KR20170086672A - Method for treating surface of aluminum can - Google Patents
Method for treating surface of aluminum can Download PDFInfo
- Publication number
- KR20170086672A KR20170086672A KR1020177019518A KR20177019518A KR20170086672A KR 20170086672 A KR20170086672 A KR 20170086672A KR 1020177019518 A KR1020177019518 A KR 1020177019518A KR 20177019518 A KR20177019518 A KR 20177019518A KR 20170086672 A KR20170086672 A KR 20170086672A
- Authority
- KR
- South Korea
- Prior art keywords
- aluminum
- acid
- treatment
- alkali
- alkali treatment
- Prior art date
Links
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 150
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 150
- 238000000034 method Methods 0.000 title claims abstract description 50
- 239000003513 alkali Substances 0.000 claims abstract description 120
- 238000010306 acid treatment Methods 0.000 claims abstract description 115
- 239000007788 liquid Substances 0.000 claims abstract description 54
- 238000005530 etching Methods 0.000 claims abstract description 47
- 238000004381 surface treatment Methods 0.000 claims abstract description 13
- 229910001414 potassium ion Inorganic materials 0.000 claims abstract description 6
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 6
- 239000004094 surface-active agent Substances 0.000 claims description 23
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- -1 ammonium ions Chemical class 0.000 claims description 15
- 239000002738 chelating agent Substances 0.000 claims description 14
- 150000007524 organic acids Chemical class 0.000 claims description 12
- 239000002270 dispersing agent Substances 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract description 2
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 abstract description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 57
- 239000000126 substance Substances 0.000 description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 239000011248 coating agent Substances 0.000 description 17
- 238000000576 coating method Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 10
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 10
- 239000002253 acid Substances 0.000 description 10
- 229910001447 ferric ion Inorganic materials 0.000 description 10
- 229910021645 metal ion Inorganic materials 0.000 description 10
- 150000007522 mineralic acids Chemical class 0.000 description 8
- 239000002585 base Substances 0.000 description 7
- 239000002736 nonionic surfactant Substances 0.000 description 7
- 235000011121 sodium hydroxide Nutrition 0.000 description 7
- 239000007921 spray Substances 0.000 description 7
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 238000011109 contamination Methods 0.000 description 6
- 238000005238 degreasing Methods 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 239000000314 lubricant Substances 0.000 description 6
- 235000015165 citric acid Nutrition 0.000 description 4
- 238000007739 conversion coating Methods 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 239000010687 lubricating oil Substances 0.000 description 4
- 238000005554 pickling Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 239000012670 alkaline solution Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 239000000174 gluconic acid Substances 0.000 description 3
- 235000012208 gluconic acid Nutrition 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 2
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical class CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 2
- 239000002280 amphoteric surfactant Substances 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000012459 cleaning agent Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000001630 malic acid Substances 0.000 description 2
- 235000011090 malic acid Nutrition 0.000 description 2
- ALTWGIIQPLQAAM-UHFFFAOYSA-N metavanadate Chemical compound [O-][V](=O)=O ALTWGIIQPLQAAM-UHFFFAOYSA-N 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 159000000001 potassium salts Chemical class 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 235000019832 sodium triphosphate Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- 239000011975 tartaric acid Substances 0.000 description 2
- 230000002087 whitening effect Effects 0.000 description 2
- 229910019617 (NH4)4Ce(SO4)4 Inorganic materials 0.000 description 1
- JSYPRLVDJYQMAI-ODZAUARKSA-N (z)-but-2-enedioic acid;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)\C=C/C(O)=O JSYPRLVDJYQMAI-ODZAUARKSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- IENXJNLJEDMNTE-UHFFFAOYSA-N acetic acid;ethane-1,2-diamine Chemical compound CC(O)=O.NCCN IENXJNLJEDMNTE-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 150000001785 cerium compounds Chemical class 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010409 ironing Methods 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 235000010199 sorbic acid Nutrition 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- 229940075582 sorbic acid Drugs 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 235000011044 succinic acid Nutrition 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- 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
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/20—Acidic compositions for etching aluminium or alloys thereof
-
- 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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
- C23G1/22—Light metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D1/00—Containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material, by deep-drawing operations performed on sheet material
- B65D1/12—Cans, casks, barrels, or drums
-
- C11D11/0029—
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/26—Organic compounds containing oxygen
-
- 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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
-
- 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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/12—Light metals
- C23G1/125—Light metals aluminium
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/14—Hard surfaces
- C11D2111/16—Metals
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Ceramic Engineering (AREA)
- Chemical Treatment Of Metals (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
- ing And Chemical Polishing (AREA)
Abstract
취급이 용이한 산처리액을 이용할 수 있을 뿐만 아니라, 에너지 코스트가 충분히 저감된 알루미늄캔의 표면 처리 방법을 제공한다.
알루미늄캔을 알칼리 처리액으로 처리하는 알칼리 처리 공정과, 상기 알칼리 처리 공정 후의 알루미늄캔을 산처리액으로 처리하는 산처리 공정, 을 포함하며, 상기 알칼리 처리 공정에서의 에칭량은, 50mg/m2 미만인 알루미늄캔의 표면 처리 방법으로서, 상기 알칼리 처리액은 나트륨 이온, 칼륨 이온 및 암모늄 이온으로 이루어진 군에서 선택되는 적어도 1종을 함유하는 것이 바람직하다.Provided is a method for surface treatment of an aluminum can which not only makes it possible to use an acid treatment liquid which is easy to handle but also has a sufficiently reduced energy cost.
An alkali treatment step of treating the aluminum can with an alkali treatment solution; and an acid treatment step of treating the aluminum can after the alkali treatment step with an acid treatment solution, wherein the etching amount in the alkali treatment step is 50 mg / m 2 , The alkali treatment liquid preferably contains at least one kind selected from the group consisting of sodium ion, potassium ion and ammonium ion.
Description
본 발명은, 알루미늄캔의 표면 처리 방법에 관한 것이다.The present invention relates to a method of treating a surface of an aluminum can.
종래, 알루미늄 또는 알루미늄 합금으로 제조되는 음료캔등의 알루미늄캔은, 드로잉 앤드 아이어닝 가공(이하, DI가공이라고 한다)이라 불리는 드로잉 가공등에 의해 제조된다. DI가공에 의해 제조된 알루미늄캔의 표면에는, 드로잉시에 깎이면서 발생된 알루미늄 분말(이하, 스머트라고 한다)이나 윤활유가 부착되어 있다.Conventionally, an aluminum can such as a beverage can made of aluminum or an aluminum alloy is manufactured by a drawing process called a drawing and ironing process (hereinafter referred to as DI process). Aluminum powder (hereinafter referred to as "smut") and lubricating oil generated while being cut at the time of drawing are adhered to the surface of the aluminum can produced by DI processing.
통상, 알루미늄캔에는 화성처리 및 도장 처리가 이루어진다. 견고한 화성처리 피막 및 도장 도막을 형성하기 위해서는, 화성처리전의 알루미늄캔의 표면에 부착된 스머트나 윤활유를 충분히 제거한 다음, 알루미늄캔의 표면에 형성되어 있는 산화 피막을 에칭에 의해 제거할 필요가 있다.Normally, the aluminum can is subjected to chemical conversion treatment and coating treatment. It is necessary to sufficiently remove the smudge or lubricant adhering to the surface of the aluminum can before the chemical conversion treatment and then remove the oxide film formed on the surface of the aluminum can by etching to form a solid chemical conversion coating film and a coating film.
알루미늄캔을 표면 처리할 때에는 알루미늄캔의 표면을 적당하게 에칭할 수 있는 산성의 표면 처리액(이하, 산처리액이라고 할 수 있다)을 이용하는 것이 일반적이다. 예를 들면, 3가의 철이온을 함유하고, 황산 또는 질산에 의해 pH를 2 이하로 조정한 산처리액에 의해 알루미늄캔의 표면을 처리하는 방법이 알려져 있다(예를 들면, 특허문헌 1 및 2 참조). 또한 유기 술폰산, 3가의 철이온, 및 황산이나 질산등의 무기산을 함유하는 산처리액에 의해 알루미늄캔의 표면을 처리하는 방법도 알려져 있다(예를 들면, 특허문헌 3 참조).When the aluminum can is surface-treated, it is common to use an acidic surface-treatment liquid (hereinafter, referred to as an acid-treated liquid) capable of appropriately etching the surface of the aluminum can. For example, there is known a method of treating an aluminum can surface with an acid treatment solution containing a trivalent iron ion and adjusting the pH to 2 or less with sulfuric acid or nitric acid (see, for example, Patent Documents 1 and 2 Reference). There is also known a method of treating the surface of an aluminum can with an acid treatment liquid containing an organic sulfonic acid, a trivalent iron ion, and an inorganic acid such as sulfuric acid or nitric acid (see, for example, Patent Document 3).
알루미늄캔이 아닌, 캔 뚜껑용 알루미늄의 기재처리에 관해서는, 5000계 합금으로 형성된 캔 뚜껑용 알루미늄의 표면을 알칼리성 용액에 의해 처리함으로써, 에칭을 수반하는 탈지를 실시한 후에, 산세정하는 방법이 알려져 있다(예를 들면, 특허문헌 4~6 참조).With respect to the base treatment of aluminum for a can lid other than an aluminum can, there is known a method in which a surface of aluminum for a can lid formed of a 5000-based alloy is treated with an alkaline solution to perform degreasing accompanied by etching, followed by pickling (See, for example, Patent Documents 4 to 6).
그런데, 알루미늄캔의 표면에 마그네슘이나 구리등의 불순물이 잔류하는 경우, 알루미늄캔의 표면에 화성 피막이나 도장 도막을 균일하게 형성할 수 없게 되고, 나아가서는 알루미늄캔의 내식성이 저하된다.However, when impurities such as magnesium or copper remain on the surface of the aluminum can, a chemical conversion coating and a coating film can not be uniformly formed on the surface of the aluminum can, and the corrosion resistance of the aluminum can is deteriorated.
이러한 사태를 회피하기 위해서는, 산처리액에 의한 에칭 속도를 올려 에칭량을 늘리는 것이 유효하다. 에칭량을 늘리기 위해서는, 산처리액에 의한 처리 온도를 고온(예를 들면, 70℃)으로 하는 것을 생각할 수 있다. 그러나, 산처리액에 의한 처리 온도를 고온으로 유지한 경우, 에너지 코스트가 올라가므로 바람직하지 않다.In order to avoid such a situation, it is effective to increase the etching rate by increasing the etching rate by the acid treatment liquid. In order to increase the etching amount, it is conceivable to set the treatment temperature by the acid treatment liquid to a high temperature (for example, 70 DEG C). However, when the treatment temperature by the acid treatment liquid is maintained at a high temperature, the energy cost is increased, which is not preferable.
특허문헌 3에서는, 유기 술폰산을 함유시킨 산처리액에 의해 알루미늄캔의 표면을 처리함으로써, 산처리액에 의한 처리 온도를 저하시킬 수 있다는 것이 개시되어 있다. 그러나, 유기 술폰산을 함유하는 산처리액을 이용한 경우라 하더라도, 낮은 온도에서는 충분히 에칭이 진행되지 않을 수 있다.Patent Document 3 discloses that the treatment temperature of the acid treatment liquid can be lowered by treating the surface of the aluminum can with the acid treatment solution containing the organic sulfonic acid. However, even when an acid treatment solution containing an organic sulfonic acid is used, the etching may not sufficiently proceed at a low temperature.
