JP6186792B2 - Surface-treated aluminum plate, organic resin-coated surface-treated aluminum plate, and can body and can lid using the same - Google Patents
Surface-treated aluminum plate, organic resin-coated surface-treated aluminum plate, and can body and can lid using the same Download PDFInfo
- Publication number
- JP6186792B2 JP6186792B2 JP2013064172A JP2013064172A JP6186792B2 JP 6186792 B2 JP6186792 B2 JP 6186792B2 JP 2013064172 A JP2013064172 A JP 2013064172A JP 2013064172 A JP2013064172 A JP 2013064172A JP 6186792 B2 JP6186792 B2 JP 6186792B2
- Authority
- JP
- Japan
- Prior art keywords
- aluminum plate
- treated aluminum
- zirconium
- organic resin
- coating
- 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.)
- Active
Links
- 229910052782 aluminium Inorganic materials 0.000 title claims description 117
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims description 116
- 229920005989 resin Polymers 0.000 title description 72
- 239000011347 resin Substances 0.000 title description 72
- 229920001225 polyester resin Polymers 0.000 claims description 57
- 239000004645 polyester resin Substances 0.000 claims description 57
- 239000000126 substance Substances 0.000 claims description 44
- 238000011282 treatment Methods 0.000 claims description 44
- 238000004381 surface treatment Methods 0.000 claims description 43
- -1 fluorine ions Chemical class 0.000 claims description 39
- 229910052726 zirconium Inorganic materials 0.000 claims description 37
- 239000007788 liquid Substances 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 26
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 20
- 229910052719 titanium Inorganic materials 0.000 claims description 20
- 239000010936 titanium Substances 0.000 claims description 20
- 238000007739 conversion coating Methods 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 229910052799 carbon Inorganic materials 0.000 claims description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 14
- 229910052731 fluorine Inorganic materials 0.000 claims description 9
- 239000011737 fluorine Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000007921 spray Substances 0.000 claims description 4
- 238000007654 immersion Methods 0.000 claims description 3
- 238000000576 coating method Methods 0.000 description 45
- 239000011248 coating agent Substances 0.000 description 42
- 238000005260 corrosion Methods 0.000 description 35
- 230000007797 corrosion Effects 0.000 description 35
- 150000003609 titanium compounds Chemical class 0.000 description 19
- 239000000463 material Substances 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 150000003755 zirconium compounds Chemical class 0.000 description 15
- 238000012545 processing Methods 0.000 description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 239000011247 coating layer Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000003973 paint Substances 0.000 description 9
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- 239000010410 layer Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 229910000838 Al alloy Inorganic materials 0.000 description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 229910052804 chromium Inorganic materials 0.000 description 6
- 239000011651 chromium Substances 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 229920000728 polyester Polymers 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical compound [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 0.000 description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 5
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 5
- WMYWOWFOOVUPFY-UHFFFAOYSA-L dihydroxy(dioxo)chromium;phosphoric acid Chemical compound OP(O)(O)=O.O[Cr](O)(=O)=O WMYWOWFOOVUPFY-UHFFFAOYSA-L 0.000 description 5
- 238000005530 etching Methods 0.000 description 5
- 238000010409 ironing Methods 0.000 description 5
- 229920005992 thermoplastic resin Polymers 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 238000011088 calibration curve Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000007769 metal material Substances 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 229920006267 polyester film Polymers 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000005238 degreasing Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 150000007519 polyprotic acids Polymers 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 3
- 125000000542 sulfonic acid group Chemical group 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229920001634 Copolyester Polymers 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- UJMDYLWCYJJYMO-UHFFFAOYSA-N benzene-1,2,3-tricarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1C(O)=O UJMDYLWCYJJYMO-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 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
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- YOYLLRBMGQRFTN-SMCOLXIQSA-N norbuprenorphine Chemical compound C([C@@H](NCC1)[C@]23CC[C@]4([C@H](C3)C(C)(O)C(C)(C)C)OC)C3=CC=C(O)C5=C3[C@@]21[C@H]4O5 YOYLLRBMGQRFTN-SMCOLXIQSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- DXIGZHYPWYIZLM-UHFFFAOYSA-J tetrafluorozirconium;dihydrofluoride Chemical compound F.F.F[Zr](F)(F)F DXIGZHYPWYIZLM-UHFFFAOYSA-J 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- ZWVMLYRJXORSEP-UHFFFAOYSA-N 1,2,6-Hexanetriol Chemical compound OCCCCC(O)CO ZWVMLYRJXORSEP-UHFFFAOYSA-N 0.000 description 1
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 1
- WHYQMPJLTUMFFV-UHFFFAOYSA-N 2-(4-sulfophenoxy)benzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1OC1=CC=C(S(O)(=O)=O)C=C1 WHYQMPJLTUMFFV-UHFFFAOYSA-N 0.000 description 1
- MMINFSMURORWKH-UHFFFAOYSA-N 3,6-dioxabicyclo[6.2.2]dodeca-1(10),8,11-triene-2,7-dione Chemical group O=C1OCCOC(=O)C2=CC=C1C=C2 MMINFSMURORWKH-UHFFFAOYSA-N 0.000 description 1
- LFBALUPVVFCEPA-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C(C(O)=O)=C1 LFBALUPVVFCEPA-UHFFFAOYSA-N 0.000 description 1
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical compound C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 description 1
- HBLRZDACQHNPJT-UHFFFAOYSA-N 4-sulfonaphthalene-2,7-dicarboxylic acid Chemical compound OS(=O)(=O)C1=CC(C(O)=O)=CC2=CC(C(=O)O)=CC=C21 HBLRZDACQHNPJT-UHFFFAOYSA-N 0.000 description 1
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- CARJPEPCULYFFP-UHFFFAOYSA-N 5-Sulfo-1,3-benzenedicarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(S(O)(=O)=O)=C1 CARJPEPCULYFFP-UHFFFAOYSA-N 0.000 description 1
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical class OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- WRAGBEWQGHCDDU-UHFFFAOYSA-M C([O-])([O-])=O.[NH4+].[Zr+] Chemical compound C([O-])([O-])=O.[NH4+].[Zr+] WRAGBEWQGHCDDU-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- ZLSPYXQZLJFBBV-UHFFFAOYSA-H F[Zr](F)(F)(F)(F)F.N Chemical compound F[Zr](F)(F)(F)(F)F.N ZLSPYXQZLJFBBV-UHFFFAOYSA-H 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- 229910017855 NH 4 F Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229920000571 Nylon 11 Polymers 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- NIDZWWNRMZPMLN-UHFFFAOYSA-N [1,4,4-tris(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCC(CO)(CO)CC1 NIDZWWNRMZPMLN-UHFFFAOYSA-N 0.000 description 1
- PFYRERIAJQIGKB-UHFFFAOYSA-H [K].F[Zr](F)(F)(F)(F)F Chemical compound [K].F[Zr](F)(F)(F)(F)F PFYRERIAJQIGKB-UHFFFAOYSA-H 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 125000004018 acid anhydride group Chemical group 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- OXAUNDBQHKIUSD-UHFFFAOYSA-N azanium;titanium;fluoride Chemical compound [NH4+].[F-].[Ti] OXAUNDBQHKIUSD-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 238000009924 canning Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- VEIOBOXBGYWJIT-UHFFFAOYSA-N cyclohexane;methanol Chemical compound OC.OC.C1CCCCC1 VEIOBOXBGYWJIT-UHFFFAOYSA-N 0.000 description 1
- WOSVXXBNNCUXMT-UHFFFAOYSA-N cyclopentane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1CC(C(O)=O)C(C(O)=O)C1C(O)=O WOSVXXBNNCUXMT-UHFFFAOYSA-N 0.000 description 1
- 239000013527 degreasing agent Substances 0.000 description 1
- 238000005237 degreasing agent Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- XWENCHGJOCJZQO-UHFFFAOYSA-N ethane-1,1,2,2-tetracarboxylic acid Chemical compound OC(=O)C(C(O)=O)C(C(O)=O)C(O)=O XWENCHGJOCJZQO-UHFFFAOYSA-N 0.000 description 1
- RWLDAJMGAVDXSH-UHFFFAOYSA-N ethane-1,1,2-tricarboxylic acid Chemical compound OC(=O)CC(C(O)=O)C(O)=O RWLDAJMGAVDXSH-UHFFFAOYSA-N 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000007765 extrusion coating Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- LYTNHSCLZRMKON-UHFFFAOYSA-L oxygen(2-);zirconium(4+);diacetate Chemical compound [O-2].[Zr+4].CC([O-])=O.CC([O-])=O LYTNHSCLZRMKON-UHFFFAOYSA-L 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- ROTJZTYLACIJIG-UHFFFAOYSA-N pentane-1,3,5-tricarboxylic acid Chemical compound OC(=O)CCC(C(O)=O)CCC(O)=O ROTJZTYLACIJIG-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 1
- MYYUWUVATCWCES-UHFFFAOYSA-L potassium;oxalate;titanium(4+);dihydrate Chemical compound O.O.[K+].[Ti+4].[O-]C(=O)C([O-])=O MYYUWUVATCWCES-UHFFFAOYSA-L 0.000 description 1
- SQTLECAKIMBJGK-UHFFFAOYSA-I potassium;titanium(4+);pentafluoride Chemical compound [F-].[F-].[F-].[F-].[F-].[K+].[Ti+4] SQTLECAKIMBJGK-UHFFFAOYSA-I 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000000992 sputter etching Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- XROWMBWRMNHXMF-UHFFFAOYSA-J titanium tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[Ti+4] XROWMBWRMNHXMF-UHFFFAOYSA-J 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 238000009966 trimming Methods 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
Landscapes
- Chemical Treatment Of Metals (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Details Of Rigid Or Semi-Rigid Containers (AREA)
- Laminated Bodies (AREA)
Description
本発明は、表面処理アルミニウム板及びこれに有機樹脂被覆層を施してなる有機樹脂被覆表面処理アルミニウム板に関するものであり、より詳細には、有機樹脂被覆層の密着性に優れ、製缶材料として優れた耐食性及び加工密着性を発現可能な表面処理アルミニウム板及び有機樹脂被覆表面処理アルミニウム板に関する。 The present invention relates to a surface-treated aluminum plate and an organic resin-coated surface-treated aluminum plate obtained by applying an organic resin coating layer to the surface-treated aluminum plate. The present invention relates to a surface-treated aluminum plate and an organic resin-coated surface-treated aluminum plate capable of exhibiting excellent corrosion resistance and work adhesion.
アルミニウム等の金属素材を有機樹脂で被覆した有機樹脂被覆金属板は、製缶材料として古くから知られており、この積層体を絞り加工或いは絞り・しごき加工に付して、飲料等を充填するためのシームレス缶とし、或いはこれをプレス成形してイージイオープンエンド等の缶蓋とすることもよく知られている。 An organic resin-coated metal plate obtained by coating a metal material such as aluminum with an organic resin has long been known as a can-making material, and this laminate is subjected to drawing processing or drawing / ironing processing to fill beverages and the like. It is also well known to make a seamless can for this purpose, or press-mold it to make a can lid such as an easy open end.
