resin amount 40 to 50% by mass). Further, a small amount of glass beads (particle size 250 μm) was added to the adhesive resin 35 to adjust the thickness of the adhesive resin 35 to 250 μm.
After overlapping, they were dried at room temperature for 30 minutes, and then heated at 170° C. for 20 minutes to carry out a thermosetting treatment. Then, it left still at room temperature for 24 hours, and produced the adhesion test body.
作製した接着試験体を、５０℃、相対湿度９５％の高温湿潤環境に３０日間保持後、引張試験機にて５０ｍｍ／分の速度で引張り、接着部分の接着樹脂の凝集破壊率を評価した。凝集破壊率は下記数式１に基づいて算出した。なお、下記数式１においては、接着試験体の引張後の片側を試験片ａ、もう片方を試験片ｂとした。 The prepared adhesion test body was kept in a high temperature and humid environment at 50° C. and a relative humidity of 95% for 30 days and then pulled at a speed of 50 mm/min by a tensile tester to evaluate the cohesive failure rate of the adhesive resin in the bonded portion. The cohesive failure rate was calculated based on the following mathematical formula 1. In Formula 1 below, one side of the adhesion test body after being pulled was designated as a test piece a and the other side was designated as a test piece b.
各試験条件とも３本ずつ作製し、凝集破壊率は３本の平均値とした。また、評価基準は、凝集破壊率が６０％未満を不良（×）、６０％以上７０％未満をやや良好（△）、７０％以上９０％未満を良好（○）、９０％以上を特に良好（◎）とし、６０％以上を合格とした。 Three pieces were produced under each test condition, and the cohesive failure rate was an average value of three pieces. In addition, the evaluation criteria are that the cohesive failure rate is less than 60% is poor (x), 60% or more and less than 70% is somewhat good (△), 70% or more and less than 90% is good (◯), and 90% or more is particularly good. (⊚), and 60% or more was passed.
以上の結果を、表１にまとめて示す。 The above results are summarized in Table 1.
上記表１に示すように、酸化皮膜中のＣｕの濃度が本発明規定の範囲から外れている比較例１のアルミニウム合金材は、凝集破壊率が６０％未満と不良であり、高温湿潤環境での接着耐久性に劣るものであった。
また、酸洗やアルカリ洗浄を経ずに作製された比較例２のアルミニウム合金材は、酸化皮膜中のＭｇの濃度が本発明規定の範囲から外れており、凝集破壊率が６０％未満と不良であり、高温湿潤環境での接着耐久性に劣るものであった。
また、ＴＥＯＳ濃度及びＢＴＳＥ濃度が本発明規定の範囲から外れている比較例３のアルミニウム合金材は、凝集破壊率が６０％未満と不良であり、高温湿潤環境での接着耐久性に劣るものであった。
As shown in Table 1 above, the aluminum alloy material of Comparative Example 1 in which the concentration of Cu in the oxide film is out of the range specified by the present invention has a poor cohesive failure rate of less than 60%, and is poor in a high temperature wet environment. Was inferior in adhesion durability.
In the aluminum alloy material of Comparative Example 2 produced without pickling or alkali washing, the concentration of Mg in the oxide film was out of the range defined by the invention, and the cohesive failure rate was less than 60%, which was a defect. And was inferior in adhesion durability in a hot and humid environment.
In addition, the aluminum alloy material of Comparative Example 3 in which the TEOS concentration and the BTSE concentration are out of the ranges defined by the present invention has a poor cohesive failure rate of less than 60% and is inferior in adhesion durability in a high temperature and humid environment. there were.
これに対して、本発明の製造方法により得られた実施例１〜８のアルミニウム合金材は、いずれも凝集破壊率が６０％以上であり、高温湿潤環境での接着耐久性が良好であった。 On the other hand, the aluminum alloy materials of Examples 1 to 8 obtained by the production method of the present invention all had a cohesive failure rate of 60% or more, and had good adhesion durability in a high temperature and humid environment. ..
１ 酸化皮膜
２ 表面処理皮膜
３ 基材
４ 接着樹脂層
５、３５ 接着樹脂
６、１０ アルミニウム合金材
１１ 接着樹脂層付きアルミニウム合金材
７ 樹脂成形体
２０、２１ａ、２１ｂ、２２、２３ａ、２３ｂ 接合体
３１ａ、３１ｂ 供試材
DESCRIPTION OF SYMBOLS 1 Oxidized film 2 Surface treatment film 3 Base material 4 Adhesive resin layer 5,35 Adhesive resin 6,10 Aluminum alloy material 11 Aluminum alloy material with an adhesive resin layer 7 Resin molded body 20, 21a, 21b, 22, 23a, 23b Bonded body 31a, 31b Test material
Claims (5)
前記酸化皮膜の少なくとも一部に、０．００５質量％以上１質量％未満のアルキルシリケートまたはそのオリゴマーと、０．００５質量％以上１質量％未満の有機シラン化合物とを含み、ｐＨが２以上７以下である水溶液を塗布することを含む表面処理皮膜形成工程と
を備えるアルミニウム合金材の製造方法。 An oxide film forming step of forming an oxide film containing Mg in an amount of 0.1 atom% or more and less than 30 atom% and Cu regulated to less than 0.6 atom% on at least a part of the surface of the aluminum alloy substrate.
At least a part of the oxide film contains 0.005% by mass or more and less than 1% by mass of an alkyl silicate or an oligomer thereof and 0.005% by mass or more and less than 1% by mass of an organic silane compound, and has a pH of 2 or more and 7 or more. A method for producing an aluminum alloy material, comprising the following steps of forming a surface treatment film including applying an aqueous solution.
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| KR20220156367A (en) | 2021-05-18 | 2022-11-25 | 한국생산기술연구원 | 2xxx aluminum alloys, and methods for producing the same |
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| GB9424711D0 (en) * | 1994-12-07 | 1995-02-01 | Alcan Int Ltd | Composition for surface treatment |
| KR101168628B1 (en) * | 2008-01-24 | 2012-07-30 | 유껜 고교 가부시기가이샤 | Member with corrosion-resistant coating film, process for production of the same, and coating composition for the production thereof |
| JP2013131595A (en) * | 2011-12-21 | 2013-07-04 | Hitachi Ltd | Method for joining metal member and resin together and assembly of metal member and resin |
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| KR20220156367A (en) | 2021-05-18 | 2022-11-25 | 한국생산기술연구원 | 2xxx aluminum alloys, and methods for producing the same |
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