또한 특허문헌 4~6에서 개시하고 있는 캔 뚜껑용 알루미늄의 기재처리에 있어서 산세정이 비교적 저온(예를 들면, 50℃)에서 이루어지고 있다. 캔 뚜껑용 알루미늄의 기재처리에 있어서는, 산세정 전에 이루어지는 알칼리성 용액에 의한 처리에 의해 기재의 표면을 에칭하고 있다. 이러한 경우의 산세정은, 알루미늄 표면에 편석(偏析)하는 마그네슘의 제거나, 산세정 전의 알칼리성 용액에 의한 처리에 의해 알칼리성이 된 알루미늄의 표면을 중화시키는 것을 목적으로 하는 것이라고 인정된다. 이와 같이, 캔 뚜껑용의 알루미늄 기재처리에 있어서의 산세정과, 알루미늄캔의 표면 처리에서 이루어지는 산처리액에 의해 기재 표면을 에칭하는 처리는, 목적이 전혀 다르다. 만일 알루미늄캔을 캔 뚜껑용 알루미늄의 기재처리 조건으로 처리한 경우, 알루미늄캔 표면의 에칭량의 컨트롤이 되지않아, 알루미늄캔의 외관 마무리를 제어할 수 없을 우려가 있다. 따라서, 캔 뚜껑용 알루미늄의 기재처리에 관한 기술을 알루미늄캔의 표면 처리에 관한 기술에 적용할 수는 없다.In the base treatment of aluminum for a can lid disclosed in Patent Documents 4 to 6, acid pickling is performed at a relatively low temperature (for example, 50 占 폚). In the base treatment of aluminum for a can lid, the surface of the substrate is etched by treatment with an alkaline solution before acid cleaning. The acid pickling in this case is considered to be aimed at neutralizing the surface of the aluminum which has become alkaline by removing magnesium segregating on the aluminum surface or by treating with an alkaline solution before acid pickling. As described above, the process of etching the substrate surface with the acid treatment liquid in the aluminum base treatment for the can lid and the surface treatment of the aluminum can has completely different purposes. If the aluminum can is treated with the base treatment conditions of the aluminum for the can lid, the amount of etching of the aluminum can surface can not be controlled and the appearance finish of the aluminum can can not be controlled. Therefore, the technique relating to the base treatment of aluminum for a can lid can not be applied to the technique relating to the surface treatment of aluminum can.
이와 같이, 취급이 용이한 산처리액을 이용할 수 있을 뿐만 아니라, 충분히 에너지 코스트가 낮은 알루미늄캔의 표면 처리 방법에 대해서는 발견해내지 못한 것이 현상이다.In this way, it is a phenomenon that not only an acid treatment liquid which can be handled easily but also a surface treatment method of an aluminum can having a sufficiently low energy cost can not be found.
본 발명은 상기 과제를 감안하여 이루어진 것으로, 그 목적은, 취급이 용이한 산처리액을 이용할 수 있을 뿐만 아니라, 충분히 에너지 코스트가 낮은 알루미늄캔의 표면 처리 방법을 제공하는 것이다.The present invention has been made in view of the above problems, and an object of the present invention is to provide a method of treating an aluminum can with a low energy cost as well as an acid treatment solution which is easy to handle.
본 발명은, 알루미늄캔을 알칼리 처리액으로 처리하는 알칼리 처리 공정 및 상기 알칼리 처리 공정 후의 알루미늄캔을 산처리액으로 처리하는 산처리 공정을 포함하고, 상기 알칼리 처리 공정에서의 에칭량은, 50mg/m2 미만인 알루미늄캔의 표면 처리 방법에 관한 것이다.The present invention includes an alkali treatment step of treating an aluminum can with an alkali treatment solution and an acid treatment step of treating the aluminum can after the alkali treatment step with an acid treatment solution, wherein the etching amount in the alkali treatment step is 50 mg / m < 2 & gt ;.
상기 알칼리 처리액은 나트륨 이온, 칼륨 이온 및 암모늄 이온으로 이루어진 군에서 선택되는 적어도 1종을 함유하는 것이 바람직하다.It is preferable that the alkali treatment liquid contains at least one kind selected from the group consisting of sodium ions, potassium ions and ammonium ions.
상기 알칼리 처리액은, 40℃~70℃이고, 상기 알칼리 처리 공정에서의 알루미늄캔의 처리 시간은, 1~30초간인 것이 바람직하다.It is preferable that the alkali treatment liquid is 40 占 폚 to 70 占 폚 and the treatment time of the aluminum can in the alkali treatment step is 1 to 30 seconds.
상기 알칼리 처리액은, 유기산, 킬레이트제, 분산제 및 계면활성제로 이루어진 군에서 선택되는 적어도 1종을 함유하는 것이 바람직하다.The alkali treatment liquid preferably contains at least one selected from the group consisting of an organic acid, a chelating agent, a dispersing agent and a surfactant.
상기 산처리액은, 황산, 질산 및 인산으로 이루어진 군에서 선택되는 적어도 1종을 함유하고, 3가의 철이온을 0.05~4g/L 함유하고, pH가 2 이하이며, 상기 산처리 공정에서의 알루미늄캔의 처리 온도는, 30℃~65℃인 것이 바람직하다.Wherein the acid treatment liquid contains at least one member selected from the group consisting of sulfuric acid, nitric acid and phosphoric acid, contains 0.05 to 4 g / L of a trivalent iron ion, has a pH of 2 or less, It is preferable that the processing temperature of the can is 30 占 폚 to 65 占 폚.
상기 산처리 공정에서의 알루미늄캔의 처리 시간은, 10~90초간인 것이 바람직하다.The treatment time of the aluminum can in the acid treatment step is preferably 10 to 90 seconds.
본 발명은, 상기 알루미늄캔의 표면 처리 방법에 의해 표면 처리된 알루미늄캔에 관한 것이다.The present invention relates to an aluminum can surface-treated by the surface treatment method of the aluminum can.
본 발명에 따르면, 취급이 용이한 산처리액을 이용할 수 있을 뿐만 아니라, 충분히 에너지 코스트가 낮은 알루미늄캔의 표면 처리 방법을 제공할 수 있다.According to the present invention, it is possible to provide a method of treating an aluminum can with a low energy cost as well as an acid treatment solution which is easy to handle.
이하, 본 발명의 실시형태에 대하여 설명한다. 그러나 본 발명은 이하의 실시형태로 한정되는 것은 아니다.Hereinafter, an embodiment of the present invention will be described. However, the present invention is not limited to the following embodiments.
본 실시형태에 따른 알루미늄캔의 표면 처리 방법(이하, 간단히 표면 처리 방법이라고도 한다)은, 알칼리 처리 공정과 산처리 공정을 가진다. 본 실시형태에 따른 표면 처리 방법에 의해 처리되는 알루미늄캔으로는, 3000계 합금등으로 형성된 알루미늄캔등을 들 수 있다.The aluminum can surface treatment method (hereinafter, simply referred to as a surface treatment method) according to the present embodiment has an alkali treatment step and an acid treatment step. Examples of the aluminum can treated by the surface treatment method according to the present embodiment include an aluminum can made of a 3000-series alloy or the like.
<알칼리 처리 공정> ≪ Alkali processing step &
알칼리 처리 공정에서는, 알루미늄캔을 알칼리 처리액으로 처리한다.In the alkali treatment step, the aluminum can is treated with an alkali treatment solution.
알칼리 처리액은, 알루미늄캔 표면의 유지(油脂) 성분을 제거한다. 또한, DI가공 후의 알루미늄캔을 처리하는 경우라면, 알칼리 처리액은 윤활제를 제거하는 역할도 담당한다.The alkali treatment liquid removes the oil (fat) component on the aluminum can surface. Further, in the case of processing the aluminum can after the DI processing, the alkali processing liquid also serves to remove the lubricant.
알칼리 처리 공정에서의 알루미늄캔 표면의 에칭량은, 50mg/m2 미만이다. 즉, 알칼리 처리 공정에서 알루미늄캔 표면은, 거의 에칭 되지 않는다. 알칼리 처리 공정에서의 에칭량이, 50mg/m2 이상이면 에칭의 컨트롤이 어려워져 알루미늄캔 표면이 백색화되어 버린다. 알칼리 처리 공정에서의 알루미늄캔 표면의 에칭량은, 알칼리 처리 공정의 전후에 알루미늄캔의 질량을 정밀하게 천칭에 의해 측정하고, 알칼리 처리 공정 전후에서의 알루미늄캔의 질량의 감소량을 알루미늄캔의 표면적으로 나눔으로써 구할 수 있다.The etching amount of the aluminum can surface in the alkali treatment step is less than 50 mg / m 2 . That is, in the alkali treatment step, the aluminum can surface is hardly etched. If the etching amount in the alkali treatment step is 50 mg / m 2 or more, it becomes difficult to control the etching and the aluminum can surface becomes whitened. The etching amount of the aluminum can surface before and after the alkali treatment step is measured by accurately weighing the aluminum can before and after the alkali treatment step and the amount of decrease in the mass of the aluminum can before and after the alkali treatment step It can be obtained by sharing.
알칼리 처리 공정에서, 알루미늄캔 표면의 에칭량을 50mg/m2 미만으로 하기 위해서는, 알칼리 처리액의 pH, 알칼리 처리액의 알칼리성 물질의 농도, 알칼리 처리 공정의 처리 시간, 알칼리 처리 공정의 처리 온도를 컨트롤 할 필요가 있다. 보다 상세하게는, 알칼리 처리액의 알칼리성 물질의 농도를 높게 한다, 즉, 알칼리 처리액의 pH를 높게 함으로써, 알루미늄캔 표면의 에칭량을 증가시킬 수 있고, 반대로 낮게 함으로써 에칭량을 감소시킬 수 있다. 또한 알칼리 처리 공정의 처리 시간을 길게 하거나, 혹은, 알칼리 처리 온도를 높게 하는 것도 알루미늄캔 표면의 에칭량은 증가시킬 수 있고, 반대로, 처리 시간을 짧게, 혹은 처리 온도를 낮게 함으로써 에칭량을 감소시킬 수 있다. 이들 요소 모두를 조정할 필요는 없고, 일부 요소를 조정해도 알루미늄캔 표면의 에칭량을 50mg/m2 미만으로 할 수 있다.In order to reduce the etching amount of the aluminum can surface to less than 50 mg / m 2 in the alkali treatment step, the pH of the alkali treatment solution, the concentration of the alkaline substance in the alkali treatment solution, the treatment time of the alkali treatment step, You need to control. More specifically, the etching amount of the aluminum can surface can be increased by increasing the concentration of the alkaline substance in the alkali treating solution, that is, by increasing the pH of the alkali treating solution. On the other hand, by lowering the etching amount, . Further, it is also possible to increase the etching amount of the aluminum can surface by lengthening the treatment time of the alkali treatment process or increasing the alkali treatment temperature. On the contrary, by shortening the treatment time or lowering the treatment temperature, . It is not necessary to adjust all of these elements, and the etching amount of the aluminum can surface can be made less than 50 mg / m 2 even if some elements are adjusted.
알칼리 처리액은, pH가 9~14인 것이 바람직하다. 알칼리 처리액의 pH를 9~14로 함으로써, 알루미늄캔의 표면에 수산화물의 피막을 형성할 수 있다. 알칼리 처리 공정에서 알루미늄캔의 표면에 형성된 수산화물의 피막은, 후술하는 산처리 공정에서의 산처리액에 의해 용해된다. 알칼리 처리 공정에서 알루미늄캔의 표면에 수산화물의 피막을 효율적으로 형성시키면서, 에칭량을 억제하기 위해 알칼리 처리액의 pH는, 10.0~13.0인 것이 보다 바람직하다.It is preferable that the alkali treatment liquid has a pH of 9 to 14. A hydroxide coating can be formed on the surface of the aluminum can by adjusting the pH of the alkali treatment liquid to 9 to 14. The coating of the hydroxide formed on the surface of the aluminum can in the alkali treatment step is dissolved by the acid treatment solution in the acid treatment step described later. In order to efficiently form a coating of hydroxide on the surface of the aluminum can in the alkali treatment process and to suppress the amount of etching, the pH of the alkali treatment solution is more preferably 10.0 to 13.0.