このような有機樹脂被覆金属板において、アルミニウム板と有機樹脂被覆層との密着性或いはアルミニウム板の耐食性が不十分であるため、アルミニウム板の表面を無機或いは有機の表面処理剤で処理を行うことが行われている。例えばリン酸クロメート系表面処理材があり、皮膜単独の耐食性に優れ、かつ、各種有機樹脂を塗装した際の密着性にも優れていることから広く使用されている。現在利用されているクロメート処理の多くは、最終製品中に６価クロムが残存しないタイプのものであるが、処理液中に有害物質である６価クロムを含んでいることや、また廃棄後においてクロムの土壌環境中への溶出の可能性が懸念されることなどから、クロムを含有しないノンクロム系の表面処理が望まれている。 In such an organic resin-coated metal plate, since the adhesion between the aluminum plate and the organic resin coating layer or the corrosion resistance of the aluminum plate is insufficient, the surface of the aluminum plate is treated with an inorganic or organic surface treatment agent. Has been done. For example, there is a phosphate chromate-based surface treatment material, which is widely used because it is excellent in corrosion resistance of the coating alone and also in adhesion when various organic resins are coated. Many of the chromate treatments currently used are of the type that does not leave hexavalent chromium in the final product, but the treatment liquid contains hexavalent chromium, which is a hazardous substance, and after disposal. In view of the possibility of elution of chromium into the soil environment, a non-chromium surface treatment not containing chromium is desired.
製缶材料におけるノンクロム系の表面処理も種々提案されており、アルミニウム合金系金属板のノンクロム表面処理として、例えば、ジルコニウム、チタン、またはこれらの化合物と、リン酸塩およびフッ化物を含有し、約ｐＨ１．０〜４．０の酸性処理液を用い、アルミニウム含有金属材料の表面上にジルコニウム及び／又はチタンの酸化物を主成分とする化成皮膜 (特許文献１)や、カーボンを主成分とする有機化合物とリン化合物とジルコニウムあるいはチタン化合物を含む有機−無機複合被膜を形成する方法（特許文献２)、或いは本出願人により、アルミニウム板にも鋼板にも適用でき、容器用としても利用できるノンクロム処理としてＺｒ，Ｏ，Ｆを主成分とし、リン酸イオンを含有しないことを特徴とする表面処理金属材料が提案されている（特許文献３）。 Various non-chromium-based surface treatments for can-making materials have also been proposed. As the non-chromium surface treatment for aluminum alloy metal plates, for example, zirconium, titanium, or a compound thereof, and phosphate and fluoride are contained. An acidic treatment solution having a pH of 1.0 to 4.0 is used, and a chemical conversion film (Patent Document 1) mainly containing an oxide of zirconium and / or titanium on the surface of an aluminum-containing metal material, or carbon as a main component. A method for forming an organic-inorganic composite coating containing an organic compound, a phosphorus compound, and zirconium or a titanium compound (Patent Document 2), or by the applicant, non-chromium that can be applied to both an aluminum plate and a steel plate, and can be used for containers. A surface-treated metal material characterized in that it contains Zr, O, and F as its main components and does not contain phosphate ions is proposed. (Patent Document 3).
しかしながら、上述した化成処理皮膜では、有機樹脂被覆層を形成し、プレコート材料として缶体或いは缶蓋の製造に用いた場合には、十分な耐食性を得ることができなかった。またカーボンを主成分とする有機化合物とリン化合物とジルコニウム或いはチタン化合物を含む有機−無機複合被膜を形成する方法では、ある程度有機樹脂被覆との密着性は向上するが、耐食性が十分でなかった。更にＺｒ，Ｏ，Ｆを主成分とし、リン酸イオンを含有しない表面処理材料は有機樹脂被覆の密着性に優れ、優れた耐食性を発現し得るものであるが、電解処理によるものであるため、化成処理により、有機樹脂被覆の密着性、耐食性に優れていると共に経済性及び生産性にも優れた表面処理金属材料を提供することが望まれている。 However, when the above-mentioned chemical conversion coating is formed with an organic resin coating layer and used as a precoat material in the production of a can body or a can lid, sufficient corrosion resistance cannot be obtained. Further, in the method of forming an organic-inorganic composite coating containing an organic compound containing carbon as a main component, a phosphorus compound, and a zirconium or titanium compound, the adhesion with the organic resin coating is improved to some extent, but the corrosion resistance is not sufficient. Furthermore, the surface treatment material containing Zr, O, F as a main component and not containing phosphate ions is excellent in the adhesion of the organic resin coating and can exhibit excellent corrosion resistance, but is due to electrolytic treatment, It is desired to provide a surface-treated metal material that is excellent in adhesion and corrosion resistance of the organic resin coating and also in economic efficiency and productivity by chemical conversion treatment.
従って本発明の目的は、有機樹脂被覆層との密着性に優れ、製缶材料として優れた耐食性を発現可能な表面処理アルミニウム板を提供することである。
本発明の他の目的は、上記表面処理アルミニウム板に有機樹脂被覆層を施して成る有機樹脂被覆表面処理アルミニウム板及びこれから成る缶体及び缶蓋を提供することである。
本発明の更に他の目的は、上記表面処理アルミニウム板を形成可能な表面処理液を提供することである。
Accordingly, an object of the present invention is to provide a surface-treated aluminum plate that has excellent adhesion to an organic resin coating layer and can exhibit excellent corrosion resistance as a can-making material.
Another object of the present invention is to provide an organic resin-coated surface-treated aluminum plate obtained by applying an organic resin coating layer to the surface-treated aluminum plate, and a can body and a can lid comprising the same.
Still another object of the present invention is to provide a surface treatment liquid capable of forming the surface-treated aluminum plate.
本発明によれば、アルミニウム板を化成処理により表面処理するための表面処理液であって、水分散性のポリエステル樹脂と、フッ素イオン、ジルコニウムイオン又はチタンイオンを、前記ポリエステル樹脂が１００乃至１００００ｐｐｍ、ジルコニウムイオン又はチタンイオンが５乃至５０００ｐｐｍの量で含有することを特徴とする表面処理液が提供される。 According to the present invention, there is provided a surface treatment liquid for subjecting an aluminum plate to a surface treatment by chemical conversion treatment, wherein a water-dispersible polyester resin and fluorine ions, zirconium ions or titanium ions are contained in 100 to 10,000 ppm of the polyester resin, surface treatment solution of zirconium ion or titanium ion is characterized in that it contains in an amount of 5 to 5000ppm is Ru are provided.
本発明によればまた、ｐＨ１．０乃至４．０、温度３５乃至７０℃に調整された上記表面処理液を用いて、２乃至２０秒間の浸漬処理、或いはスプレー処理によりアルミニウム板に化成処理皮膜を形成することを特徴とする表面処理アルミニウム板の製造方法が提供される。
本発明の表面処理アルミニウム板の製造方法においては、前記化成処理皮膜における炭素量Ｃと、ジルコニウム又はチタン量Ｍの比Ｃ／Ｍが、１乃至８０の範囲にあることが好適である。
本発明によれば更に、上記表面処理液を用いて形成された化成処理皮膜を有する表面処理アルミニウム板であって、該化成処理皮膜における炭素量Ｃと、ジルコニウム又はチタン量Ｍの比Ｃ／Ｍが、１乃至８０の範囲にあることを特徴とする表面処理アルミニウム板が提供される。
According to the present invention, a chemical conversion treatment film is formed on an aluminum plate by immersion treatment or spray treatment for 2 to 20 seconds using the surface treatment liquid adjusted to pH 1.0 to 4.0 and temperature 35 to 70 ° C. A method for producing a surface-treated aluminum plate is provided.
In the method for producing a surface-treated aluminum sheet of the present invention, it is preferable that the ratio C / M of the carbon content C and the zirconium or titanium content M in the chemical conversion coating is in the range of 1 to 80 .
According to the present invention, there is further provided a surface-treated aluminum plate having a chemical conversion treatment film formed using the surface treatment liquid, wherein the ratio C / M of the carbon amount C and the zirconium or titanium amount M in the chemical conversion treatment film. Is in the range of 1 to 80, a surface-treated aluminum plate is provided.
本発明の表面処理アルミニウム板は、優れた耐食性及び有機樹脂被覆層の密着性を有し、この表面処理アルミニウム板に有機樹脂を被覆して成る有機樹脂被覆表面処理アルミニウム板は、絞りしごき加工等の過酷な加工に賦された場合にも耐食性及び加工密着性に優れており、従来より製缶材料に使用されていたリン酸クロメート処理と比べても格段に優れた耐食性及び加工密着性を有しており、缶体或いは缶蓋用の製缶材料として好適に用いることができる。
また有機樹脂被覆層としてポリエステルフィルムを用いたプレコート材料とする場合にも、化成処理皮膜とポリエステルフィルムとの間にプライマー等の塗装層を介在させる必要がなく、生産性及び経済性に優れている。
更に本発明の表面処理アルミニウム板の製造に用いられる表面処理液は、水分散性のポリエステル樹脂を用いることにより、化成処理皮膜中に、ジルコニウム化合物又はチタン化合物と共にポリエステル樹脂を存在させることが可能になり、優れた耐食性及び加工密着性を得ることが可能になる。
The surface-treated aluminum plate of the present invention has excellent corrosion resistance and adhesion of the organic resin coating layer, and the organic resin-coated surface-treated aluminum plate formed by coating the surface-treated aluminum plate with an organic resin is drawn and ironed. Even when subjected to severe processing, it has excellent corrosion resistance and work adhesion, and has much better corrosion resistance and work adhesion than the phosphoric acid chromate treatment conventionally used in canning materials. And can be suitably used as a can-making material for a can body or a can lid.
In addition, when a pre-coating material using a polyester film as the organic resin coating layer is used, it is not necessary to interpose a coating layer such as a primer between the chemical conversion film and the polyester film, which is excellent in productivity and economy. .
Furthermore, the surface treatment liquid used for the production of the surface-treated aluminum plate of the present invention can make the polyester resin present together with the zirconium compound or the titanium compound in the chemical conversion film by using a water-dispersible polyester resin. Thus, excellent corrosion resistance and work adhesion can be obtained.
本発明の表面処理アルミニウム板は、アルミニウム板の少なくとも一方の表面に、ポリエステル樹脂、及びジルコニウム化合物又はチタン化合物を含有する化成処理皮膜が形成されて成ることを特徴とするものである。
従来より、ジルコニウム化合物又はチタン化合物を含有する無機化成処理皮膜は知られているが、本発明の表面処理アルミニウム板における化成処理皮膜は、これらの無機物質に加えてポリエステル樹脂が存在することにより、従来の無機化成処理皮膜に比して、優れた耐食性及び加工密着性を有することが分かった。すなわち、本発明の表面処理アルミニウム板における化成処理皮膜は、ポリエステル樹脂が、ジルコニウム化合物またはチタン化合物と共に、アルミニウム板表面を一様に覆うことによって、優れた耐食性及び有機樹脂被覆との密着性を発現する。また、アルミニウム板側に位置するジルコニウム化合物又はチタン化合物によって、ポリエステル樹脂がアルミニウム板に固定され、化成処理皮膜とアルミニウム板間の密着性が確保されることで、加工密着性を向上させることが可能となる。
The surface-treated aluminum plate of the present invention is characterized in that a chemical conversion film containing a polyester resin and a zirconium compound or a titanium compound is formed on at least one surface of the aluminum plate.
Conventionally, an inorganic chemical conversion treatment film containing a zirconium compound or a titanium compound is known, but the chemical conversion treatment film in the surface-treated aluminum plate of the present invention has a polyester resin in addition to these inorganic substances. It has been found that it has excellent corrosion resistance and work adhesion as compared with conventional inorganic chemical conversion coatings. That is, the chemical conversion coating on the surface-treated aluminum plate of the present invention expresses excellent corrosion resistance and adhesion with an organic resin coating when the polyester resin uniformly covers the surface of the aluminum plate together with the zirconium compound or the titanium compound. To do. In addition, the polyester resin is fixed to the aluminum plate by the zirconium compound or titanium compound located on the aluminum plate side, and the adhesion between the chemical conversion film and the aluminum plate is secured, so that the work adhesion can be improved. It becomes.
本発明のこのような優れた効果は、後述する実施例の結果からも明らかである。
すなわち、化成処理皮膜中にポリエステル樹脂が含有されていない場合には、満足する耐食性が得られていない（比較例１）。また、塗布方式により、ジルコニウムまたはチタン化合物を含まず、ポリエステル樹脂のみからなる被膜をアルミニウム板上に形成させた場合には、満足する加工密着性が得られていない（比較例２）。これら比較例に対して、本発明の表面処理アルミニウム板では、耐食性及び加工密着性共に満足する結果が得られている（実施例１〜１１）。
Such excellent effects of the present invention are also apparent from the results of Examples described later.
That is, when the polyester resin is not contained in the chemical conversion film, satisfactory corrosion resistance is not obtained (Comparative Example 1). In addition, when a coating film containing only a polyester resin and not containing zirconium or a titanium compound is formed on an aluminum plate by a coating method, satisfactory work adhesion is not obtained (Comparative Example 2). In contrast to these comparative examples, the surface-treated aluminum plate of the present invention has obtained results that satisfy both corrosion resistance and work adhesion (Examples 1 to 11).
本発明の表面処理アルミニウム板においては、化成処理膜中のポリエステル樹脂に由来する炭素量Ｃ（ｍｇ／ｍ２）と、ジルコニウム化合物又はチタン化合物に由来するジルコニウム又はチタン量Ｍ（ｍｇ／ｍ２）の比で表わされる有機／無機比（Ｃ／Ｍ）が、１乃至８０、特に２乃至７０、特に１０乃至４０の範囲にあることが好適である。
Ｃ／Ｍが上記範囲にある表面処理アルミニウム板は、表面処理に際してジルコニウムイオン又はチタンイオンが適切に析出して、ポリエステル樹脂と共に良好な化成処理皮膜が形成されており、優れた耐食性及び加工密着性を備えた表面処理アルミニウム板を確実に得ることが可能になるが、上記範囲よりもＣ／Ｍの値が小さいと耐食性が劣るようになり、一方上記範囲よりもＣ／Ｍの値が大きいと、生産性に劣る。
また、析出皮膜量としては特に制限されるものではないが、上記炭素量Ｃが５ｍｇ/ｍ２乃至１０００ｍｇ/ｍ２、特に５０ｍｇ/ｍ２乃至５００ｍｇ/ｍ２の範囲にあることが好まく、またジルコニウム又はチタン量Ｍが、１ｍｇ/ｍ２乃至２００ｍｇ/ｍ２、特に２ｍｇ/ｍ２乃至１００ｍｇ/ｍ２の範囲にあることが好ましい。上述した範囲よりも少ない場合には、アルミニウム板の被覆が十分に行われず耐食性が劣るようになり、一方、上述した範囲よりも多い場合は、皮膜量の増加に応じた性能向上の効果が得られないため、生産性に劣る。
尚、化成処理皮膜中の炭素量Ｃ（ｍｇ/ｍ２）及びジルコニウム又はチタン量Ｍ（ｍｇ/ｍ２）は、市販の蛍光Ｘ線分析装置によって膜厚を定量することができる。この場合、予め炭素及びジルコニウム又はチタンについて重量膜厚が既知の複数のサンプルからこれらの重量膜厚とＸ線強度の関係を示す検量線を作成しておき、試料を用いて測定したＸ線強度を、検量線に基づき重量膜厚に換算する。
In the surface-treated aluminum plate of the present invention, the carbon content C (mg / m 2 ) derived from the polyester resin in the chemical conversion film, and the zirconium or titanium content M (mg / m 2 ) derived from the zirconium compound or titanium compound. It is preferable that the organic / inorganic ratio (C / M) represented by the ratio is in the range of 1 to 80, particularly 2 to 70, particularly 10 to 40.
The surface-treated aluminum plate having C / M in the above range has zirconium ions or titanium ions appropriately deposited during the surface treatment, and a good chemical conversion coating film is formed together with the polyester resin. Excellent corrosion resistance and work adhesion However, if the value of C / M is smaller than the above range, the corrosion resistance will be inferior, whereas if the value of C / M is larger than the above range, Inferior to productivity.
Further, although the amount of the deposited film is not particularly limited, the carbon amount C is preferably in the range of 5 mg / m 2 to 1000 mg / m 2 , particularly 50 mg / m 2 to 500 mg / m 2 , Further, it is preferable that the amount M of zirconium or titanium is in the range of 1 mg / m 2 to 200 mg / m 2 , particularly 2 mg / m 2 to 100 mg / m 2 . When the amount is less than the above range, the aluminum plate is not sufficiently coated and the corrosion resistance becomes inferior. On the other hand, when the amount is more than the above range, the effect of improving the performance according to the increase in the coating amount is obtained. It is inferior in productivity.
The carbon amount C (mg / m 2 ) and the zirconium or titanium amount M (mg / m 2 ) in the chemical conversion coating can be quantified with a commercially available fluorescent X-ray analyzer. In this case, a calibration curve indicating the relationship between the weight film thickness and the X-ray intensity is prepared in advance from a plurality of samples with known weight film thicknesses for carbon and zirconium or titanium, and the X-ray intensity measured using the sample. Is converted into a weight film thickness based on a calibration curve.
また本発明の有機樹脂被覆表面処理アルミニウム板においては、上記表面処理アルミニウム板の化成処理皮膜上に有機樹脂被覆を形成してなるものであるが、本発明においては、表面処理アルミニウム板及び有機樹脂被覆の密着性に優れているため、化成処理皮膜に直接、すなわちプライマー等を施すことなく、有機樹脂被覆を形成することができる。
図１は、本発明の有機樹脂被覆表面処理アルミニウム板の一例の断面構造を示す図であり、アルミニウム板２の両面に化成処理皮膜３，３が形成されており、この化成処理皮膜３，３の上に直接有機樹脂被覆４，４が形成されている。
In the organic resin-coated surface-treated aluminum plate of the present invention, an organic resin coating is formed on the chemical conversion film of the surface-treated aluminum plate. In the present invention, the surface-treated aluminum plate and the organic resin are used. Since the coating has excellent adhesion, an organic resin coating can be formed directly on the chemical conversion coating film, that is, without applying a primer or the like.
FIG. 1 is a diagram showing a cross-sectional structure of an example of an organic resin-coated surface-treated aluminum plate of the present invention. Chemical conversion coatings 3 and 3 are formed on both surfaces of an aluminum plate 2. The organic resin coatings 4 and 4 are formed directly on the top.
（表面処理液）
本発明の表面処理アルミニウム板の表面処理に用いる表面処理液としては、水分散性のポリエステル樹脂と、フッ素イオン、ジルコニウムイオン又はチタンイオンを含有することを特徴とする水溶液から成るものである。
本処理液を用いてアルミニウム材の表面を処理した場合、フッ素イオンによりアルミニウムが溶解して、その結果ｐＨが上昇するため、ジルコニウム又はチタン化合物が析出する。このときに、表面処理液中に分散体の形態で存在するポリエステル樹脂も共に析出するものと考えられる。表面処理されたアルミニウム板は、未反応物を除去するため水で洗浄し、乾燥後、表面処理アルミニウム板を得ることができる。このようにして、ポリエステル樹脂を、ジルコニウム化合物又はチタン化合物と共に一様にアルミニウム板表面に存在させることにより、耐食性及び加工密着性に優れた化成処理皮膜を提供することが可能になる。
また本発明の表面処理液においては、ポリエステル樹脂が１００乃至１００００ｐｐｍ、特に５００乃至１００００ｐｐｍ、特に１０００乃至５０００ｐｐｍ、ジルコニウムイオン又はチタンイオンが５乃至５０００ｐｐｍ、特に５０乃至２０００ｐｐｍ、特に５０乃至５００ｐｐｍの量で含有されていることが好適である。
後述する表面処理の条件等と共に、表面処理液中の各成分が上記範囲にあることにより、化成処理皮膜におけるＣ／Ｍの値が上述した範囲となるが、上記範囲よりも各成分が少ない場合には、ポリエステル樹脂及びジルコニウム化合物又はチタン化合物の付着量が十分でなく、満足する耐食性及び密着性を得ることができず、その一方、上記範囲よりも各成分が多いと、処理液の安定性が劣るようになるおそれがあると共に、更なる耐食性等の向上も得られず、経済性も低下する。
(Surface treatment liquid)
The surface treatment liquid used for the surface treatment of the surface-treated aluminum plate of the present invention comprises a water-dispersible polyester resin and an aqueous solution containing fluorine ions, zirconium ions or titanium ions.
When the surface of the aluminum material is treated using this treatment liquid, aluminum is dissolved by fluorine ions, and as a result the pH rises, so that zirconium or a titanium compound is precipitated. At this time, it is considered that the polyester resin present in the form of a dispersion in the surface treatment liquid is also precipitated. The surface-treated aluminum plate can be washed with water to remove unreacted materials, and dried to obtain a surface-treated aluminum plate. Thus, it becomes possible to provide the chemical conversion treatment film excellent in corrosion resistance and work adhesion by making the polyester resin uniformly present on the surface of the aluminum plate together with the zirconium compound or the titanium compound.
In the surface treatment solution of the present invention, the polyester resin is contained in an amount of 100 to 10,000 ppm, particularly 500 to 10,000 ppm, particularly 1000 to 5000 ppm, zirconium ion or titanium ion is contained in an amount of 5 to 5000 ppm, particularly 50 to 2000 ppm, particularly 50 to 500 ppm. It is preferred that
When each component in the surface treatment liquid is in the above range along with the conditions for the surface treatment described later, the C / M value in the chemical conversion coating is within the above range, but each component is less than the above range. In addition, the adhesion amount of the polyester resin and the zirconium compound or the titanium compound is not sufficient, and satisfactory corrosion resistance and adhesion cannot be obtained. On the other hand, if there are more components than the above ranges, the stability of the treatment liquid May become inferior, and further improvement in corrosion resistance or the like cannot be obtained, resulting in a decrease in economic efficiency.