알칼리 처리액은, 나트륨 이온, 칼륨 이온 및 암모늄 이온으로 이루어진 군에서 선택되는 적어도 1종을 함유하는 것이 바람직하다. 알칼리 처리액이, 이들 이온을 함유함으로써, 알루미늄캔의 표면에 효과적으로 수산화물의 피막을 형성할 수 있다. 나트륨 이온, 칼륨 이온 및 암모늄 이온의 공급원으로는, 수산화 나트륨, 수산화 칼륨, 탄산나트륨, 탄산수소나트륨, 탄산수소암모늄등의 무기물이나, 글루콘산이나 구연산등의 유기산의 나트륨염, 칼륨염, 암모늄염의 유기물을 들 수 있다. 이들 화합물은 2종 이상을 조합하여 사용할 수 있다. 수산화 나트륨등의 무기물은 알칼리성 물질이며, 나트륨 이온, 칼륨 이온 또는 암모늄 이온의 공급원이 되는 한편, 수산화물 이온의 공급원도 된다.The alkali treatment liquid preferably contains at least one kind selected from the group consisting of sodium ions, potassium ions and ammonium ions. By containing these ions in the alkali treatment liquid, a coating of hydroxide can be effectively formed on the surface of the aluminum can. Examples of the source of sodium ion, potassium ion and ammonium ion include inorganic substances such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate and ammonium hydrogencarbonate, organic substances such as sodium salts, potassium salts and ammonium salts of organic acids such as gluconic acid and citric acid . These compounds may be used in combination of two or more. An inorganic substance such as sodium hydroxide is an alkaline substance and serves as a source of sodium ions, potassium ions or ammonium ions, and also a source of hydroxide ions.
알칼리 처리액은, 수산화 나트륨을 포함하는 수용액인 것이 바람직하다. 알칼리 처리액으로서 알칼리성이 강한 수산화 나트륨 수용액을 이용함으로써, 알루미늄캔의 표면에 보다 효과적으로 수산화물의 피막을 형성할 수 있다.The alkali treatment solution is preferably an aqueous solution containing sodium hydroxide. A hydroxide film can be more effectively formed on the surface of the aluminum can by using an aqueous solution of sodium hydroxide having high alkalinity as the alkali treatment solution.
알칼리 처리액에서의 수산화 나트륨등의 알칼리성 물질의 농도는, 0.01~10g/L인 것이 바람직하다. 알칼리 처리액에서의 알칼리성 물질의 농도가 0.01g/L보다 작으면 알루미늄캔 표면에 수산화물의 피막이 형성되기 어려운 경향이 있고, 10g/L보다 크면 알루미늄캔의 표면이 과도하게 에칭됨으로써 백색화되어 버리는 경우가 있다.The concentration of the alkaline substance such as sodium hydroxide in the alkali treatment liquid is preferably 0.01 to 10 g / L. If the concentration of the alkaline substance in the alkali treatment solution is less than 0.01 g / L, the hydroxide film tends to be hardly formed on the surface of the aluminum can, while if it is larger than 10 g / L, the surface of the aluminum can is excessively etched, .
또한, 알칼리 처리액은, 유기산, 킬레이트제, 분산제 및 계면활성제로 이루어진 군에서 선택되는 적어도 1종을 함유하는 것이 바람직하다. 알칼리 처리액이, 유기산, 킬레이트제, 분산제 또는 계면활성제를 함유하는 경우에는, 온화한 조건(예를 들면, 저온도?단시간)에서 알칼리 처리 공정을 실시해도 알루미늄캔의 표면의 스머트를 효율적으로 제거하여 수산화물의 피막의 형성을 촉진할 수 있다.The alkali treatment liquid preferably contains at least one selected from the group consisting of an organic acid, a chelating agent, a dispersing agent and a surfactant. When the alkali treating solution contains an organic acid, a chelating agent, a dispersing agent or a surfactant, even if the alkali treatment step is performed under mild conditions (for example, at low temperature or for short time), the smut on the surface of the aluminum can is efficiently removed Thereby promoting the formation of a coating of a hydroxide.
알칼리 처리액에 포함되는 유기산으로는, 글루콘산, 구연산, 옥살산, 사과산, 주석산, 소르빈산, 호박산 및 이들의 나트륨염이나 칼륨염 등의 알칼리 금속염을 들 수 있다. 이들 중에서도 알칼리 처리액은, 글루콘산, 구연산, 옥살산, 사과산, 주석산으로 이루어진 군에서 선택되는 적어도 1종을 함유하는 것이 보다 바람직하다.Examples of the organic acid contained in the alkali treatment liquid include alkali metal salts such as gluconic acid, citric acid, oxalic acid, malic acid, tartaric acid, sorbic acid, succinic acid and their sodium or potassium salts. Among them, the alkali treatment liquid preferably contains at least one selected from the group consisting of gluconic acid, citric acid, oxalic acid, malic acid and tartaric acid.
알칼리 처리액에 포함되는 킬레이트제로서는, 아미노카르본산계 킬레이트제나 포스폰산계 킬레이트제, 축합 인산염이 들 수 있다. 구체적으로는 에틸렌디아민 사아세트산(EDTA), 1-히드록시에틸리덴-1, 1-디포스폰산나트륨(HEDP), 니트릴로트리아세트산(NTA), 트리폴리인산나트륨(STPP) 등을 들 수 있다. 이들 중에서도 알칼리 처리액은, 에틸렌디아민사아세트산(EDTA) 및 1-히드록시에틸리덴-1, 1-디포스폰산나트륨(HEDP)이 적어도 일방을 함유하는 것이 보다 바람직하다.Examples of the chelating agent to be contained in the alkali treatment liquid include aminocarboxylic acid type chelating agents, phosphonic acid type chelating agents and condensed phosphate salts. Specific examples thereof include ethylenediaminetetraacetic acid (EDTA), 1-hydroxyethylidene-1, 1-diphosphonate sodium (HEDP), nitrilotriacetic acid (NTA) and sodium tripolyphosphate (STPP). Among them, it is more preferable that the alkali treatment liquid contains at least one of ethylenediamine acetic acid (EDTA) and 1-hydroxyethylidene-1,1-diphosphonate sodium (HEDP).
알칼리 처리액에 포함되는 분산제로서는, 아크릴산말레산코폴리머, 그 나트륨염, 폴리카르본산, 폴리에틸렌글리콜등을 들 수 있다. 이들 중에서도 알칼리 처리액은, 아크릴산말레산코폴리머를 함유하는 것이 보다 바람직하다.Examples of the dispersant contained in the alkali treatment liquid include maleic acid acrylic acid copolymer, sodium salt thereof, polycarboxylic acid, and polyethylene glycol. Among them, it is more preferable that the alkali treatment liquid contains a maleic acid copolymer of acrylic acid.
알칼리 처리액에 포함되는 계면활성제로서는, 비이온계, 양이온계, 음이온계, 양성 이온계의 계면활성제가 이용된다. 이들 중, 특히 비이온계가 바람직하고, 예를 들면 탄화수소 유도체, 아비에트산 유도체, 알코올 에톡실레이트, 변성 폴리에톡시화 알코올등이 바람직하게 이용된다.As the surfactant contained in the alkali treatment solution, a nonionic, cationic, anionic or amphoteric surfactant is used. Among these, a nonionic system is preferable, and for example, hydrocarbon derivatives, abietic acid derivatives, alcohol ethoxylates, and modified polyethoxylated alcohols are preferably used.
또한 알칼리 처리액은, 유기산, 킬레이트제 및 분산제로 이루어진 군에서 선택되는 적어도 1종과 계면활성제를 함유하는 것이 보다 바람직하다. 즉, 알칼리 처리액에 함유되는 첨가제의 바람직한 조합은, 유기산, 킬레이트제 및 분산제로 이루어진 군에서 선택되는 적어도 1종과 계면활성제와의 조합이다.It is more preferable that the alkali treatment liquid contains at least one member selected from the group consisting of an organic acid, a chelating agent and a dispersing agent and a surfactant. That is, a preferable combination of the additives contained in the alkali treatment liquid is a combination of at least one member selected from the group consisting of an organic acid, a chelating agent and a dispersing agent and a surfactant.
이러한 조합의 첨가제를 알칼리 처리액이 함유함으로써, 상기와 같이 온화한 조건(예를 들면, 저온도-단시간)에서 알칼리 처리 공정을 실시해도, 알루미늄캔 표면의 스머트 및 윤활유 양쪽 모두를 효율적으로 제거하여 수산화물 피막의 형성을 보다 촉진시킬 수 있다. 이와 같이 알칼리 처리액이 유기산, 킬레이트제 및 분산제로 이루어진 군에서 선택되는 적어도 1종과 계면활성제를 함유하면, 온화한 조건에서 알칼리 처리를 실시한다 해도, 결과적으로 표면 처리 후의 알루미늄캔의 탈스머트성을 보다 향상시킬 수 있다.By containing such an additive in the alkali treatment solution, even if the alkali treatment step is performed under the mild conditions (for example, low temperature and short time) as described above, both the smut and the lubricant on the aluminum can surface are efficiently removed The formation of the hydroxide film can be further promoted. If the alkaline treatment liquid contains at least one selected from the group consisting of an organic acid, a chelating agent, and a dispersant and a surfactant, even if the alkali treatment is performed under mild conditions, as a result, Can be improved.
알칼리 처리 공정에서의 알루미늄캔의 처리 시간은, 1~30초인 것이 바람직하다. 알칼리 처리 공정에서의 알루미늄캔의 처리 시간이, 1초보다 짧으면 알루미늄캔 표면에 수산화물의 피막이 형성되기 어려운 경향이 있고, 30초보다 길면 알루미늄캔의 표면이 과도하게 에칭됨으로써 백색화되어 버리는 경우가 있다. 알칼리 처리 공정에서의 알루미늄캔의 처리 시간은, 3~20초인 것이 보다 바람직하다.The treatment time of the aluminum can in the alkali treatment step is preferably 1 to 30 seconds. If the treatment time of the aluminum can in the alkali treatment process is shorter than 1 second, the hydroxide film tends to be hardly formed on the surface of the aluminum can. If it is longer than 30 seconds, the surface of the aluminum can is excessively etched, . The treatment time of the aluminum can in the alkali treatment process is more preferably 3 to 20 seconds.
알칼리 처리 공정에서의 알루미늄캔의 처리 온도(알칼리 처리액의 온도)는, 40℃~70℃인 것이 바람직하다. 알칼리 처리 공정에서의 알루미늄캔의 처리 온도가, 40℃보다 낮으면 알루미늄캔 표면에 수산화물의 피막이 형성되기 어려운 경향이 있고, 70℃보다 높으면 알루미늄캔의 표면이 과도하게 에칭됨으로써 백색화되어 버리는 경우가 있다. 알칼리 처리 공정에서의 알루미늄캔의 처리 온도는, 45℃~60℃인 것이 보다 바람직하다.The treatment temperature of the aluminum can in the alkali treatment step (temperature of the alkali treatment solution) is preferably 40 ° C to 70 ° C. When the treatment temperature of the aluminum can in the alkali treatment process is lower than 40 ° C, a hydroxide film tends to be hardly formed on the surface of the aluminum can, while when it is higher than 70 ° C, the surface of the aluminum can is excessively etched, have. It is more preferable that the treatment temperature of the aluminum can in the alkali treatment step is 45 ° C to 60 ° C.