本発明の表面処理液に用いる水分散性ポリエステル樹脂としては、親水基を成分として含むポリエステル樹脂を挙げることができる。これらの成分は、ポリエステル分散体表面に物理的に吸着していても良いし、好ましくはポリステル樹脂骨格中に共重合されていても良い。
親水基としては、水酸基、アミノ基、カルボキシル基、スルホン酸基、又はこれらの誘導体や金属塩、エーテル等であり、これらを分子内に含むことにより水に分散可能な状態で存在する。
親水性基を含むモノマーとしては、具体的にはポリエチレングリコール，ポリプロピレングリコール，グリセリン，ポリグリセリン等の水酸基含有ポリエーテルモノマー、５−スルホイソフタル酸，４−スルホナフタレン−２，７−ジカルボン酸，５（４−スルホフェノキシ）イソフタル酸等のスルホン酸含有モノマーの金属塩等を挙げることができる。
また親水性基を有するビニル系モノマーをポリエステル樹脂にグラフト重合させたものでもよく、親水性基を有するビニル系モノマーとしては、カルボキシル基、水酸基、スルホン酸基、アミド基等を含むもの、親水性基に変化させることができる基としては酸無水物基、グリシジル基、クロル基等を含むものを挙げることができる。
本発明においては、水分散性ポリエステル樹脂としては、親水基としてスルホン酸基を有するものを好適に用いることができる。
Examples of the water-dispersible polyester resin used in the surface treatment liquid of the present invention include a polyester resin containing a hydrophilic group as a component. These components may be physically adsorbed on the surface of the polyester dispersion, and may be preferably copolymerized in the polyester resin skeleton.
The hydrophilic group is a hydroxyl group, an amino group, a carboxyl group, a sulfonic acid group, or a derivative or metal salt thereof, ether, or the like, and exists in a state dispersible in water by including these in the molecule.
Specific examples of the monomer containing a hydrophilic group include a hydroxyl group-containing polyether monomer such as polyethylene glycol, polypropylene glycol, glycerin and polyglycerin, 5-sulfoisophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, 5 Examples thereof include metal salts of sulfonic acid-containing monomers such as (4-sulfophenoxy) isophthalic acid.
Also, a vinyl monomer having a hydrophilic group may be graft-polymerized to a polyester resin. Examples of the vinyl monomer having a hydrophilic group include those containing a carboxyl group, a hydroxyl group, a sulfonic acid group, an amide group, etc. Examples of the group that can be changed into a group include an acid anhydride group, a glycidyl group, a chloro group, and the like.
In the present invention, as the water dispersible polyester resin, those having a sulfonic acid group as a hydrophilic group can be suitably used.
また、前記親水性基を含むモノマーと組み合わせて、水分散性ポリエステル樹脂を形成するその他のモノマー成分としては、一般的なポリエステルに用いられるモノマーであれば特に限定されるものではないが、例えば多価カルボン酸として例えばフタル酸、イソフタル酸、テレフタル酸、ナフタレンジカルボン酸等の芳香族多価カルボン酸、コハク酸、アジピン酸、アゼライン酸、セバシン酸，シクロヘキサンジカルボン酸、ダイマー酸等の脂肪族多価カルボン酸が挙げられる。グリコール成分としては、例えばエチレングリコール、プロピレングリコール、ジエチレングリコール、トリエチレングリコール、ブチレングリコール、ネオペンチルグリコール、１，６ーヘキサンジオールなどが挙げられる。
また、これら水分散性ポリエステル樹脂のガラス転移温度は、−４０℃〜１４０℃が好ましく、２０℃乃至１２０℃がより好ましい。また、水分散性ポリエステル樹脂の数平均分子量は１０００乃至１０万が好ましく、３０００乃至８万がより好ましい。
In addition, the other monomer component that forms the water-dispersible polyester resin in combination with the monomer containing the hydrophilic group is not particularly limited as long as it is a monomer used for general polyester, for example, many Examples of polyvalent carboxylic acids include aromatic polyvalent carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid, aliphatic polyvalent carboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, cyclohexanedicarboxylic acid, and dimer acid. Carboxylic acid is mentioned. Examples of the glycol component include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, butylene glycol, neopentyl glycol, 1,6-hexanediol, and the like.
Further, the glass transition temperature of these water-dispersible polyester resins is preferably -40 ° C to 140 ° C, more preferably 20 ° C to 120 ° C. The number average molecular weight of the water-dispersible polyester resin is preferably 1000 to 100,000, more preferably 3000 to 80,000.
表面処理液に、ジルコニウムイオン又はチタンイオンを供給可能なジルコニウム化合物又はチタン化合物としては、これに限定されないが、ヘキサフルオロジルコニウム酸、ヘキサフルオロジルコニウムカリウム（ＫＺｒＦ６）やヘキサフルオロジルコニウムアンモニウム（（ＮＨ４）２ＺｒＦ６）、炭酸ジルコニウムアンモニウム溶液（（ＮＨ４）２ＺｒＯ（ＣＯ３）２）、オキシ硝酸ジルコニウムＺｒＯ（ＮＯ３）２、オキシ酢酸ジルコニウム（ＺｒＯ（ＣＨ３ＣＯＯ）２）等、或いはヘキサフルオロチタン酸（Ｈ２ＴｉＦ６）、チタンフッ化カリウム（Ｋ２ＴｉＦ６）、チタンフッ化アンモニウム（（ＮＨ４）２ＴｉＦ６）、チタンフッ化ソーダ（Ｎａ２ＴｉＦ６）、シュウ酸チタンカリウム２水和物（Ｋ２ＴｉＯ（Ｃ２Ｏ４）２・２Ｈ２Ｏ）、塩化チタン（III）溶液（ＴｉＣｌ３）、塩化チタン（IV）溶液（ＴｉＣｌ４）等を挙げることができる。
尚、本発明の表面処理液においては、フッ素イオンを含有することにより、アルミニウムが溶解し、ジルコニウム化合物又はチタン化合物を適切に析出させることができる。従って上記のうちフッ素イオンを供給可能な化合物以外を用いる場合は、フッ素化合物としてフッ化ナトリウム（ＮａＦ）、フッ化カリウム（ＫＦ）、フッ化アンモニウム（ＮＨ４Ｆ）等を組み合わせて用いることもできる。
Zirconium compounds or titanium compounds that can supply zirconium ions or titanium ions to the surface treatment liquid are not limited to these, but include hexafluorozirconic acid, hexafluorozirconium potassium (KZrF 6 ), and hexafluorozirconium ammonium ((NH 4 ) 2 ZrF 6 ), ammonium zirconium carbonate solution ((NH 4 ) 2 ZrO (CO 3 ) 2 ), zirconium oxynitrate ZrO (NO 3 ) 2 , zirconium oxyacetate (ZrO (CH 3 COO) 2 ), etc., or hexa Fluorotitanic acid (H 2 TiF 6 ), Titanium potassium fluoride (K 2 TiF 6 ), Titanium ammonium fluoride ((NH 4 ) 2 TiF 6 ), Titanium fluoride (Na 2 TiF 6 ), Titanium potassium oxalate dihydrate object( 2 TiO (C 2 O 4) 2 · 2H 2 O), titanium (III) chloride solution (TiCl 3), titanium (IV) chloride solution (may be mentioned TiCl 4) or the like.
In addition, in the surface treatment liquid of this invention, by containing a fluorine ion, aluminum melt | dissolves and a zirconium compound or a titanium compound can be precipitated appropriately. Therefore, in the case where a compound other than the compound capable of supplying fluorine ions is used, sodium fluoride (NaF), potassium fluoride (KF), ammonium fluoride (NH 4 F) or the like can be used in combination as the fluorine compound. .
本発明の表面処理液においては、ポリエスエステル樹脂を分散させるための界面活性剤や、或いは酸化剤等を配合する必要は特になく、水、或いは水と少量の有機溶媒から成る水性媒体に、水分散型ポリエステル樹脂、ジルコニウム化合物又はチタン化合物を、上述した濃度でポリエステル樹脂、及びジルコニウムイオン又はチタンイオンが存在するように、配合することにより調製することができる。
尚、表面処理液中にフッ素イオンを存在させる場合には、フッ素イオンが５乃至５００ｐｐｍの範囲にあることが望ましい。上記範囲よりもフッ素イオン濃度が低いと、フッ素イオンのエッチング効果を得ることができず、一方上記範囲よりもフッ素イオン濃度が高いと析出効率をかえって阻害するおそれがある。
In the surface treatment liquid of the present invention, it is not particularly necessary to add a surfactant for dispersing the polyester ester resin or an oxidizing agent, and water or an aqueous medium composed of water and a small amount of an organic solvent is used. The dispersion type polyester resin, zirconium compound or titanium compound can be prepared by blending the polyester resin and zirconium ion or titanium ion at the above-mentioned concentrations.
In the case where fluorine ions are present in the surface treatment liquid, the fluorine ions are preferably in the range of 5 to 500 ppm. When the fluorine ion concentration is lower than the above range, the fluorine ion etching effect cannot be obtained. On the other hand, when the fluorine ion concentration is higher than the above range, the deposition efficiency may be hindered.
（表面処理方法）
本発明の表面処理液を用いたアルミニウム板の表面処理方法は、上述した水分散性ポリエステル樹脂及びジルコニウム化合物又はチタン化合物を水性媒体に配合し、ポリエステル樹脂が１００乃至１００００ｐｐｍ、ジルコニウムイオン又はチタンイオンが５乃至５０００ｐｐｍの量となるように調製された表面処理液を用い、浸漬処理或いはスプレー処理、ロールコーターによる処理によって行うことができる。
表面処理液のｐＨは、１．０乃至４．０、特に１．５乃至４．０の範囲にあることが好ましく、必要に応乃至て硝酸又はアンモニアを添加して調整する。上記範囲よりもｐＨが小さいと十分な皮膜を得ることができず、一方上記範囲よりもｐＨが大きいと、皮膜形成速度が遅くなり、生産性に劣る。
また表面処理液の温度は、特に限定されないが、３５乃至７０℃の範囲にあることが、安定して被膜を形成する上で望ましい。
表面処理液への浸漬に先立って、アルミニウム板は、常法により、脱脂、水洗、必要に応じて、エッチング処理、水洗、更に酸洗、水洗の前処理を行う。次いで、上記ｐＨ及び温度範囲に調整された表面処理液に２乃至２０秒間浸漬、或いはスプレー処理した後、水洗し、乾燥することによって、化成処理被膜が形成された表面処理アルミニウム板を得ることができる。
尚、アルミニウム板は、従来製缶材料に用いられていたアルミニウム板を全て使用することができ、アルミニウム合金板の他、純アルミニウム板であってもよく、またその厚みはこれに限定されないが、１００乃至５００μｍの範囲にあるものを好適に使用することができる。
また、表面処理の方法によっては、基板のアルミニウムが溶解することもあり、化成処理皮膜にアルミニウム化合物が含有する場合がある。
(Surface treatment method)
The surface treatment method for an aluminum plate using the surface treatment liquid of the present invention comprises mixing the above-described water-dispersible polyester resin and zirconium compound or titanium compound in an aqueous medium, the polyester resin being 100 to 10,000 ppm, zirconium ion or titanium ion being Using a surface treatment liquid prepared so as to have an amount of 5 to 5000 ppm, it can be carried out by dipping treatment or spray treatment, or treatment by a roll coater.