알칼리 처리 공정에서의 알루미늄캔의 처리 방법은 특별히 한정되지 않는다. 알칼리 처리 공정에서의 알루미늄캔의 처리 방법으로는, 스프레이법이나 침지법을 들 수 있다.The method of treating the aluminum can in the alkali treatment step is not particularly limited. Examples of the method of treating the aluminum can in the alkali treatment step include a spray method and a dipping method.
알칼리 처리 공정에서는, 상술한 알칼리 처리액에 의한 처리를 1회 실시할 수 있고, 복수회 실시할 수도 있다.In the alkali treatment step, the treatment with the above-described alkali treatment solution can be performed once or plural times.
알칼리 처리 공정에서, 알칼리 처리액에 의한 처리를 복수회 실시하는 경우에는, 각각의 처리에서의 처리 조건(알칼리 처리액의 pH, 처리 온도, 처리 시간 등)을 동일하게 할 수 있고, 변경할 수도 있다.In the alkali treatment step, when the treatment with the alkali treatment solution is carried out a plurality of times, the treatment conditions (pH of the alkali treatment solution, treatment temperature, treatment time, etc.) in each treatment can be the same and can be changed .
*<산처리 공정>* <Acid treatment process>
산처리 공정에서는, 알칼리 처리 공정 후의 알루미늄캔을 산처리액에 의해 처리한다.In the acid treatment step, the aluminum can after the alkali treatment step is treated with an acid treatment solution.
알루미늄캔의 표면은, 상술한 알칼리 처리 공정에서 부동태화 되지 않고, 수산화물의 피막이 형성된다. 수산화물의 피막은 산처리액에 의해 용이하게 녹으므로, 산처리 공정에서는 저온의 산처리액에 의해 알루미늄캔 표면을 에칭하는 것이 가능하다. 만일, 알칼리 처리 공정을 실시하지 않고, 산처리 공정으로 알루미늄캔 표면을 처리한 경우에는, 알루미늄캔 표면이 부동태화되어 버리기 때문에, 에칭을 진행시키기 위해 산처리액의 온도를 올릴 필요가 있다. 산처리 공정에서의 알루미늄캔의 처리 온도(산처리액의 온도)가 높으면 알루미늄캔의 표면 처리에서의 에너지 코스트가 너무 높아지므로 바람직하지 않다. 산처리 공정 전에 알칼리 처리 공정을 실시함으로써, 알칼리 처리 공정을 실시하지 않는 경우에 비해 산처리액의 온도를 5℃~20℃ 저온화 시킬 수 있다.The surface of the aluminum can is not passivated in the alkali treatment step described above, and a coating of hydroxide is formed. Since the coating of the hydroxide is easily dissolved by the acid treatment liquid, it is possible to etch the surface of the aluminum can with the acid treatment liquid at a low temperature in the acid treatment step. If the aluminum can surface is treated with the acid treatment without the alkali treatment, the surface of the aluminum can becomes passivated. Therefore, it is necessary to raise the temperature of the acid treatment to advance the etching. If the treatment temperature of the aluminum can in the acid treatment step (the temperature of the acid treatment solution) is high, the energy cost in the surface treatment of the aluminum can becomes too high. By performing the alkali treatment step before the acid treatment step, the temperature of the acid treatment solution can be lowered by 5 占 폚 to 20 占 폚 compared with the case where the alkali treatment step is not performed.
산처리 공정에서 산처리의 저온화가 가능해진다는 점에서, 작업 환경의 개선을 가져올 뿐만 아니라, 알루미늄캔을 처리하는 라인 정지 후 가동시에 필요로 하는 소요 시간을 단축할 수 있고, 생산성을 향상시킬 수 있다. 또한 산에 의한 설비 부식의 진행이 늦어져 설비의 갱신 빈도를 줄일 수 있다. It is possible not only to improve the working environment but also to shorten the time required for operation after the line stop for processing the aluminum can and to improve the productivity . In addition, the progress of corrosion of equipment by acid is delayed, and the frequency of updating the facility can be reduced.
산처리액은, pH가 2 이하인 것이 바람직하다. 산처리액의 pH가 2보다 크면 알루미늄캔 표면의 에칭이 불충분해지는 경향이 있다.The pH of the acid treatment solution is preferably 2 or less. If the pH of the acid treatment liquid is larger than 2, the etching of the aluminum can surface tends to be insufficient.
산처리액은, 무기산을 함유하는 것이 바람직하다.The acid treatment liquid preferably contains an inorganic acid.
무기산은, 에칭 촉진제로서의 기능을 가진다. 무기산의 구체적인 예로서는, 황산, 질산, 인산을 들 수 있고, 이들 무기산이 단독 사용 혹은 병용된다. 질소프리 및 인프리의 관점에서, 황산이 보다 바람직하게 이용된다.The inorganic acid has a function as an etching promoter. Specific examples of the inorganic acid include sulfuric acid, nitric acid and phosphoric acid, and these inorganic acids are used alone or in combination. From the viewpoint of nitrogen-free and on-site, sulfuric acid is more preferably used.
산처리액에서의 무기산의 함유량은, 0.01~25g/L인 것이 바람직하다. 산처리액에서의 무기산의 함유량이 0.01g/L 미만인 경우에는, 에칭 속도가 극단적으로 저하되고, 25g/L를 넘는 경우에는, 에칭에 대해서 그 이상의 효과가 인정되지 않아 경제적으로 불리하다. 보다 바람직한 산처리액에서의 무기산의 함유량은, 0.5~20g/L이다.The content of the inorganic acid in the acid treatment liquid is preferably 0.01 to 25 g / L. When the content of the inorganic acid in the acid treatment liquid is less than 0.01 g / L, the etching rate is extremely lowered. When the content is more than 25 g / L, no further effect is obtained in etching, which is economically disadvantageous. More preferably, the content of the inorganic acid in the acid treatment liquid is 0.5 to 20 g / L.
산처리액은, 산화형 금속 이온을 함유하는 것이 바람직하다.The acid treatment liquid preferably contains oxidized metal ions.
통상, 산처리 공정에서의 알루미늄의 에칭 반응은, 알루미늄이 알루미늄 이온(Al3+)이 되는 애노드 반응과, 산처리액중의 H+가 환원되어 1/2H2가 되는 캐소드 반응으로 이루어진다. 이 때문에, 산처리액중에 제2 철이온(Fe3+)과 같은 산화형 금속 이온을 첨가하면, 이 Fe3 +가 Fe2 +로 환원되는 애노드 반응이 상기 H+의 환원과 동시에 일어나, 알루미늄의 에칭 반응이 촉진된다. 또한 산처리액이 산화형 금속 이온을 함유함으로써, 산처리 공정 후의 화성처리에 의해 형성되는 화성처리 피막과 금속과의 밀착성이 향상된다.Normally, the etching reaction of aluminum in the acid treatment step consists of an anode reaction in which aluminum becomes aluminum ion (Al 3+ ) and a cathode reaction in which H + in the acid treatment solution is reduced to 1 / 2H 2 . Therefore, when an oxidizing metal ion such as ferric ion (Fe 3+ ) is added to the acid treatment solution, the anode reaction in which the Fe 3 + is reduced to Fe 2 + occurs simultaneously with the reduction of the H + Is promoted. Further, since the acid treatment liquid contains oxidized metal ions, the adhesion between the chemical conversion coating film formed by the chemical treatment after the acid treatment process and the metal is improved.
산화형 금속 이온으로는, 제2 철이온(Fe3 +) 외에, 메타바나듐산 이온(VO3-), 제2 세륨 이온(Ce4+), 코발트 이온(Co5+), 제2 주석 이온(Sn4+) 등을 들 수 있다.Examples of the oxidized metal ion include, besides ferric ion (Fe 3 + ), metavanadate ion (VO 3- ), cerium ion (Ce 4+ ), cobalt ion (Co 5+ ) (Sn 4+ ), and the like.
본 실시형태에서는, 산화형 금속 이온으로서 3가의 철이온(제2 철이온: Fe3+)이 바람직하게 이용된다. 산화형 금속 이온은, 황산염 또는 질산염과 같은 수용성염으로 공급되는 것이 바람직하기 때문에, 3가의 철이온은, 황산 제2 철 또는 질산 제2 철로서 공급되는 것이 바람직하다. 에칭 반응이 진행됨에 따라 제1 철이온(Fe2+) 농도가 증대하기 때문에, 산화 환원 전위(이하, ORP: oxidation-reduction potential이라고 한다)가 저하되고(세정제의 노화라고도 한다), 알루미늄 표면의 에칭 촉진 효과가 소실되어 버린다. 그래서, ORP를 컨트롤 하는 산화제를 수시 첨가 또는 당초부터 첨가하여, 제1 철이온을 제2 철이온으로 산화시킬 수 있다. 이 때의 ORP 컨트롤용의 산화제로서는, 과산화 수소(H2O2), 과황산염(예를 들면, NaS2O8 2-), 오존(O3), 세륨 화합물(예를 들면, 황산세륨암모늄: (NH4)4Ce(SO4)4), 아질산염(예를 들면 NaNO2, KNO2) 등을 들 수 있다. 산화형 금속 이온으로서 메타바나듐산 이온을 이용하는 경우에는, 메타바나듐산염을 수시 보급할 수 있다.In the present embodiment, trivalent iron ions (ferric ion: Fe 3+ ) are preferably used as the oxidized metal ions. Since the oxidized metal ion is preferably supplied as a water-soluble salt such as a sulfate or a nitrate, the trivalent iron ion is preferably supplied as ferric sulfate or ferric nitrate. Since the iron (Fe 2+ ) concentration increases as the etching reaction progresses, the oxidation-reduction potential (ORP) is lowered (hereinafter also referred to as aging of the cleaning agent) The etching promoting effect is lost. Thus, an oxidant that controls ORP can be added or added from time to time to oxidize ferrous ions to ferric ions. As the oxidizing agent for the ORP control at this time, hydrogen peroxide (H 2 O 2 ), persulfate (for example, NaS 2 O 8 2- ), ozone (O 3 ), cerium compound (for example, : and the like (NH 4) 4 Ce (SO 4) 4), nitrites (e.g., NaNO 2, KNO 2). In the case of using meta vanadium acid ion as the oxidized metal ion, meta vanadate can be supplied at any time.
산처리액에서의 산화형 금속 이온의 함유량은, 0.05~4g/L인 것이 바람직하다. 산처리액에서의 산화형 금속 이온의 함유량이 0.05g/L 미만인 경우에는, 에칭량이 부족하여 탈스머트성이 저하되고, 4g/L를 넘는 경우에는, 그 이상의 세정성을 기대할 수 없어 경제적으로 불리하다. 보다 바람직한 산처리액에서의 산화형 금속 이온의 함유량은, 0.1~1g/L이다.The content of the oxidized metal ion in the acid treatment liquid is preferably 0.05 to 4 g / L. When the content of the oxidized metal ion in the acid treatment solution is less than 0.05 g / L, the etching amount is insufficient and the detergency property is deteriorated. When the content is more than 4 g / L, further detergency can not be expected, Do. More preferably, the content of the oxidized metal ion in the acid treatment liquid is 0.1 to 1 g / L.
산처리액은, 계면활성제를 함유하는 것이 바람직하다.The acid treatment liquid preferably contains a surfactant.
계면활성제는 주로 알루미늄캔의 표면에 잔존하는 유지 성분이나 윤활제를 제거하는 기능을 가진다. 또한, 제거된 유지 성분이나 윤활제 성분이, 세정제중에 부유 하는 것을 방지하는 기능도 가진다. 즉 유지 성분이나 윤활제 성분이 세정제중에 부유될 경우에는 알루미늄캔의 표면에 재흡착되어 버릴 우려가 있는데, 산처리액에 계면활성제를 함유시킴으로써 이 문제를 회피할 수 있다.The surfactant mainly has a function of removing a residual component and a lubricant remaining on the surface of the aluminum can. It also has a function of preventing the removed retained component or the lubricant component from floating in the cleaning agent. That is, when the holding component or the lubricant component is suspended in the detergent, there is a possibility that the surfactant is adsorbed on the surface of the aluminum can. However, this problem can be avoided by containing a surfactant in the acid treating solution.
계면활성제로는, 비이온계, 양이온계, 음이온계, 양성 이온계의 계면활성제가 이용된다. 이들 중, 특히 비이온계가 바람직하고, 예를 들면 에톡시화 알킬페놀계, 탄화수소 유도체, 아비에트산 유도체, 제1급 에톡시화 알코올, 변성 폴리에톡시화 알코올등이 바람직하게 이용된다.As the surfactant, nonionic, cationic, anionic, and amphoteric surfactants are used. Of these, particularly preferred are nonionic systems, and ethoxylated alkylphenols, hydrocarbon derivatives, abietic acid derivatives, primary ethoxylated alcohols, modified polyethoxylated alcohols and the like are preferably used.
산처리액에서의 계면활성제의 함유량은, 0.01~10g/L인 것이 바람직하다. 산처리액에서의 계면활성제의 함유량이 0.01g/L 미만인 경우에는, 세정성, 특히 탈지성이 저하되고, 10g/L를 넘는 경우에는, 산처리제가 발포하여 처리가 곤란해지고, 폐수 처리에 부하가 걸린다. 보다 바람직한 산처리액에서의 계면활성제의 함유량은, 0.1~5g/L이다.The content of the surfactant in the acid treatment liquid is preferably 0.01 to 10 g / L. When the content of the surfactant in the acid treatment solution is less than 0.01 g / L, the cleaning property, particularly the degreasing property, deteriorates. When the content of the surfactant exceeds 10 g / L, the acid treatment agent becomes brittle and difficult to treat, . The content of the surfactant in the acid treatment solution is more preferably 0.1 to 5 g / L.
산처리액에서의 유기 술폰산은, 0.01~25g/L인 것이 바람직하다. 산처리액에서의 유기 술폰의 함유량이 0.01g/L 미만인 경우에는, 충분한 에칭량을 얻을 수 없을 우려가 있고, 25g/L를 넘는 경우에는 산처리액의 액안정성이 저하되어 버리는 경향이 있다. 배수 부하를 저감시킨다는 관점에서, 보다 바람직한 산처리액에서의 유기 술폰산의 함유량은, 0.1~5g/L이다.The amount of the organic sulfonic acid in the acid treatment solution is preferably 0.01 to 25 g / L. When the content of the organic sulfone in the acid treatment solution is less than 0.01 g / L, sufficient etching amount may not be obtained. When the content is more than 25 g / L, the solution stability of the acid treatment solution tends to be lowered. From the viewpoint of reducing the drainage load, the content of the organic sulfonic acid in the acid treatment solution is more preferably 0.1 to 5 g / L.
산처리 공정에서의 알루미늄캔 표면의 에칭량은, 60~100mg/m2이다. 산처리 공정에서의 에칭량이, 60mg/m2 미만이면 에칭이 불충분하기 때문에, 알루미늄캔 표면에 후술하는 화성처리 피막이나 도장 피막을 형성하기 어려운 경향이 있다. 산처리 공정에서의 에칭량이, 100mg/m2보다 많으면, 에칭이 너무 진행되어 알루미늄캔 표면이 백색화되어 버리는 경우가 있다. 산처리 공정에서의 알루미늄캔 표면의 에칭량은, 산처리 공정 전후의 알루미늄캔의 질량을 정밀 천칭에 의해 측정하고, 산처리 공정 전후에서의 알루미늄캔의 질량 감소량을 알루미늄캔의 표면적으로 나눔으로써 구할 수 있다.The etching amount of the aluminum can surface in the acid treatment step is 60 to 100 mg / m 2 . If the etching amount in the acid treatment step is less than 60 mg / m 2 , the etching is insufficient, so that it is difficult to form a chemical conversion coating film or a coating film to be described later on the aluminum can surface. If the etching amount in the acid treatment step is more than 100 mg / m 2 , the etching proceeds too much and the aluminum can surface may become whitened. The etching amount of the aluminum can surface before and after the acid treatment process can be obtained by measuring the mass of the aluminum can before and after the acid treatment process by a precision balance and dividing the amount of reduction in mass of the aluminum can before and after the acid treatment process by the surface area of the aluminum can .
산처리 공정에서의 알루미늄캔의 처리 방법은 특별히 한정되지 않는다. 산처리 공정에서의 알루미늄캔의 처리 방법으로는, 스프레이법이나 침지법을 들 수 있다.The method of treating the aluminum can in the acid treatment step is not particularly limited. Examples of the method of treating the aluminum can in the acid treatment step include a spray method and a dipping method.
산처리 공정에서의 알루미늄캔의 처리 시간은, 10~90초인 것이 바람직하다. 산처리 공정에서의 알루미늄캔의 처리 시간이 10초보다 짧으면 처리 시간이 너무 짧아 알루미늄캔 표면의 에칭이 불충분해지는 경향이 있고, 90초보다 길면 알루미늄캔 표면이 과도하게 에칭 되어 산처리제의 노화가 빨라지는 경향이 있다. 산처리 공정에서의 알루미늄캔의 처리 시간은, 30~45초인 것이 보다 바람직하다.The treatment time of the aluminum can in the acid treatment step is preferably 10 to 90 seconds. If the treatment time of the aluminum can in the acid treatment process is shorter than 10 seconds, the treatment time is too short, and the etching of the aluminum can surface tends to be insufficient. If the treatment time is longer than 90 seconds, the aluminum can surface is excessively etched, . The treatment time of the aluminum can in the acid treatment step is more preferably 30 to 45 seconds.
산처리 공정에서의 알루미늄캔의 처리 온도는, 30℃~65℃인 것이 바람직하다. 산처리 공정에서의 알루미늄캔의 처리 온도가 30℃ 미만이면, 처리 온도의 관리가 어려워지는 경향이 있고, 65보다 높으면 에너지 코스트가 너무 높아지는 경향이 있다. 산처리 공정에서의 알루미늄캔의 처리 온도는, 40℃~60℃인 것이 보다 바람직하다.The treatment temperature of the aluminum can in the acid treatment step is preferably 30 占 폚 to 65 占 폚. If the treatment temperature of the aluminum can in the acid treatment process is less than 30 占 폚, the treatment temperature tends to be difficult to control. If it is higher than 65, the energy cost tends to become too high. It is more preferable that the treatment temperature of the aluminum can in the acid treatment step is 40 占 폚 to 60 占 폚.
<화성처리 및 도장 처리>≪ Chemical conversion treatment and coating treatment >
산처리 공정 후의 알루미늄캔은, 종래 공지의 방법에 따라 물 세정 후, 인산염계나 지르콘계의 화성처리액에 의한 화성처리에 제공된다.The aluminum can after the acid treatment process is provided for the conversion treatment with a phosphatizing or zircon-based chemical conversion treatment solution after water cleaning according to a conventionally known method.
화성처리 후의 알루미늄캔은, 필요에 따라 물 세정한 후에, 도장 처리에 제공된다.After the chemical treatment, the aluminum can is provided for the coating treatment after water rinsing if necessary.
본 실시형태에 따른 알루미늄캔의 표면 처리 방법에 의해 표면 처리된 알루미늄캔은, 표면의 스머트나 윤활유가 충분히 제거되었기 때문에 견고한 화성처리 피막 및 도장 피막을 형성할 수 있다.The aluminum can surface treated by the surface treatment method of the aluminum can according to the present embodiment can form a chemically treated coating film and a coating film which are solid because the surface smudge and the lubricating oil are sufficiently removed.
[실시예][Example]
다음에 본 발명을 실시예에 근거하여 더욱 상세하게 설명하나, 본 발명은 이들로 한정되는 것은 아니다. 특히 언급이 없는 한, 부 및 %는, 모두 질량 기준이다.Next, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. Unless otherwise noted, parts and percentages are all on a mass basis.
<실시예 1> ≪ Example 1 >
알루미늄캔으로서, 3004 합금의 알루미늄판을 DI가공하여 얻은, 윤활유와 스머트가 부착된 뚜껑 없는 용기를 준비하였다. 이것을, 알칼리성 물질인 수산화 나트륨에 의해 pH가 12.5로 조정된 알칼리 처리액을 이용하여, 처리 온도 40℃에서 10초간 스프레이 처리하였다(알칼리 처리). 이어서, 알칼리 처리 후의 알루미늄캔을, 1g/L의 제2 철이온과 2g/L의 비이온계 계면활성제를 함유하고 산성 물질인 황산에 의해 pH가 1.0으로 조정된 산처리액을 이용하여, 처리 온도 50℃에서 40초간 스프레이 처리하였다(산처리). 산처리액의 제2 철이온의 공급원은, 황산 제2철이다.As the aluminum can, a lid-free container with a lubricating oil and a smooter obtained by DI processing of an aluminum plate of a 3004 alloy was prepared. This was spray-treated (alkali treatment) for 10 seconds at a treatment temperature of 40 占 폚 by using an alkali treatment solution whose pH was adjusted to 12.5 with sodium hydroxide which is an alkaline substance. Subsequently, the aluminum can after the alkali treatment was treated with an acid treatment solution containing 1 g / L of ferric ion and 2 g / L of a nonionic surfactant and adjusted to pH 1.0 with sulfuric acid as an acidic substance, And sprayed at a temperature of 50 占 폚 for 40 seconds (acid treatment). The source of the ferric ion of the acid treatment solution is ferric sulfate.
그 다음에, 15초간 수도물로 세정하고, 화성처리제(알르서프 450 일본페인트사 제조)에 의해, 피막 Zr량이 11mg/m2가 되도록 처리 조건을 조정하여 화성처리를 실시하였다(40℃, 12초간). 화성처리후, 15초간 수도물로 세정하고, 계속하여 5초간 탈이온수로 스프레이 세정하고, 195℃에서 3분간 건조시켰다.Subsequently, the substrate was rinsed with tap water for 15 seconds, and a chemical conversion treatment was carried out by adjusting the treatment conditions such that the coating Zr amount was 11 mg / m 2 by a chemical conversion treatment agent (Alsaur 450, manufactured by Nippon Paint Co., Ltd.) ). After the chemical treatment, the substrate was rinsed with tap water for 15 seconds, spray-rinsed with deionized water for 5 seconds, and dried at 195 캜 for 3 minutes.