The pH of the surface treatment solution is preferably in the range of 1.0 to 4.0, particularly 1.5 to 4.0, and is adjusted by adding nitric acid or ammonia as necessary. If the pH is lower than the above range, a sufficient film cannot be obtained. On the other hand, if the pH is higher than the above range, the film formation rate becomes slow and the productivity is poor.
The temperature of the surface treatment liquid is not particularly limited, but is preferably in the range of 35 to 70 ° C. in order to stably form a film.
Prior to the immersion in the surface treatment solution, the aluminum plate is subjected to pretreatments such as degreasing, water washing, and if necessary, etching treatment, water washing, further acid pickling, and water washing in a conventional manner. Subsequently, after being immersed or sprayed in a surface treatment solution adjusted to the above pH and temperature range for 2 to 20 seconds, washed with water and dried to obtain a surface-treated aluminum plate on which a chemical conversion film has been formed. it can.
In addition, the aluminum plate can use all the aluminum plates conventionally used for can-made materials, and may be a pure aluminum plate other than an aluminum alloy plate, and the thickness is not limited to this, Those in the range of 100 to 500 μm can be preferably used.
Further, depending on the surface treatment method, the aluminum of the substrate may be dissolved, and the chemical conversion treatment film may contain an aluminum compound.
(有機樹脂被覆表面処理アルミニウム板)
本発明の有機樹脂被覆表面処理アルミニウム板は、上記表面処理アルミニウム板の化成処理皮膜上に有機樹脂から成る層を被覆して成るものであり、上述した表面処理アルミニウム板を用いることから、有機樹脂被覆層の密着性、特に加工密着性に優れており、このため優れた耐食性、耐デント性を有している。
本発明の有機樹脂被覆表面処理アルミニウム板において、化成処理皮膜上に設ける有機樹脂としては、特に限定はなく、熱可塑性樹脂から成るフィルム、或いは熱硬化性乃至熱可塑性樹脂から成る塗膜を挙げることができる。
(Organic resin coated aluminum plate)
The organic resin-coated surface-treated aluminum plate of the present invention is formed by coating a layer made of an organic resin on the chemical conversion film of the surface-treated aluminum plate. Since the above-mentioned surface-treated aluminum plate is used, the organic resin It is excellent in the adhesion of the coating layer, particularly in the processing adhesion, and therefore has excellent corrosion resistance and dent resistance.
In the organic resin-coated surface-treated aluminum plate of the present invention, the organic resin provided on the chemical conversion coating is not particularly limited, and examples thereof include a film made of a thermoplastic resin or a coating film made of a thermosetting or thermoplastic resin. Can do.
フィルム形成可能な熱可塑性樹脂としては、ポリエチレン、ポリプロピレン、エチレン−プロピレン共重合体、エチレン−酢酸ビニル共重合体、エチレン−アクリルエステル共重合体、アイオノマー等のオレフィン系樹脂フィルム、またはポリエチレンテレフタレート等のポリエステルフィルム、もしくはナイロン６、ナイロン６，６、ナイロン１１、ナイロン１２等のポリアミドフィルム、ポリ塩化ビニルフィルム、ポリ塩化ビニリデンフィルム等を挙げることができ、かかる熱可塑性樹脂フィルムの未延伸または二軸延伸したものであってもよい。
更に塗膜形成可能な塗料としては、フェノールエポキシ、アミノ−エポキシ等の変性エポキシ塗料、塩化ビニル−酢酸ビニル共重合体、塩化ビニル−酢酸ビニル共重合体けん化物、塩化ビニル−酢酸ビニル−無水マレイン酸共重合体、エポキシ変性−、エポキシアミノ変性−、エポキシフェノール変性−ビニル塗料または変性ビニル塗料、アクリル塗料、ポリエステル系塗料、スチレン−ブタジェン系共重合体等の合成ゴム系塗料等を挙げることができ、これらの２種以上の組合わせであってもよい。
Examples of the thermoplastic resin capable of forming a film include polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic ester copolymer, olefin resin film such as ionomer, or polyethylene terephthalate. Polyester film, polyamide film such as nylon 6, nylon 6,6, nylon 11, nylon 12, etc., polyvinyl chloride film, polyvinylidene chloride film, etc. can be mentioned. Unstretched or biaxially stretched of such a thermoplastic resin film It may be what you did.
Further, paints capable of forming a coating include modified epoxy paints such as phenol epoxy and amino-epoxy, vinyl chloride-vinyl acetate copolymer, saponified vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-anhydrous maleic anhydride. Examples include acid copolymers, epoxy-modified, epoxy-amino-modified, epoxy-phenol-modified vinyl paints or modified vinyl paints, acrylic paints, polyester paints, and styrene-butadiene copolymers. It may be a combination of two or more of these.
これらの中でも、製缶材料としてポリエステル樹脂フィルムから成る被覆が最も好適に用いられる。
ポリエステル樹脂としては、ホモポリエチレンテレフタレートも勿論使用可能であるが、フィルムの到達し得る最高結晶化度を下げることが耐衝撃性や加工性の点で望ましく、この目的のためにポリエステル中にエチレンテレフタレート以外の共重合エステル単位を導入するのがよい。エチレンテレフタレート単位を主体とし、他のエステル単位の少量を含む共重合ポリエステル樹脂を用いることが特に好ましい。
一般に共重合ポリエステル中の二塩基酸成分の７０モル％以上、特に７５モル％以上がテレフタル酸成分から成り、ジオール成分の７０モル％以上、特に７５モル％以上がエチレングリコールから成り、二塩基酸成分の１乃至３０モル％、特に５乃至２５モル％がテレフタル酸以外の二塩基酸成分から成ることが好ましい。
テレフタル酸以外の二塩基酸としては、イソフタル酸、フタル酸、ナフタレンジカルボン酸等の芳香族ジカルボン酸：シクロヘキサンジカルボン酸等の脂環族ジカルボン酸：コハク酸、アジピン酸、セバチン酸、ドデカンジオン酸等の脂肪族ジカルボン酸：の１種又は２種以上の組合せが挙げられ、エチレングリコールまたはブチレングリコール以外のジオール成分としては、プロピレングリコール、ジエチレングリコール、１，６−ヘキシレングリコール、シクロヘキサンジメタノール、ビスフェノールＡのエチレンオキサイド付加物等の１種又は２種以上が挙げられる。
Among these, a coating made of a polyester resin film is most preferably used as a can-making material.
Of course, homopolyethylene terephthalate can be used as the polyester resin, but it is desirable in terms of impact resistance and workability to lower the maximum crystallinity that the film can reach. For this purpose, ethylene terephthalate is contained in the polyester. It is preferable to introduce copolymer ester units other than the above. It is particularly preferable to use a copolymerized polyester resin mainly composed of ethylene terephthalate units and containing a small amount of other ester units.
In general, 70 mol% or more, particularly 75 mol% or more of the dibasic acid component in the copolyester is composed of a terephthalic acid component, and 70 mol% or more, particularly 75 mol% or more of the diol component is composed of ethylene glycol. It is preferable that 1 to 30 mol%, particularly 5 to 25 mol% of the components are composed of a dibasic acid component other than terephthalic acid.
Dibasic acids other than terephthalic acid include aromatic dicarboxylic acids such as isophthalic acid, phthalic acid and naphthalenedicarboxylic acid: alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid: succinic acid, adipic acid, sebacic acid, dodecanedioic acid, etc. Or a combination of two or more of the aliphatic dicarboxylic acids: As the diol component other than ethylene glycol or butylene glycol, propylene glycol, diethylene glycol, 1,6-hexylene glycol, cyclohexane dimethanol, bisphenol A 1 type, or 2 or more types, such as an ethylene oxide adduct.
また、このポリエステル樹脂は、成形時の溶融流動特性を改善するために、三官能以上の多塩基酸及び多価アルコールから成る群より選択された少なくとも１種の分岐乃至架橋成分を含有することができる。これらの分岐乃至架橋成分は、３．０モル％以下、好適には０．０５乃至３．０モル％の範囲にあるのがよい。
三官能以上の多塩基酸及び多価アルコールとしては、トリメリット酸、ピロメリット酸、ヘミメリット酸、１，１，２，２−エタンテトラカルボン酸、１，１，２−エタントリカルボン酸、１，３，５−ペンタントリカルボン酸、１，２，３，４−シクロペンタンテトラカルボン酸、ビフェニル−３，４，３’，４’−テトラカルボン酸等の多塩基酸や、ペンタエリスリトール、グリセロール、トリメチロールプロパン、１，２，６−ヘキサントリオール、ソルビトール、１，１，４，４−テトラキス（ヒドロキシメチル）シクロヘキサン等の多価アルコールが挙げられる。
In addition, the polyester resin may contain at least one branching or crosslinking component selected from the group consisting of trifunctional or higher polybasic acids and polyhydric alcohols in order to improve the melt flow characteristics during molding. it can. These branching or crosslinking components should be in the range of 3.0 mol% or less, preferably 0.05 to 3.0 mol%.
Examples of the trifunctional or higher polybasic acid and polyhydric alcohol include trimellitic acid, pyromellitic acid, hemimellitic acid, 1,1,2,2-ethanetetracarboxylic acid, 1,1,2-ethanetricarboxylic acid, 1 , 3,5-pentanetricarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, polybasic acids such as biphenyl-3,4,3 ′, 4′-tetracarboxylic acid, pentaerythritol, glycerol, Examples include polyhydric alcohols such as trimethylolpropane, 1,2,6-hexanetriol, sorbitol, 1,1,4,4-tetrakis (hydroxymethyl) cyclohexane.