<실시예 2~26, 비교예 1~15 및 참고예 1~3><Examples 2 to 26, Comparative Examples 1 to 15 and Reference Examples 1 to 3>
알칼리 처리 공정에서, 표 1 및 표 2에 나타낸 알칼리성 물질을 이용하고, 표 1 및 표 2에 나타낸 pH로 조정된 알칼리 처리액을 이용하여 표 1 및 표 2에 나타낸 처리 온도와 처리 시간으로, 실시예 1과 동일한 알루미늄캔을 스프레이 처리하였다(알칼리 처리). 산처리 공정에서는, 표 1 및 표 2에 나타낸 농도로 제2 철이온과, 비이온계 계면활성제와, 필요에 따라 유기 술폰산(HSO3-CH2CH(OH)CH2OH), 을 함유하며, 표 1 및 표 2에 나타낸 pH로 조정된 산처리액을 이용하여 표 1 및 표 2에 나타낸 처리 온도와 처리 시간으로, 알칼리 처리 후의 알루미늄캔을 스프레이 처리하였다(산처리).In the alkali treatment process, the alkaline substance shown in Table 1 and Table 2 was used and the alkali treatment solution adjusted to the pH shown in Table 1 and Table 2 was used and the treatment temperature and treatment time shown in Tables 1 and 2 were used The same aluminum can as in Example 1 was spray-treated (alkali treatment). In the acid treatment step, ferric ion, a nonionic surfactant and, if necessary, an organic sulfonic acid (HSO 3 -CH 2 CH (OH) CH 2 OH) are contained at the concentrations shown in Tables 1 and 2 , And the acid treatment liquid adjusted to the pH shown in Tables 1 and 2 was used to spray the aluminum can after the alkali treatment with the treatment temperature and treatment time shown in Tables 1 and 2 (acid treatment).
이와 같이 표 1 및 표 2에 나타낸 바와 같이 조건을 변경하는 이외는, 실시예 1과 동일한 조건으로 알루미늄캔을 처리하였다.The aluminum can was treated under the same conditions as in Example 1, except that the conditions were changed as shown in Tables 1 and 2.
실시예 21 및 비교예 11에서는, 황산 및 질산(질량비: 10 대 1)의 혼합물을, 실시예 22 및 비교예 12에서는, 황산 및 인산(질량비: 10 대 1)의 혼합물을, 실시예 23 및 비교예 13에서는, 황산 및 플루오린화수소산(질량비: 10 대 1)의 혼합물을, 각각 산성 물질로서 이용하였다.(Mass ratio: 10: 1) in Example 21 and Comparative Example 11, and a mixture of sulfuric acid and phosphoric acid (mass ratio: 10: 1) in Example 22 and Comparative Example 12, and a mixture of sulfuric acid and nitric acid In Comparative Example 13, a mixture of sulfuric acid and hydrofluoric acid (weight ratio: 10: 1) was used as an acidic substance, respectively.
또한, 비교예 5~15 및 참고예 1~3에서는, 알칼리 처리 공정을 실시하지 않고, 알루미늄캔을 다음 공정인 산처리 공정에서 사용하는 산처리액을 2분의 1의 농도로 희석시킨 액으로, 산처리와 동일한 온도에서 10초간 세정한 후에, 산처리 공정에 제공하였다. 실시예 23 및 비교예 13에서는 제2 철이온을, 비교예 3 및 6에서는 계면활성제를, 각각 산처리액에 함유시키지 않았다.In Comparative Examples 5 to 15 and Reference Examples 1 to 3, the aluminum can was used as a solution obtained by diluting an acid treatment solution used in an acid treatment step in the next step to a concentration of one-half, without performing the alkali treatment step , And was washed at the same temperature as the acid treatment for 10 seconds, and then supplied to the acid treatment process. Ferric ions were not added in Example 23 and Comparative Example 13, and surfactants in Comparative Examples 3 and 6 were not contained in the acid treatment solution.
<비교예 16>≪ Comparative Example 16 >
비교예 16에서는, 알칼리 처리 공정을 실시하지 않고, 계면활성제와 킬레이트제를 함유하며, 알칼리성 물질로서 수산화 나트륨에 의해 pH가 12.5로 조정된 알칼리 탈지액에 의해, 처리 온도 60℃에서 60초간 스프레이 처리하였다(알칼리 탈지 처리). 계속해서, 알칼리 처리 후의 알루미늄캔을, 표 2에 나타낸 조건에서 이루어지는 산처리 공정에 제공하였다.In Comparative Example 16, the alkali treatment step was not performed, and the alkali treatment was carried out at 60 ° C for 60 seconds by an alkaline degreasing solution containing a surfactant and a chelating agent and adjusted to pH 12.5 with sodium hydroxide as an alkaline substance (Alkali degreasing treatment). Subsequently, an aluminum can after the alkali treatment was provided to the acid treatment step under the conditions shown in Table 2. [
<실시예 27~44 및 비교예 17>≪ Examples 27 to 44 and Comparative Example 17 >
알칼리 처리 공정에서, 표 3에 나타낸 농도로 유기산과, 킬레이트제와, 분산제와, 계면활성제, 를 함유하며, 표 3에 나타낸 알칼리성 물질을 이용하여 표 3에 나타낸 pH로 조정한 알칼리 처리액을 이용하여 표 3에 나타낸 처리 온도와 처리 시간으로, 실시예 1과 동일한 알루미늄캔을 스프레이 처리하였다(알칼리 처리). 산처리 공정에서는, 표 3에 나타낸 농도로 제2 철이온과 비이온계 계면활성제를 함유하고, 표 3에 나타낸 pH로 조정한 산처리액을 이용하여 표 3에 나타낸 처리 온도와 처리 시간으로, 알칼리 처리 후의 알루미늄캔을 스프레이 처리하였다(산처리).In the alkali treatment step, an alkali treatment solution containing the organic acid, the chelating agent, the dispersing agent and the surfactant at the concentrations shown in Table 3 and adjusted to the pH shown in Table 3 was used by using the alkaline substance shown in Table 3 The same aluminum cans as in Example 1 were sprayed (alkali treatment) at the treatment temperature and treatment time shown in Table 3. In the acid treatment step, an acid treatment solution containing ferric ion and nonionic surfactant at the concentrations shown in Table 3 and adjusted to the pH shown in Table 3 was used and the treatment temperature and treatment time shown in Table 3 were used, The aluminum can after the alkali treatment was spray-treated (acid treatment).
이와 같이 표 3에 나타낸 바와 같이 조건을 변경하는 이외에는, 실시예 1과 동일한 조건으로 알루미늄캔을 처리하였다. 알칼리 처리액에 계면활성제를 함유시키는 경우에는, 2g/L의 비이온계 계면활성제를 함유시켰다. 또한, 실시예 35에서 함유되는 아크릴산말레산 코폴리머는, BASF 재팬사 제조의 SOKALAN CP5이다.Thus, except that the conditions were changed as shown in Table 3, the aluminum can was treated under the same conditions as in Example 1. [ When the surfactant was contained in the alkali treatment solution, 2 g / L of a nonionic surfactant was contained. In addition, the acrylic acid maleic acid copolymer contained in Example 35 is SOKALAN CP5 manufactured by BASF Japan.
또한, 비교예 17에서는, 알칼리 처리 공정을 실시하지 않고, 구연산을 0.5g/L 함유하는 산성 용액을 이용하여 표 3에 나타낸 처리 온도와 처리 시간으로, 실시예 1과 동일한 알루미늄캔을 스프레이 처리하였다. 계속하여, 산처리 공정에서는, 표 3에 나타낸 농도로 제2 철이온과 비이온계 계면활성제를 함유하고, 표 3에 나타낸 pH로 조정한 산처리액을 이용하여 표 3에 나타낸 처리 온도와 처리 시간으로, 알루미늄캔을 스프레이 처리하였다.In Comparative Example 17, the same aluminum can as in Example 1 was spray-treated at the treatment temperature and treatment time shown in Table 3 using an acid solution containing 0.5 g / L of citric acid without conducting the alkali treatment . Subsequently, in the acid treatment step, the acid treatment solution containing ferric ion and nonionic surfactant at the concentrations shown in Table 3 and adjusted to the pH shown in Table 3 was used and the treatment temperature shown in Table 3 and the treatment temperature Hour, the aluminum can was sprayed.
[평가][evaluation]
(a) 에칭량(a) the etching amount
알칼리 처리 공정 전후에, 알루미늄캔의 질량을 정밀 천칭에 의해 측정하였다. 알칼리 처리 공정 전후에서의 알루미늄캔의 질량 감소량을 알루미늄캔의 표면적으로 나눈 수치를 에칭량으로 하고, 에칭량을 이하의 2 단계로 평가하였다. 결과를 표 1, 표 2 및 표 3에 나타낸다.Before and after the alkali treatment process, the mass of the aluminum can was measured by a precision balance. The value obtained by dividing the amount of reduction in mass of the aluminum can before and after the alkali treatment step by the surface area of the aluminum can is regarded as the etching amount, and the etching amount was evaluated in the following two steps. The results are shown in Tables 1, 2 and 3.
A: 50mg/m2 미만A: less than 50 mg / m 2
B: 50~100mg/m2 B: 50 to 100 mg / m 2
(b) 외관(b) Appearance
건조 후의 용기내의 흰 정도를 육안으로 판정하였다. 탈지 및 탈스머트가 완전하고 충분히 에칭된 흰 외관을 가지는 경우에 양호로 하고, 백화의 정도로 따라 이하의 5 단계로 평가하였다. 결과를 표 1, 표 2 및 표 3에 나타낸다.The degree of whitening in the container after drying was visually determined. The degreasing and degumming were considered to be good when they had a complete and well-etched white appearance and were evaluated in the following five stages according to the degree of whitening. The results are shown in Tables 1, 2 and 3.
A: 전체면 백색A: Whole surface white
B: 부분적으로 엷은 회색B: Partly light gray
C: 전체에 엷은 회색C: Whole-pale gray
D: 부분적으로 회색D: Partly gray
E: 전체면 회색E: Full surface gray
(c) 물 젖음성(c) Water wettability
화성처리 후의 스프레이 물 세정 직후의 용기를 3회 흔들어 물기를 빼고, 용기를 상향으로 정치(靜置)시켜 30초 후의 용기 외표면의 물 젖은 면적(%)을 측정하였다. 결과를 표 1, 표 2 및 표 3에 나타낸다.After the chemical treatment, the container immediately after washing with water was shaken three times to remove water, and the container was allowed to stand upwards, and the area (%) of water on the outer surface of the container after 30 seconds was measured. The results are shown in Tables 1, 2 and 3.
(d) 탈스머트성(d)
본 실시예, 비교예 및 참고예에서 얻은 표면 처리 후의 알루미늄캔의 표면에 투명 점착 테이프를 밀착시키고, 다음에 이것을 박리하여 백색 대지(臺紙) 위에 붙여, 테이프 붙인 면의 흰 정도를 다른 대지 부분과 비교하였다. 완전하게 스머트가 제거되어 오염이 없는 경우를 양호로 하고, 오염 정도에 따라 이하의 5 단계로 평가하였다. 결과를 표 1, 표 2 및 표 3에 나타낸다.A transparent adhesive tape was adhered to the surface of the aluminum can after the surface treatment obtained in this example, the comparative example and the reference example, and then peeled off and stuck on the surface of the white board to measure the whiteness of the tape- . The case where the smut was completely removed and no contamination was judged to be good was evaluated in the following five stages according to the degree of contamination. The results are shown in Tables 1, 2 and 3.
5: 오염 없음5: No pollution
4: 흔적 정도의 오염4: Contamination of contamination
3: 미미한 오염3: Minimal contamination
2: 중 정도의 오염2: Moderate pollution
1: 다대한 오염1: Dirty contamination
(e) 내비수흑변성(耐沸水變性, 내식성)(e) Viscosity change (boiling water resistance, corrosion resistance)
본 실시예, 비교예 및 참고예에서 얻은 표면 처리 후의 알루미늄캔을, 비등 수도물 중에서 30분간 침지한 후의 외관 평가를 다음의 기준으로 실시하였다. 결과를 표 1, 표 2 및 표 3에 나타낸다.After the surface-treated aluminum cans obtained in this example, the comparative example and the reference example were dipped in boiling water for 30 minutes, the external appearance evaluation was carried out based on the following criteria. The results are shown in Tables 1, 2 and 3.