ホモポリエステル或いは共重合ポリエステルは、フィルム形成範囲の分子量を有するべきであり、溶媒として、フェノール／テトラクロロエタン混合溶媒を用いて測定した固有粘度〔η〕は０．５乃至１．５、特に０．６乃至１．５の範囲にあるのがよい。
本発明の有機樹脂被覆に用いるポリエステル樹脂層は、単層の樹脂層であってもよく、また同時押出などによる多層の樹脂層であってもよい。多層のポリエステル樹脂層を用いると、下地層、すなわち表面処理アルミニウム板側に接着性に優れた組成のポリエステル樹脂を選択し、表層に耐内容物性、すなわち耐抽出性やフレーバー成分の非吸着性に優れた組成のポリエステル樹脂を選択できるので有利である。
上記ポリエステル樹脂層には、それ自体公知の樹脂用配合剤、例えば非晶質シリカ等のアンチブロッキング剤、無機フィラー、各種帯電防止剤、滑剤、酸化防止剤、紫外線吸収剤等を公知の処方に従って配合することができる。
本発明において、有機樹脂被覆がポリエステル樹脂等の熱可塑性樹脂から成る被覆である場合の厚みは、一般に３乃至５０μｍの範囲にあることが望ましく、有機樹脂被覆が塗膜である場合には、０．５乃至２０ｇ／ｍ２の塗工量であることが望ましい。有機樹脂被覆の厚みが、上記範囲よりも小さいと耐食性が不十分となり、一方上記範囲よりも大きいと加工性の点で問題を生じやすい。
The homopolyester or copolyester should have a molecular weight in the film forming range, and the intrinsic viscosity [η] measured using a phenol / tetrachloroethane mixed solvent as the solvent is 0.5 to 1.5, especially 0. It may be in the range of 6 to 1.5.
The polyester resin layer used for the organic resin coating of the present invention may be a single resin layer or a multilayer resin layer formed by coextrusion or the like. When a multilayer polyester resin layer is used, a polyester resin having a composition with excellent adhesiveness is selected for the base layer, that is, the surface-treated aluminum plate, and the surface layer has content resistance, that is, extraction resistance and non-adsorption of flavor components. This is advantageous because a polyester resin having an excellent composition can be selected.
In the polyester resin layer, known compounding agents for resins, for example, antiblocking agents such as amorphous silica, inorganic fillers, various antistatic agents, lubricants, antioxidants, ultraviolet absorbers, etc., according to known formulations Can be blended.
In the present invention, the thickness when the organic resin coating is a coating made of a thermoplastic resin such as a polyester resin is generally desirably in the range of 3 to 50 μm, and when the organic resin coating is a coating film, the thickness is 0. The coating amount is desirably 5 to 20 g / m 2 . If the thickness of the organic resin coating is smaller than the above range, the corrosion resistance becomes insufficient. On the other hand, if the thickness is larger than the above range, a problem is likely to occur in terms of workability.
（有機樹脂被覆表面処理アルミニウム板の製造）
本発明において、表面処理アルミニウム板への有機樹被覆の形成は任意の手段で行うことができ、例えば、ポリエステル樹脂被覆の場合では、押出コート法、キャストフィルム熱接着法、二軸延伸フィルム熱接着法等により行うことができ、熱硬化性塗料による被覆等の場合には、ロールコート法、スプレー法等、従来公知の方法で塗工できる。
また前述した通り、本発明においては、表面処理アルミニウム板の有機樹脂被覆の密着性に優れていることから、化成処理膜と有機樹脂被覆、特にポリエステル樹脂から成る被覆との間に、接着用プライマー等の塗膜を設ける必要はないが、勿論設けることを除外するものではなく、密着性と耐食性とに優れた従来公知のフェノールエポキシ系塗料等のプライマー塗料を用いることもでき、表面処理アルミニウム板或いはポリエステルフィルムの何れに予め設けてもよい。
(Manufacture of organic resin-coated surface-treated aluminum plate)
In the present invention, formation of the organic resin coating on the surface-treated aluminum plate can be performed by any means. For example, in the case of polyester resin coating, extrusion coating, cast film thermal bonding, biaxially stretched film thermal bonding. In the case of coating with a thermosetting paint, it can be applied by a conventionally known method such as a roll coating method or a spray method.
In addition, as described above, in the present invention, since the adhesion of the organic resin coating of the surface-treated aluminum plate is excellent, the primer for adhesion between the chemical conversion treatment film and the organic resin coating, particularly a coating made of a polyester resin. It is not necessary to provide a coating film such as, but of course, it does not exclude the provision of a primer paint such as a conventionally known phenol epoxy paint excellent in adhesion and corrosion resistance. Or you may provide in any of polyester films beforehand.
（缶体）
本発明の缶体は、前述した有機樹脂被覆表面処理アルミニウム板から形成されている限り、従来公知の任意の製缶法により成形することができ、側面継ぎ目を有するスリーピース缶であることもできるが、一般にシームレス缶（ツーピース缶）であることが好ましい。このシームレス缶は、有機樹脂被覆表面処理アルミニウム板の有機樹脂被覆面が少なくとも缶内面側となるように、絞り・再しぼり加工、絞り・再絞りによる曲げ伸ばし加工（ストレッチ加工）、絞り・再絞りによる曲げ伸ばし・しごき加工或いは絞り・しごき加工等の従来公知の手段に付すことによって製造される。
(Can body)
As long as the can body of the present invention is formed from the aforementioned organic resin-coated surface-treated aluminum plate, it can be formed by any conventionally known can-making method, and can also be a three-piece can having a side seam. In general, a seamless can (two-piece can) is preferable. This seamless can is drawn and re-squeezed, bent and stretched by drawing and redrawing (stretching), and drawn and redrawn so that the organic resin-coated surface of the organic resin-coated surface-treated aluminum plate is at least the inside of the can. It is manufactured by attaching to a conventionally known means such as bending / stretching or ironing by drawing or drawing / ironing.
（缶蓋）
本発明の缶蓋は、前述した有機樹脂被覆表面処理アルミニウム板から形成されている限り、従来公知の任意の製蓋法により成形することができ、一般には、ステイ・オン・タブタイプのイージーオープン缶蓋やフルオープンタイプのイージーオープン缶蓋に適用することができる。
(Can lid)
The can lid of the present invention can be formed by any conventionally known lid-making method as long as it is formed from the above-mentioned organic resin-coated surface-treated aluminum plate, and is generally a stay-on-tab type easy open. It can be applied to a can lid or a full open type easy open can lid.
本発明を次の実施例により更に説明するが、本発明は次の例により何らかの制限を受けるものではない。実施例および比較例で使用した供試板の試験方法について述べる。 The present invention is further illustrated by the following examples, but the invention is not limited in any way by the following examples. The test method of the test plate used in the examples and comparative examples will be described.
（炭素量）
化成処理皮膜中のポリエステル樹脂に由来する炭素原子の量は、蛍光Ｘ線分析装置を用いて測定した。測定に用いた検量線は、濃度が既知の水分散型ポリエステル水溶液を、清浄なアルミニウム合金上に塗装焼き付けして炭素量が既知の標準板を作製し、これらの蛍光Ｘ線強度と測定炭素量との相関から測定した。
(Carbon content)
The amount of carbon atoms derived from the polyester resin in the chemical conversion coating was measured using a fluorescent X-ray analyzer. The calibration curve used for the measurement was to prepare a standard plate with a known carbon content by painting and baking a water-dispersed polyester aqueous solution with a known concentration on a clean aluminum alloy. These fluorescent X-ray intensities and measured carbon content It was measured from the correlation.
（ジルコニウム又はチタン量）
化成処理皮膜中のジルコニウムまたはチタン化合物に由来するジルコニウムまたはチタン量は、蛍光Ｘ線分析装置を用いて測定した。検量線は、皮膜量が既知のジルコニウム析出標準板を用意し、これらの蛍光Ｘ線強度と皮膜量の相関から測定した。
(Zirconium or titanium content)
The amount of zirconium or titanium derived from the zirconium or titanium compound in the chemical conversion film was measured using a fluorescent X-ray analyzer. The calibration curve was measured from the correlation between the fluorescent X-ray intensity and the coating amount by preparing a zirconium deposition standard plate with a known coating amount.
（有機／無機比の算出方法）
化成処理皮膜中の、ポリエステル樹脂に由来する炭素量Ｃと、ジルコニウム化合物又はチタン化合物に由来するジルコニウム量及びチタン量Ｍの比で表わされる有機／無機比の算出については、蛍光Ｘ線分析により得られた皮膜量を、以下の式を用いて計算することで得た。
有機／無機比＝Ｃ／Ｍ （−）
Ｃ：化成処理皮膜中の炭素量（ｍｇ／ｍ２）
Ｍ：化成処理皮膜中のジルコニウム又はチタン量（ｍｇ／ｍ２）
(Calculation method of organic / inorganic ratio)
The calculation of the organic / inorganic ratio represented by the ratio of the carbon content C derived from the polyester resin, the zirconium content derived from the zirconium compound or the titanium compound, and the titanium content M in the chemical conversion coating is obtained by fluorescent X-ray analysis. The obtained coating amount was obtained by calculating using the following formula.
Organic / inorganic ratio = C / M (-)
C: Carbon amount in the chemical conversion coating (mg / m 2 )
M: amount of zirconium or titanium in the chemical conversion coating (mg / m 2 )
（蛍光Ｘ線分析装置の測定条件）
使用機器： 理学電機製 ＺＳＸ１００ｅ
測定条件： 測定対象 Ｚｒ−Ｋα線、Ｃ−Ｋα線
測定径 ２０ｍｍ
Ｘ線出力 ５０ｋＶ-７０ｍＡ
測定時間 ２０秒（Ｚｒ）、１００秒（Ｃ）
(Measurement conditions of X-ray fluorescence analyzer)
Equipment used: ZSX100e manufactured by Rigaku Corporation
Measurement conditions: Measurement object Zr-Kα ray, C-Kα ray
Measurement diameter 20mm
X-ray output 50kV-70mA
Measurement time 20 seconds (Zr), 100 seconds (C)
（耐食試験）
作製した表面処理アルミニウム板の耐食性能は、２１０℃×１８０秒間の熱処理を行った後、塩化物イオンを含有する酸性水溶液に浸漬し、性状の変化を経時で観察することで行った。アルミ供試板の耐食性が不足している場合、露出部の金属基板が溶解し、腐食により金属化合物が発生するので、これらに由来する白錆を確認することで評価した。
試験に用いたモデル水溶液は、食塩を１０００ｐｐｍとし、これにクエン酸を加えてｐＨが３．０となるよう調整したものを用いた。また、試験時の保管温度は３７℃で行った。
耐食性 可 ：経時１週間の時点で、リン酸クロメート処理板より優れるもの
耐食性 不可：経時１週間の時点で、リン酸クロメート処理板に比べ、同等もしくは劣
るもの
(Corrosion resistance test)
The corrosion resistance of the produced surface-treated aluminum plate was measured by immersing it in an acidic aqueous solution containing chloride ions after heat treatment at 210 ° C. for 180 seconds and observing changes in properties over time. When the corrosion resistance of the aluminum test plate was insufficient, the exposed metal substrate was dissolved and a metal compound was generated due to corrosion. Therefore, the evaluation was made by confirming white rust derived therefrom.
The model aqueous solution used for the test was adjusted to a pH of 3.0 by adding sodium chloride to 1000 ppm and adding citric acid thereto. The storage temperature during the test was 37 ° C.
Corrosion resistance Yes: Superior to phosphate chromate treated plate at 1 week
Corrosion resistance not possible: equivalent or inferior to phosphate-chromated plate at 1 week
Things
（加工密着性評価）
作製した缶体の缶側壁部の缶底から高さ４５ｍｍ〜９５ｍｍの部分を幅１５ｍｍで短冊状に切り出し、短冊状の先端から３５ｍｍ位置（缶底からの高さ８０ｍｍの位置に相当）に缶外面側素地に達する傷を入れた。予め入れた傷を起点として折り曲げを繰り返すことにより金属片のみを切断し、樹脂フィルムだけで繋がっている部分を作った後、この部分を内面側になるようにし、ピール試験機を用いて１８０度剥離試験を２３℃下、引張速度５ｍｍ／ｍiｎで行って密着強度を測定した。
評価結果は
加工後密着力 可 ：密着強度が、１．０Ｎ／１５ｍｍ以上
加工後密着力 不可：密着強度が、１．０Ｎ／１５ｍｍ以下
で示した。
(Processing adhesion evaluation)
Cut out the 45mm to 95mm height portion from the bottom of the can side wall of the can body into a strip shape with a width of 15mm, and place it at the 35mm position from the strip tip (equivalent to a position of 80mm height from the bottom) Scratches reaching the outer side substrate were made. By cutting the metal piece only by repeating bending with the scratches made in advance as the starting point, and making a part connected only by the resin film, this part is made to be the inner surface side, and 180 degrees using a peel tester A peel test was performed at 23 ° C. and a tensile speed of 5 mm / min to measure the adhesion strength.
Evaluation result: Adhesion strength after processing Possible: Adhesion strength is 1.0 N / 15 mm or more. Adhesion strength after processing Impossibility: Adhesion strength is 1.0 N / 15 mm or less.
（実施例１）
アルミニウム合金板（３１０４材）を準備し、日本ペイント社製の脱脂剤「サーフクリーナーＥＣ３７１」（商品名）の２％水溶液中（５０℃）に、６秒間浸漬して脱脂処理を行った。脱脂処理後、水洗してから、日本ペイント社製のエッチング剤「サーフクリーナー４２０Ｎ−２」（商品名）の２％水溶液中（５０℃）に、６秒間浸漬してアルカリエッチング処理を行った。エッチング処理後、水洗してから、２％硫酸水溶液中（５０℃）に６秒間浸漬して酸洗浄を行った。
水洗を行った後、水分散ポリエステル樹脂Ａ（東洋紡績社製「バイロナ−ルＭＤ２０００,Ｔｇ＝６７℃」）、及びジルコニウム化合物（アルドリッチ社製「ヘキサフルオロジルコニウム酸」）を、それぞれポリエステル樹脂Ａが５０００ｐｐｍ、ジルコニウムイオンが５０ｐｐｍとなるように、純水中に添加して調製した表面処理液中（５０℃）に、６秒間浸漬して化成処理皮膜を形成させた後、水洗、風乾することで表面処理アルミニウム板を得た。
Example 1
An aluminum alloy plate (3104 material) was prepared, and degreased by being immersed in a 2% aqueous solution (50 ° C.) of a degreasing agent “Surf Cleaner EC371” (trade name) manufactured by Nippon Paint Co., Ltd. for 6 seconds. After degreasing, the substrate was washed with water and then immersed in a 2% aqueous solution (50 ° C.) of an etching agent “Surf Cleaner 420N-2” (trade name) manufactured by Nippon Paint Co., Ltd. for 6 seconds to perform an alkali etching treatment. After the etching treatment, the substrate was washed with water and then immersed in a 2% aqueous sulfuric acid solution (50 ° C.) for 6 seconds for acid cleaning.
After washing with water, water-dispersed polyester resin A (Toyobo Co., Ltd. “Vylonal MD2000, Tg = 67 ° C.”) and zirconium compound (Aldrich “hexafluorozirconic acid”) were respectively added to polyester resin A. After forming a chemical conversion film by dipping in a surface treatment solution (50 ° C) prepared by adding in pure water so that the concentration of 5000 ppm and zirconium ions is 50 ppm, it is washed with water and air-dried. A surface-treated aluminum plate was obtained.
作製した表面処理アルミニウム板を、予め板温度２５０℃に加熱しておき、アルミニウム板の両面に、有機樹脂被覆として、イソフタル酸１５ｍｏｌ％共重合のポリエチレンテレフタレートフィルム（フィルム厚み：１６μｍ）を、ラミネートロールを介して熱圧着した後、直ちに水冷することにより、有機樹脂被覆表面処理アルミニウム板を得た。
得られた有機樹脂被覆表面処理アルミニウム板の両面に、パラフィンワックスを静電塗油した後、直径１５６ｍｍの円形に打ち抜き、浅絞りカップを作成した。次いで、この浅絞りカップを、再絞り−しごき加工及びドーミング成形を行い、続いて開口端縁部のトリミング加工を行うことにより、缶体を得た。缶体の諸特性は以下の通りであった。
缶体径：６６ｍｍ
缶体高さ：１６８ｍｍ
元板厚に対する缶側壁部の平均板厚減少率：６０％
The prepared surface-treated aluminum plate was previously heated to a plate temperature of 250 ° C., and a polyethylene terephthalate film (film thickness: 16 μm) copolymerized with 15 mol% isophthalic acid as an organic resin coating was laminated on both surfaces of the aluminum plate. After the thermocompression bonding via, an organic resin-coated surface-treated aluminum plate was obtained by immediately cooling with water.
Paraffin wax was electrostatically applied to both surfaces of the obtained organic resin-coated surface-treated aluminum plate, and then punched into a circular shape with a diameter of 156 mm to produce a shallow drawn cup. Next, this shallow drawn cup was subjected to redrawing-ironing processing and doming forming, followed by trimming of the opening edge portion to obtain a can body. Various characteristics of the can body were as follows.
Can body diameter: 66 mm
Can height: 168mm
Average thickness reduction rate of can side wall relative to original thickness: 60%
（実施例２）
実施例１において、処理液のジルコニウムイオン量を１００ｐｐｍとする以外は実施例１と同様の方法で、表面処理アルミニウム板、有機樹脂被覆表面処理アルミニウム板、及び缶体を得た。
(Example 2)
In Example 1, a surface-treated aluminum plate, an organic resin-coated surface-treated aluminum plate, and a can were obtained in the same manner as in Example 1 except that the amount of zirconium ions in the treatment liquid was 100 ppm.
（実施例３）
実施例１において、処理液のジルコニウムイオン量を１５０ｐｐｍとする以外は実施例１と同様の方法で、表面処理アルミニウム板、有機樹脂被覆表面処理アルミニウム板、及び缶体を得た。
(Example 3)
In Example 1, a surface-treated aluminum plate, an organic resin-coated surface-treated aluminum plate, and a can were obtained in the same manner as in Example 1 except that the amount of zirconium ions in the treatment liquid was 150 ppm.
（実施例４）
実施例１において、処理液のジルコニウムイオン量を２５０ｐｐｍとする以外は実施例１と同様の方法で、表面処理アルミニウム板、有機樹脂被覆表面処理アルミニウム板、及び缶体を得た。
Example 4
In Example 1, a surface-treated aluminum plate, an organic resin-coated surface-treated aluminum plate, and a can were obtained in the same manner as in Example 1 except that the amount of zirconium ions in the treatment liquid was 250 ppm.
（実施例５）
実施例１において、処理液のジルコニウムイオン量を５００ｐｐｍとする以外は実施例１と同様の方法で、表面処理アルミニウム板、有機樹脂被覆表面処理アルミニウム板、及び缶体を得た。
(Example 5)
In Example 1, a surface-treated aluminum plate, an organic resin-coated surface-treated aluminum plate, and a can were obtained in the same manner as in Example 1 except that the amount of zirconium ions in the treatment liquid was 500 ppm.
（実施例６）
実施例１において、処理液のジルコニウムイオン量を２０００ｐｐｍとする以外は実施例１と同様の方法で、表面処理アルミニウム板、有機樹脂被覆表面処理アルミニウム板、及び缶体を得た。
(Example 6)
In Example 1, a surface-treated aluminum plate, an organic resin-coated surface-treated aluminum plate, and a can were obtained in the same manner as in Example 1 except that the amount of zirconium ions in the treatment liquid was 2000 ppm.
（実施例７）
実施例１おいて、処理液の水分散ポリエステル樹脂Ａを１０００ｐｐｍ、ジルコニウムイオン量を５００ｐｐｍとする以外は実施例１と同様の方法で、表面処理アルミニウム板、有機樹脂被覆表面処理アルミニウム板、及び缶体を得た。
(Example 7)
In Example 1, a surface-treated aluminum plate, an organic resin-coated surface-treated aluminum plate, and a can in the same manner as in Example 1 except that the water-dispersed polyester resin A in the treatment liquid was 1000 ppm and the amount of zirconium ions was 500 ppm. Got the body.
（実施例８）
実施例１において、処理液のジルコニウムイオン量を１００ｐｐｍとし、処理時間を１０秒とする以外は実施例１と同様の方法で、表面処理アルミニウム板、有機樹脂被覆表面処理アルミニウム板、及び缶体を得た。
(Example 8)
In Example 1, the surface-treated aluminum plate, the organic resin-coated surface-treated aluminum plate, and the can were prepared in the same manner as in Example 1 except that the amount of zirconium ions in the treatment liquid was 100 ppm and the treatment time was 10 seconds. Obtained.
（実施例９）
実施例１において、水分散ポリエステル樹脂Ａを水分散ポリエステル樹脂Ｂ（互応化学工業社製「プラスコートＺ−６８７,Ｔｇ＝１１０℃」）に変更し、処理液のポリエステル樹脂Ｂを３０００ｐｐｍ、ジルコニウムイオン量を５００ｐｐｍとする以外は実施例１と同様の方法で、表面処理アルミニウム板、有機樹脂被覆表面処理アルミニウム板、及び缶体を得た。
Example 9
In Example 1, the water-dispersed polyester resin A was changed to the water-dispersed polyester resin B (“Plus Coat Z-687, Tg = 110 ° C.” manufactured by Kyoyo Chemical Industry Co., Ltd.), and the polyester resin B of the treatment liquid was 3000 ppm, zirconium ion A surface-treated aluminum plate, an organic resin-coated surface-treated aluminum plate, and a can were obtained in the same manner as in Example 1 except that the amount was 500 ppm.
（実施例１０）
実施例１において水分散ポリエステル樹脂Ａを水分散ポリエステル樹脂Ｃ（東洋紡社製 「バイロナ−ルＭＤ１４８０,Ｔｇ＝２０℃」）に変更し、処理液のポリエステル樹脂Ｃを５０００ｐｐｍ、ジルコニウムイオン量を５００ｐｐｍとする以外は実施例１と同様の方法で、表面処理アルミニウム板、有機樹脂被覆表面処理アルミニウム板、及び缶体を得た。
(Example 10)
In Example 1, the water-dispersed polyester resin A was changed to the water-dispersed polyester resin C (Toyobo Co., Ltd. “Vironal MD1480, Tg = 20 ° C.”), the polyester resin C in the treatment liquid was 5000 ppm, and the amount of zirconium ions was 500 ppm. A surface-treated aluminum plate, an organic resin-coated surface-treated aluminum plate, and a can were obtained in the same manner as in Example 1 except that.