5: 외관의 변화 없음5: No change in appearance
4: 부분적으로 엷게 흑변4: Partially lightly blackened
3: 전체적 엷게 흑변3: overall lightly blackened
2: 부분적으로 진하게 흑변2: partially darkened black
1: 전체면 흑변1: Whole surface black
실시예 1~11, 13~15, 17과 비교예 5와의 비교등에서 명확한 바와 같이, 알칼리 처리를 하지 않고 산처리하는 경우, 알루미늄캔을 알칼리 처리한 후에 산처리하는 경우에 비해, 알루미늄캔의 외관, 물젖음성, 탈스머트성, 내비수흑변성(내식성)에서 양호한 결과를 얻을 수 없음을 알 수 있다. 이 결과는, 알칼리 처리를 하지 않으면 산처리 공정에서 알루미늄캔 표면이 충분히 에칭되지 않는 것에 기인하는 것이라고 생각된다. 또한 참고예 2에 나타난 바와 같이, 알칼리 처리를 하지 않고 산처리하는 경우라도, 산처리의 온도를 올리면, 알루미늄캔 표면이 충분히 에칭되어 외관, 물젖음성, 탈스머트성, 내비수흑변성(내식성)이 양호한 알루미늄캔을 얻을 수 있다.As apparent from comparison with Examples 1 to 11, 13 to 15, and 17 and Comparative Example 5, in the case of acid treatment without alkali treatment, compared with the case of acid treatment after alkali treatment of aluminum can, , Water wettability, desmutting property, and weathering resistance (corrosion resistance) can not be obtained. This result is considered to be due to the fact that the aluminum can surface is not sufficiently etched in the acid treatment step unless the alkali treatment is performed. Also, as shown in Reference Example 2, even when the acid treatment is performed without alkali treatment, if the temperature of the acid treatment is raised, the aluminum can surface is sufficiently etched so that the appearance, water wettability, desmutting property, A good aluminum can can be obtained.
실시예 1~11, 13~15, 17과 참고예 1을 비교하면, 실시예 1~11, 13~15, 17은, 참고예 1과 동일하게 양호한 평가 결과를 얻는 한편, 산처리 공정에서의 처리 온도는 참고예 1의 경우보다 20℃ 낮다. 이와 같이, 산처리 공정에 앞서 알칼리 처리 공정을 미리 실시함으로써, 산처리 공정의 온도를 20℃ 저하시킬 수 있었다.Comparing Examples 1 to 11, 13 to 15, and 17 with Reference Example 1, it is understood that Examples 1 to 11, 13 to 15, and 17 obtain good evaluation results in the same manner as in Reference Example 1, The treatment temperature is 20 占 폚 lower than that of Reference Example 1. Thus, by performing the alkali treatment step in advance of the acid treatment step, the temperature of the acid treatment step can be lowered by 20 占 폚.
또한, 실시예 25, 26과 비교예 14, 15와의 비교에서, 산처리액에 유기 술폰산을 함유시켜도, 알칼리 처리를 실시하지 않으면, 특히 탈스머트성, 내비수흑변성(내식성)에서 충분히 만족할 수 있는 평가 결과를 얻을 수 없음이 분명하다. 또한 유기 술폰산을 과잉 함유시킨 경우, 산처리액의 폐수 처리가 번잡해져 버리는 경향이 있다.Further, in comparison between Examples 25 and 26 and Comparative Examples 14 and 15, even if the acid treatment liquid contains an organic sulfonic acid, it is possible to obtain a satisfactory result in the case where the alkaline treatment is not carried out, It is clear that the evaluation results can not be obtained. When the organic sulfonic acid is contained in an excessive amount, the treatment of the acid treatment liquid wastewater tends to be complicated.
또한, 실시예 25와 참고예 2를 비교하면, 실시예 25는, 참고예 2와 동일하게 양호한 평가 결과를 얻는 한편, 산처리 공정에서의 처리 온도는 참고예 2의 경우보다 20℃ 낮다. 이와 같이, 산처리액이 유기 술폰산을 함유하는 경우라도, 산처리 공정에 앞서 알칼리 처리 공정을 미리 실시함으로써, 산처리 공정의 온도를 20℃ 저하시킬 수 있었다.Further, when Example 25 is compared with Reference Example 2, in Example 25, a good evaluation result is obtained in the same manner as in Reference Example 2, while the treatment temperature in the acid treatment step is 20 占 폚 lower than that in Reference Example 2. Thus, even in the case where the acid treatment solution contains an organic sulfonic acid, the temperature of the acid treatment step can be lowered by 20 占 폚 by performing the alkali treatment step in advance of the acid treatment step.
또한, 실시예 26과 참고예 3을 비교하면, 실시예 26은, 참고예 3과 동일하게 양호한 평가 결과를 얻는 한편, 산처리 공정에서의 처리 온도는 참고예 3의 경우보다 10℃ 낮다. 이와 같이, 산처리액이 유기 술폰산을 많이(25g/L) 함유하는 경우라도, 산처리 공정에 앞서 알칼리 처리 공정을 미리 실시함으로써, 산처리 공정의 온도를 10℃ 저하시킬 수 있었다.Further, when Example 26 is compared with Reference Example 3, a good evaluation result is obtained in the same manner as in Reference Example 3 in Example 26, while the treatment temperature in the acid treatment step is 10 占 폚 lower than that in Reference Example 3. Thus, even in the case where the acid treatment solution contains a large amount of organic sulfonic acid (25 g / L), the temperature of the acid treatment step can be lowered by 10 캜 by performing the alkali treatment step in advance of the acid treatment step.
또한, 비교예 1~4와 같이, 산처리 공정 전에 알칼리 처리 공정을 실시한 경우라도, 알칼리 처리 공정에서의 에칭량이 50mg/m2 이상이면, 알루미늄캔의 외관이 악화되고, 전면적으로 회색화되어 버리는 것을 알았다. 이러한 결과는, 알칼리 처리 공정에서 에칭량이 증가하면, 에칭의 컨트롤이 어려워져 버리는 것에 기인한다고 생각된다.Further, even when the alkali treatment step is performed before the acid treatment step as in the comparative examples 1 to 4, if the etching amount in the alkali treatment step is 50 mg / m 2 or more, the appearance of the aluminum can becomes worse, . These results are considered to be due to the fact that control of etching becomes difficult when the amount of etching is increased in the alkali treatment step.
또한, 비교예 16과 같이, 캔 뚜껑용 알루미늄의 기재처리와 같이, 산처리 공정에 앞서, 알칼리 탈지 공정에서 충분히 에칭을 진행시킨 경우에는, 알루미늄캔의 외관이 악화되고, 전면적으로 회색화되어 버리는 것을 알았다.In addition, as in Comparative Example 16, when the etching was sufficiently advanced in the alkali degreasing step prior to the acid treatment step as in the base treatment of aluminum for the can lid, the appearance of the aluminum can was deteriorated, .
또한, 실시예 27과 실시예 28~44와의 비교에서 분명한 바와 같이, 알칼리 처리액에 유기산, 킬레이트제, 분산제 혹은 계면활성제를 함유시키지 않는 경우보다 이들을 함유 시키는 것이, 알칼리 처리 공정을 온화한 조건(단시간)에서 실시했다 하더라도, 표면 처리된 알루미늄캔의 탈스머트성이 양호해지는 것을 알았다. 이 결과는, 알칼리 처리액이 유기산, 킬레이트제 혹은 분산제를 함유하는 경우에는, 알루미늄캔 표면의 스머트가 효율적으로 제거됨으로써 수산화물의 피막 형성이 촉진되는 것에 기인하는 것이라 예상된다. 또한, 알칼리 처리액이 계면활성제를 함유하는 경우에는, 알루미늄캔 표면의 윤활유가 효율적으로 제거됨으로써 수산화물의 피막 형성이 촉진된다고 예상된다.Further, as is clear from the comparison between Example 27 and Examples 28 to 44, it is preferable that the alkali treatment solution contains the organic acid, the chelating agent, the dispersant, or the surface active agent in the alkaline treatment solution in a mild condition ), It was found that the desmutting property of the surface-treated aluminum can was improved. This result is expected to result from the fact that when the alkali treatment liquid contains an organic acid, a chelating agent or a dispersing agent, the coating of the hydroxide is promoted by effectively removing the smut on the surface of the aluminum can. Further, in the case where the alkali treatment liquid contains a surfactant, it is expected that the formation of the hydroxide film is promoted by efficiently removing the lubricating oil on the aluminum can surface.
Claims (6)
상기 알칼리 처리 공정 후의 알루미늄캔을 산처리액으로 처리하는 산처리 공정을 포함하고,
상기 알칼리 처리 공정에서의 에칭량은, 50mg/m2 미만이고,
상기 알칼리 처리액은, 40℃~70℃이고,
상기 알칼리 처리 공정에서의 알루미늄캔의 처리 시간은, 1초간~30초간이며,
상기 산처리 공정에서의 에칭량은, 60~100mg/m2인 알루미늄캔의 표면 처리 방법.
An alkali treatment step of treating the aluminum can with an alkali treatment solution,
And an acid treatment step of treating the aluminum can after the alkali treatment step with an acid treatment solution,
The etching amount in the alkali treatment step is less than 50 mg / m 2 ,
The alkali treatment liquid is 40 占 폚 to 70 占 폚,
The treatment time of the aluminum can in the alkali treatment step is from 1 second to 30 seconds,
Wherein the etching amount in the acid treatment step is 60 to 100 mg / m 2 .
상기 알칼리 처리액은 나트륨 이온, 칼륨 이온 및 암모늄 이온으로 이루어진 군에서 선택되는 적어도 1종을 함유하는 알루미늄캔의 표면 처리 방법.
The method according to claim 1,
Wherein the alkali treatment liquid contains at least one selected from the group consisting of sodium ions, potassium ions and ammonium ions.
상기 알칼리 처리액은, 유기산, 킬레이트제, 분산제 및 계면활성제로 이루어진 군에서 선택되는 적어도 1종을 함유하는 알루미늄캔의 표면 처리 방법.
The method according to claim 1,
Wherein the alkali treatment liquid contains at least one member selected from the group consisting of an organic acid, a chelating agent, a dispersant, and a surfactant.
상기 산처리액은, 황산, 질산 및 인산으로 이루어진 군에서 선택되는 적어도 1종을 함유하고, 3가의 철이온을 0.05g/L~4g/L함유하며, pH가 2 이하이고,
상기 산처리 공정에서의 알루미늄캔의 처리 온도는, 30℃~65℃인 알루미늄캔의 표면 처리 방법.
The method according to claim 1,
Wherein the acid treatment liquid contains at least one member selected from the group consisting of sulfuric acid, nitric acid and phosphoric acid, contains 0.05 g / L to 4 g / L of a trivalent iron ion, has a pH of 2 or less,
Wherein the aluminum can process temperature in the acid treatment process is 30 占 폚 to 65 占 폚.
상기 산처리 공정에서의 알루미늄캔의 처리 시간은, 10~90초간인 알루미늄캔의 표면 처리 방법.
The method according to claim 1,
Wherein the treatment time of the aluminum can in the acid treatment step is 10 to 90 seconds.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JPJP-P-2013-201803 | 2013-09-27 | ||
| JP2013201803 | 2013-09-27 | ||
| JPJP-P-2014-008999 | 2014-01-21 | ||
| JP2014008999A JP5580948B1 (en) | 2013-09-27 | 2014-01-21 | Surface treatment method for aluminum cans |
| PCT/JP2014/073834 WO2015045855A1 (en) | 2013-09-27 | 2014-09-09 | Method for treating surface of aluminum can |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020167008750A Division KR20160052660A (en) | 2013-09-27 | 2014-09-09 | Method for treating surface of aluminum can |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020187007891A Division KR20180031086A (en) | 2013-09-27 | 2014-09-09 | Method for treating surface of aluminum can |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| KR20170086672A true KR20170086672A (en) | 2017-07-26 |
Family
ID=51579165
Family Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020177019518A KR20170086672A (en) | 2013-09-27 | 2014-09-09 | Method for treating surface of aluminum can |
| KR1020167008750A KR20160052660A (en) | 2013-09-27 | 2014-09-09 | Method for treating surface of aluminum can |
| KR1020187007891A KR20180031086A (en) | 2013-09-27 | 2014-09-09 | Method for treating surface of aluminum can |
Family Applications After (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020167008750A KR20160052660A (en) | 2013-09-27 | 2014-09-09 | Method for treating surface of aluminum can |
| KR1020187007891A KR20180031086A (en) | 2013-09-27 | 2014-09-09 | Method for treating surface of aluminum can |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US20160230290A1 (en) |
| EP (1) | EP3051005A4 (en) |
| JP (1) | JP5580948B1 (en) |
| KR (3) | KR20170086672A (en) |
| CN (1) | CN105579619A (en) |
| RU (1) | RU2016115927A (en) |
| TW (1) | TW201518548A (en) |
| WO (1) | WO2015045855A1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102017206940A1 (en) * | 2017-04-25 | 2018-10-25 | Mahle International Gmbh | Method for producing a heat exchanger |
| CN109064902B (en) * | 2018-09-20 | 2020-12-11 | 武汉天马微电子有限公司 | Display panel and display device |
| CN109504976A (en) * | 2018-11-30 | 2019-03-22 | 佛山市海明威生态科技股份有限公司 | A kind of ferro-aluminum is collinearly cleaned with removing oil solution and preparation method thereof |
| CN110387546A (en) * | 2019-07-12 | 2019-10-29 | 国家电网有限公司 | A kind of cleaning method of aluminum hardware |
Family Cites Families (28)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1290410C2 (en) * | 1963-11-12 | 1974-05-30 | Pennsalt Chemicals Corp | AQUATIC, ACID FLUORIDE IONS AND AN INORGANIC INHIBITOR CONTAINING SOLUTION, PRACTICALLY FREE OF CHLORIDIONS, AND METHOD FOR PURIFYING ALUMINUM AND ALUMINUM ALLOYS |
| US3464870A (en) * | 1965-06-25 | 1969-09-02 | North American Aluminum Corp | Aluminum polishing process |
| US3728188A (en) * | 1971-07-29 | 1973-04-17 | Amchem Prod | Chrome-free deoxidizing and desmutting composition and method |
| JPS61106783A (en) | 1984-10-30 | 1986-05-24 | Nippon Paint Co Ltd | Cleaner for surface of aluminum |
| US4599116A (en) * | 1984-11-08 | 1986-07-08 | Parker Chemical Company | Alkaline cleaning process |
| CA1273861A (en) * | 1986-01-21 | 1990-09-11 | Thomas H. Fick | Process for cleaning aluminum |
| JP2719612B2 (en) * | 1986-01-21 | 1998-02-25 | ヘンケル コーポレイション | How to clean aluminum |
| US4861440A (en) * | 1986-07-24 | 1989-08-29 | Covino Charles P | Electrolytic formation of an aluminum oxide surface |
| DE3637764A1 (en) * | 1986-11-06 | 1988-05-11 | Hoechst Ag | CARRIER MATERIAL BASED ON ALUMINUM OR ITS ALLOYS FOR OFFSET PRINTING PLATES AND METHOD FOR THE PRODUCTION THEREOF |
| US5064500A (en) * | 1987-06-01 | 1991-11-12 | Henkel Corporation | Surface conditioner for formed metal surfaces |
| DE3838334C2 (en) * | 1987-11-12 | 1999-08-12 | Fuji Photo Film Co Ltd | Process for producing an aluminum support for a lithographic printing plate |
| JPH0273983A (en) * | 1988-09-07 | 1990-03-13 | Nippon Parkerizing Co Ltd | Acidic washing solution for aluminum |
| JPH0432588A (en) * | 1990-05-29 | 1992-02-04 | Furukawa Alum Co Ltd | Production of aluminum alloy sheet for can body |
| US5200114A (en) * | 1990-08-24 | 1993-04-06 | Man-Gill Chemical Company | Alkaline cleaner for reducing stain on aluminum surfaces |
| US5746837A (en) * | 1992-05-27 | 1998-05-05 | Ppg Industries, Inc. | Process for treating an aluminum can using a mobility enhancer |
| DE69404711T2 (en) * | 1993-03-26 | 1998-01-15 | Nippon Paint Co Ltd | Use of an acidic, aqueous cleaning solution for aluminum and aluminum alloys and cleaning methods |
| EP0789094A4 (en) * | 1994-10-21 | 1998-01-14 | Nippon Paint Co Ltd | Aqueous acid cleaning solution for aluminum metal and method for cleaning the metal |
| JP3465998B2 (en) * | 1995-05-30 | 2003-11-10 | 日本パーカライジング株式会社 | Acidic cleaning composition for aluminum-based metal material and cleaning method |
| US6596150B2 (en) * | 1998-05-28 | 2003-07-22 | Fuji Photo Film Co., Ltd. | Production method for an aluminum support for a lithographic printing plate |
| JP4303365B2 (en) | 1998-07-30 | 2009-07-29 | 日本ペイント株式会社 | Cleaning aqueous solution of aluminum metal and cleaning method thereof |
| JP2000309839A (en) * | 1999-04-21 | 2000-11-07 | Furukawa Electric Co Ltd:The | Aluminum alloy for resin-coated can barrel and resin- coated aluminum alloy sheet for can barrel |
| EP1157854A3 (en) * | 2000-05-15 | 2004-05-12 | Fuji Photo Film Co., Ltd. | Support for lithographic printing plate and presensitized plate |
| JP3850253B2 (en) | 2001-10-15 | 2006-11-29 | 古河スカイ株式会社 | Aluminum substrate treatment material with excellent coating adhesion and corrosion resistance |
| JP2004018992A (en) | 2002-06-20 | 2004-01-22 | Furukawa Sky Kk | Nonchromium type aluminum underlayer treatment material having excellent coating film adhesion and acid elution resistance |
| JP4757042B2 (en) | 2006-01-26 | 2011-08-24 | 日本ペイント株式会社 | Acid cleaning agent for aluminum metal material and cleaning method thereof |
| JP2008127625A (en) | 2006-11-21 | 2008-06-05 | Furukawa Sky Kk | Aluminum plate for forming cap having excellent resin adhesiveness after forming, and its manufacturing method |
| JP4909178B2 (en) * | 2007-05-28 | 2012-04-04 | 新日本製鐵株式会社 | Continuous processing method for aluminum alloy sheet |
| JP5390821B2 (en) * | 2008-09-30 | 2014-01-15 | 中央精機株式会社 | Aluminum wheel surface treatment method and alkaline etching solution |
-
2014
- 2014-01-21 JP JP2014008999A patent/JP5580948B1/en active Active
- 2014-09-09 US US15/024,233 patent/US20160230290A1/en not_active Abandoned
- 2014-09-09 CN CN201480052254.6A patent/CN105579619A/en active Pending
- 2014-09-09 WO PCT/JP2014/073834 patent/WO2015045855A1/en active Application Filing
- 2014-09-09 RU RU2016115927A patent/RU2016115927A/en not_active Application Discontinuation
- 2014-09-09 KR KR1020177019518A patent/KR20170086672A/en active Application Filing
- 2014-09-09 EP EP14849358.8A patent/EP3051005A4/en not_active Withdrawn
- 2014-09-09 KR KR1020167008750A patent/KR20160052660A/en active Search and Examination
- 2014-09-09 KR KR1020187007891A patent/KR20180031086A/en not_active Application Discontinuation
- 2014-09-15 TW TW103131785A patent/TW201518548A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| WO2015045855A1 (en) | 2015-04-02 |
| TW201518548A (en) | 2015-05-16 |
| KR20160052660A (en) | 2016-05-12 |
| RU2016115927A (en) | 2017-11-01 |
| EP3051005A4 (en) | 2017-08-09 |
| US20160230290A1 (en) | 2016-08-11 |
| JP2015086466A (en) | 2015-05-07 |
| EP3051005A1 (en) | 2016-08-03 |
| CN105579619A (en) | 2016-05-11 |
| KR20180031086A (en) | 2018-03-27 |
| JP5580948B1 (en) | 2014-08-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5052421A (en) | Treatment of aluminum with non-chrome cleaner/deoxidizer system followed by conversion coating | |
| JP5051679B2 (en) | Alkali cleaning method for aluminum or aluminum alloy DI can | |
| CN104746091A (en) | Cast aluminum alloy white washing descaling solution | |
| KR20170086672A (en) | Method for treating surface of aluminum can | |
| JP2947695B2 (en) | Aqueous cleaning aqueous solution of aluminum-based metal and cleaning method thereof | |
| KR100231390B1 (en) | Acidic cleaning aqueous soultion for aluminium based metal and method for cleaning the same | |
| KR20150126969A (en) | Alkaline cleaning compositions for metal substrates | |
| AU2022259754B2 (en) | Method and compositions for cleaning aluminum cans | |
| JP3465998B2 (en) | Acidic cleaning composition for aluminum-based metal material and cleaning method | |
| EP0976852B1 (en) | Aqueous cleaning solution and method for cleaning aluminium-based metals | |
| JP2007197775A (en) | Acidic cleaning agent for aluminum based metallic material and cleaning method therefor | |
| US5514293A (en) | Acidic cleaning aqueous solution for aluminum and aluminum alloy and process for cleaning the same | |
| CN104060282A (en) | Spring rust cleaning liquid and rust cleaning process | |
| JP7329472B2 (en) | Method for removing scale and/or carbon, and method for producing metal material | |
| JP3192562B2 (en) | Aqueous cleaning aqueous solution of aluminum-based metal and cleaning method thereof | |
| EP1126048A2 (en) | Pickling kit for aluminum substrates and method of pickling | |
| WO2021132154A1 (en) | Acidic cleaning agent for aluminum-based metal materials, and method for cleaning aluminum-based metal material | |
| JP7462105B1 (en) | Method for inhibiting decomposition of surfactant, method for cleaning aluminum or aluminum alloy, and method for producing aluminum material having cleaned surface | |
| JPWO2020071372A1 (en) | Surface treatment agent | |
| EP0351771B1 (en) | Non-chrome cleaner/deoxidizer system | |
| JP6290595B2 (en) | Cleaning solution for aluminum or aluminum alloy | |
| CN103498185B (en) | Cryogenic polishing liquid | |
| CN107829122A (en) | A kind of chain inactivating treatment liquid and its passivation process | |
| JP3038111B2 (en) | Aqueous cleaning aqueous solution of aluminum-based metal and cleaning method | |
| CN112538622A (en) | Environment-friendly process for oxidation pretreatment of aluminum profile |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A107 | Divisional application of patent | ||
| A201 | Request for examination | ||
| E902 | Notification of reason for refusal | ||
| E601 | Decision to refuse application | ||
| E601 | Decision to refuse application | ||
| E801 | Decision on dismissal of amendment | ||
| A107 | Divisional application of patent |