（実施例１１）
実施例１においてジルコニウム化合物をチタン化合物（アルドリッチ社製「ヘキサフルオロチタン酸」）に変更し、チタンイオン量を５００ｐｐｍとし、処理時間を１０秒とする以外は実施例１と同様の方法で、表面処理アルミニウム板、有機樹脂被覆表面処理アルミニウム板、及び缶体を得た。
(Example 11)
In Example 1, except that the zirconium compound was changed to a titanium compound (“Hexafluorotitanic acid” manufactured by Aldrich), the titanium ion amount was 500 ppm, and the treatment time was 10 seconds, A treated aluminum plate, an organic resin-coated surface-treated aluminum plate, and a can were obtained.
（比較例１）
実施例１において、水分散型ポリエステル樹脂を配合しないこと、及びジルコニウムイオンを５００ｐｐｍとしたこと以外は実施例１と同様の方法で、表面処理アルミニウム板、有機樹脂被覆表面処理アルミニウム板、及び缶体を得た。
(Comparative Example 1)
In Example 1, the surface-treated aluminum plate, the organic resin-coated surface-treated aluminum plate, and the can body were the same as in Example 1 except that the water-dispersed polyester resin was not blended and the zirconium ion was 500 ppm. Got.
（比較例２）
アルミニウム合金板（３１０４材）を実施例１と同様の方法で、脱脂処理、エッチング処理、酸洗浄を行った後、水洗し、乾燥させてから水分散ポリエステル樹脂Ａを乾燥質量として表１に示す値となるようにバーコーターで塗布し、熱風炉で１００℃×６０秒間の条件で焼付け乾燥することでポリエステル樹脂Ａ塗布アルミニウム板を得た。得られたアルミニウム板を用いる以外は実施例１と同様の方法で有機樹脂被覆表面処理アルミニウム板、及び缶体を得た。
(Comparative Example 2)
The aluminum alloy plate (3104 material) is subjected to degreasing treatment, etching treatment and acid washing in the same manner as in Example 1, then washed with water and dried, and then the water-dispersed polyester resin A is shown in Table 1 as the dry mass. It applied with the bar coater so that it might become a value, and the polyester resin A application | coating aluminum plate was obtained by baking and drying on 100 degreeC x 60 second conditions with a hot air oven. An organic resin-coated surface-treated aluminum plate and a can were obtained in the same manner as in Example 1 except that the obtained aluminum plate was used.
（比較例３）
市販のリン酸クロメート処理板を用いる他は実施例１と同様の方法で、有機樹脂被覆表面処理アルミニウム板、及び缶体を得た。
実施例及び比較例の試験評価結果を、表１に示した。
(Comparative Example 3)
An organic resin-coated surface-treated aluminum plate and a can were obtained in the same manner as in Example 1 except that a commercially available phosphoric acid chromate-treated plate was used.
The test evaluation results of Examples and Comparative Examples are shown in Table 1.
表１から、本発明の表面処理アルミニウム板の耐食性は、実施例１及び１１に示す領域において、缶材として使用されているリン酸クロメート処理板に比べて、耐食性及び加工密着性が優れていることが分かる。
以上の理由から、厳しい加工及び金属基板保護が要求される缶体および缶蓋として、実用上極めて有用であると言える。
From Table 1, the corrosion resistance of the surface-treated aluminum plate of the present invention is superior to the phosphate chromate-treated plate used as a can material in the regions shown in Examples 1 and 11 in terms of corrosion resistance and work adhesion. I understand that.
For the above reasons, it can be said that it is extremely useful practically as a can body and a can lid that require strict processing and metal substrate protection.
本発明の表面処理アルミニウム板は、優れた耐食性及び有機樹脂被覆の密着性を有し、この表面処理アルミニウム板に有機樹脂を被覆して成る有機樹脂被覆表面処理アルミニウム板は、過酷な加工に賦された場合にも加工密着性に優れており、絞りしごき缶等の過酷な加工により成形される缶体、或いはリベット加工やスコア加工等が施されるイージーオープン蓋等の缶蓋に有効に利用できる。
また耐食性にも優れていることから、腐食性の強い内容物の缶体或いは缶蓋用の製缶材料として好適に用いることができる。
The surface-treated aluminum plate of the present invention has excellent corrosion resistance and adhesion of an organic resin coating. The organic resin-coated surface-treated aluminum plate obtained by coating the surface-treated aluminum plate with an organic resin is suitable for severe processing. Even when it is applied, it has excellent processing adhesion and can be used effectively for cans formed by severe processing such as squeezing and ironing cans, or can lids such as easy open lids that are subjected to rivet processing and score processing, etc. it can.
Moreover, since it is excellent also in corrosion resistance, it can be used suitably as a can-making material for can bodies or can lids of strongly corrosive contents.
１：有機樹脂被覆表面処理アルミニウム板、２：アルミニウム合金材料、３：化成処理皮膜、４：有機樹脂被覆材料 1: Organic resin-coated surface-treated aluminum plate, 2: Aluminum alloy material, 3: Chemical conversion coating, 4: Organic resin coating material
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013064172A JP6186792B2 (en) | 2012-03-30 | 2013-03-26 | Surface-treated aluminum plate, organic resin-coated surface-treated aluminum plate, and can body and can lid using the same |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012082181 | 2012-03-30 | ||
| JP2012082181 | 2012-03-30 | ||
| JP2013064172A JP6186792B2 (en) | 2012-03-30 | 2013-03-26 | Surface-treated aluminum plate, organic resin-coated surface-treated aluminum plate, and can body and can lid using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2013227666A JP2013227666A (en) | 2013-11-07 |
| JP6186792B2 true JP6186792B2 (en) | 2017-08-30 |
Family
ID=49675571
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2013064172A Active JP6186792B2 (en) | 2012-03-30 | 2013-03-26 | Surface-treated aluminum plate, organic resin-coated surface-treated aluminum plate, and can body and can lid using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6186792B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016104579A1 (en) * | 2014-12-26 | 2016-06-30 | 新日鐵住金株式会社 | Film-laminated metal sheet for food container, twist cap in which said sheet is used, and can lid |
| AT518457B1 (en) * | 2016-04-04 | 2018-03-15 | Constantia Teich Gmbh | Packaging laminate with a carrier layer and a polyolefin layer |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4099307B2 (en) * | 2000-04-20 | 2008-06-11 | 日本ペイント株式会社 | Non-chromium anti-rust treatment agent for aluminum, anti-rust treatment method and anti-rust treated aluminum products |
| JP3844643B2 (en) * | 2000-08-21 | 2006-11-15 | 日本パーカライジング株式会社 | Ground treatment agent and ground treatment method |
| JP2005120469A (en) * | 2003-09-26 | 2005-05-12 | Nippon Parkerizing Co Ltd | Composition for surface treatment of metal material and surface treatment method |
| JP4487651B2 (en) * | 2004-06-22 | 2010-06-23 | 東洋製罐株式会社 | Surface-treated metal material and surface treatment method thereof, resin-coated metal material, metal can, metal lid |
| JP4575047B2 (en) * | 2004-06-29 | 2010-11-04 | 関西ペイント株式会社 | Metal surface treatment composition and metal surface treatment steel plate |
| US7947333B2 (en) * | 2006-03-31 | 2011-05-24 | Chemetall Gmbh | Method for coating of metallic coil or sheets for producing hollow articles |
| JP2008069413A (en) * | 2006-09-14 | 2008-03-27 | Nippon Steel & Sumikin Stainless Steel Corp | Lubricant steel sheet |
| JP5077651B2 (en) * | 2007-05-31 | 2012-11-21 | 東洋製罐株式会社 | Resin-coated metal plate and molded body using the same |
| JP5192733B2 (en) * | 2007-05-31 | 2013-05-08 | 日本ペイント株式会社 | Can processing for cans |
| JP2009079252A (en) * | 2007-09-26 | 2009-04-16 | Furukawa Sky Kk | Non-chromium type aluminum alloy plate chemical-converted material, and its coated material |
| JP5380033B2 (en) * | 2008-10-09 | 2014-01-08 | Ｊｆｅ建材株式会社 | Painted metal material with excellent corrosion resistance and paint adhesion |
| JP2010275610A (en) * | 2009-05-29 | 2010-12-09 | Furukawa-Sky Aluminum Corp | Surface treated aluminum material |
-
2013
- 2013-03-26 JP JP2013064172A patent/JP6186792B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2013227666A (en) | 2013-11-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2013147146A1 (en) | Surface-treated aluminum sheet, organic-resin-coated surface -treated aluminum sheet, and can body and can lid produced using same | |
| JP6812968B2 (en) | Surface-treated metal plate and organic resin-coated surface-treated metal plate | |
| KR101444566B1 (en) | Surface treatment agent for laminated metal material and method for producing laminated metal material | |
| JP5718752B2 (en) | Metal surface treatment agent and metal material treated with the treatment agent | |
| WO2005123991A1 (en) | Surface-treated metal material and surface treatment method therefor, resin-coated metal material, can and lid of can | |
| JP2008296440A (en) | Resin-coated metal plate and molding using the same | |
| WO2011118846A1 (en) | Surface treated steel plate, manufacturing method therefor, and resin-coated steel plate using same | |
| US10557205B2 (en) | Organic resin-covered surface-treated metal sheet | |
| JP6186792B2 (en) | Surface-treated aluminum plate, organic resin-coated surface-treated aluminum plate, and can body and can lid using the same | |
| JP6428857B2 (en) | Surface treatment liquid, method for producing surface treated aluminum plate using the surface treatment liquid, and surface treated aluminum plate | |
| JP6701874B2 (en) | Organic resin coated surface-treated metal plate | |
| AU634652B2 (en) | Process of aftertreating conversion layers | |
| JP6160162B2 (en) | Surface-treated aluminum plate, organic resin-coated surface-treated aluminum plate, and can body and can lid using the same | |
| JP5377817B2 (en) | Can body applicable to cap with excellent corrosion resistance | |
| JP4915068B2 (en) | Aluminum alloy can lid with excellent corrosion resistance and adhesion and method for producing the same | |
| JP6428856B2 (en) | Surface treatment liquid, method for producing surface treated aluminum plate using the surface treatment liquid, and surface treated aluminum plate | |
| JP5311266B2 (en) | Resin-coated seamless aluminum can with excellent corrosion resistance and adhesion | |
| JP2003138382A (en) | Metal surface treatment chemical for adhesive base and treatment method | |
| JP4569247B2 (en) | Press-molded cans and lids with excellent resistance to sulfur discoloration and corrosion | |
| JP4352227B2 (en) | Resin-coated aluminum alloy can body excellent in corrosion resistance and adhesion and method for forming the same | |
| JP6672948B2 (en) | Organic resin-coated seamless cans |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20160216 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20161209 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20161220 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20170220 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20170704 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20170717 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6186792 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |