JP2020084319A - Method for removing electrode surface deposit containing lead compound from electrolysis electrode to which lead compound is attached - Google Patents
Method for removing electrode surface deposit containing lead compound from electrolysis electrode to which lead compound is attached Download PDFInfo
- Publication number
- JP2020084319A JP2020084319A JP2019172596A JP2019172596A JP2020084319A JP 2020084319 A JP2020084319 A JP 2020084319A JP 2019172596 A JP2019172596 A JP 2019172596A JP 2019172596 A JP2019172596 A JP 2019172596A JP 2020084319 A JP2020084319 A JP 2020084319A
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- JP
- Japan
- Prior art keywords
- electrode
- electrolysis
- lead
- metal
- acid
- 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.)
- Granted
Links
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 162
- 150000002611 lead compounds Chemical class 0.000 title claims abstract description 94
- 238000000034 method Methods 0.000 title claims abstract description 84
- 239000003513 alkali Substances 0.000 claims abstract description 47
- 239000007864 aqueous solution Substances 0.000 claims abstract description 46
- 238000007654 immersion Methods 0.000 claims abstract description 15
- 150000007524 organic acids Chemical class 0.000 claims abstract description 15
- 239000000243 solution Substances 0.000 claims abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims description 53
- 239000002184 metal Substances 0.000 claims description 53
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 claims description 30
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 24
- 238000010306 acid treatment Methods 0.000 claims description 23
- 239000000758 substrate Substances 0.000 claims description 23
- 238000004140 cleaning Methods 0.000 claims description 22
- 229910000464 lead oxide Inorganic materials 0.000 claims description 22
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims description 22
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 21
- 239000003054 catalyst Substances 0.000 claims description 21
- 238000007598 dipping method Methods 0.000 claims description 20
- 238000000576 coating method Methods 0.000 claims description 17
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 17
- 150000001340 alkali metals Chemical class 0.000 claims description 16
- 239000011248 coating agent Substances 0.000 claims description 16
- 229910044991 metal oxide Inorganic materials 0.000 claims description 14
- 150000004706 metal oxides Chemical class 0.000 claims description 13
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 229910052715 tantalum Inorganic materials 0.000 claims description 12
- 239000010936 titanium Substances 0.000 claims description 12
- 229910052719 titanium Inorganic materials 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 10
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 9
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims description 8
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 8
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims description 8
- 150000002739 metals Chemical class 0.000 claims description 8
- 229910052758 niobium Inorganic materials 0.000 claims description 8
- 239000010955 niobium Substances 0.000 claims description 8
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 7
- 239000000956 alloy Substances 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 6
- 229910045601 alloy Inorganic materials 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 5
- 235000019253 formic acid Nutrition 0.000 claims description 5
- 229910052735 hafnium Inorganic materials 0.000 claims description 5
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 4
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 4
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 239000011975 tartaric acid Substances 0.000 claims description 4
- 235000002906 tartaric acid Nutrition 0.000 claims description 4
- 235000011054 acetic acid Nutrition 0.000 claims description 3
- 235000015165 citric acid Nutrition 0.000 claims description 3
- 150000001735 carboxylic acids Chemical class 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 24
- 238000007747 plating Methods 0.000 abstract description 15
- 239000011889 copper foil Substances 0.000 abstract description 13
- 238000004519 manufacturing process Methods 0.000 abstract description 13
- 229910052802 copper Inorganic materials 0.000 abstract description 10
- 239000010949 copper Substances 0.000 abstract description 10
- 239000002253 acid Substances 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 229910021514 lead(II) hydroxide Inorganic materials 0.000 description 25
- MFEVGQHCNVXMER-UHFFFAOYSA-L 1,3,2$l^{2}-dioxaplumbetan-4-one Chemical compound [Pb+2].[O-]C([O-])=O MFEVGQHCNVXMER-UHFFFAOYSA-L 0.000 description 18
- 229910000003 Lead carbonate Inorganic materials 0.000 description 18
- RYZCLUQMCYZBJQ-UHFFFAOYSA-H lead(2+);dicarbonate;dihydroxide Chemical compound [OH-].[OH-].[Pb+2].[Pb+2].[Pb+2].[O-]C([O-])=O.[O-]C([O-])=O RYZCLUQMCYZBJQ-UHFFFAOYSA-H 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 239000011888 foil Substances 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- 230000001680 brushing effect Effects 0.000 description 6
- -1 alkaline earth metal carbonates Chemical class 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 5
- 229910000457 iridium oxide Inorganic materials 0.000 description 5
- 238000005507 spraying Methods 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 4
- 238000005498 polishing Methods 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 238000004544 sputter deposition Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 239000012670 alkaline solution Substances 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 150000004679 hydroxides Chemical class 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- ZBUQRSWEONVBES-UHFFFAOYSA-L beryllium carbonate Chemical compound [Be+2].[O-]C([O-])=O ZBUQRSWEONVBES-UHFFFAOYSA-L 0.000 description 2
- 229910000023 beryllium carbonate Inorganic materials 0.000 description 2
- 229910001865 beryllium hydroxide Inorganic materials 0.000 description 2
- XTIMETPJOMYPHC-UHFFFAOYSA-M beryllium monohydroxide Chemical compound O[Be] XTIMETPJOMYPHC-UHFFFAOYSA-M 0.000 description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 description 2
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- JXTHNDFMNIQAHM-UHFFFAOYSA-N dichloroacetic acid Chemical compound OC(=O)C(Cl)Cl JXTHNDFMNIQAHM-UHFFFAOYSA-N 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 2
- 238000010884 ion-beam technique Methods 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- WPFGFHJALYCVMO-UHFFFAOYSA-L rubidium carbonate Chemical compound [Rb+].[Rb+].[O-]C([O-])=O WPFGFHJALYCVMO-UHFFFAOYSA-L 0.000 description 2
- 229910000026 rubidium carbonate Inorganic materials 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 229910000018 strontium carbonate Inorganic materials 0.000 description 2
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 2
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 229910001362 Ta alloys Inorganic materials 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 229960005215 dichloroacetic acid Drugs 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- YZMHQCWXYHARLS-UHFFFAOYSA-N naphthalene-1,2-disulfonic acid Chemical compound C1=CC=CC2=C(S(O)(=O)=O)C(S(=O)(=O)O)=CC=C21 YZMHQCWXYHARLS-UHFFFAOYSA-N 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
- C25D17/10—Electrodes, e.g. composition, counter electrode
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
- C25D1/04—Wires; Strips; Foils
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/08—Rinsing
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
Description
本発明は、電解銅箔製造、または銅メッキ等の工業電解における電解により、表面に鉛化合物を含む電極表面付着物が付着した電解用電極から電極表面付着物を除去する方法に関するものである。 TECHNICAL FIELD The present invention relates to a method for removing electrode surface deposits from an electrode for electrolysis having electrode surface deposits containing a lead compound attached to the surface thereof by electrolytic copper foil production or electrolysis in industrial electrolysis such as copper plating.
従来、電解銅箔製造、または銅メッキ等の工業電解における電解においては、チタン、タンタル等のバルブメタル、またはバルブメタル合金からなる電極基体の表面に、直接、イリジウム酸化物を含有する電極触媒層が被覆された酸素発生用電極が用いられている。 Conventionally, in electrolysis in the production of electrolytic copper foil or in industrial electrolysis such as copper plating, an electrode catalyst layer containing iridium oxide is directly formed on the surface of an electrode substrate made of a valve metal such as titanium or tantalum, or a valve metal alloy. An oxygen generating electrode coated with is used.
しかしながら、この種の酸素発生用電極は、一定期間以上使用すると、チタン、タンタル等のバルブメタル、またはバルブメタル合金からなる電極基体とイリジウム酸化物等の電極触媒層との界面が腐食し、電極基体の表面に不働態層が形成されるため電解を行うことが困難となる。そのため、電極基体表面を新しい表面が出るまで物理的方法で削るか、若しくは新たに電解用電極を電極基体から製作する必要があった。 However, when this type of oxygen generating electrode is used for a certain period of time or longer, the interface between the electrode base made of a valve metal such as titanium or tantalum or a valve metal alloy and the electrode catalyst layer such as iridium oxide is corroded, and the electrode Since a passive layer is formed on the surface of the substrate, it becomes difficult to perform electrolysis. Therefore, it is necessary to physically grind the surface of the electrode substrate until a new surface appears, or to manufacture a new electrode for electrolysis from the electrode substrate.
また、酸素発生用電極として、チタン、タンタル等のバルブメタル、またはバルブメタル合金からなる電極基体の表面に、０.５〜２０μｍのタンタル、ニオブ等の金属、または金属酸化物、若しくは金属合金を含む層を形成し、該層の表面にイリジウム酸化物を含有する電極触媒層が被覆された電解用電極を用いた場合、電極基体と触媒層の界面腐食が抑制されることが分かっている。 Further, as an oxygen generating electrode, 0.5 to 20 μm of a metal such as tantalum or niobium, or a metal oxide or a metal alloy is formed on the surface of an electrode base made of a valve metal such as titanium or tantalum or a valve metal alloy. It has been known that when an electrode for electrolysis in which a layer containing the same is formed and the surface of the layer is coated with an electrode catalyst layer containing iridium oxide is used, interfacial corrosion between the electrode substrate and the catalyst layer is suppressed.
しかしながら、上記酸素発生用電極であっても、これを電解銅箔製造、または銅メッキにおける電解に使用した場合、電解用電極の電極表面に、硫酸鉛または酸化鉛を含む鉛化合物が付着する。電解時においては、電解液中に含まれる鉛は、良導電体である酸化鉛として電極表面に付着するが、電解停止時には、導電体の酸化鉛から不良導電体である硫酸鉛に変化する。更に、電極表面付着物である鉛化合物（硫酸鉛、または酸化鉛）は、電解開始・停止時若しくは電解中に、電解用電極の表面から脱落する。その結果、上記の酸素発生用電極は、電解用電極として、電流分布が不均一となり、銅箔厚み不良の原因となり、電解用電極として長期間、継続使用できないという課題を有していた。 However, even in the case of the oxygen generating electrode, when it is used for electrolytic copper foil production or electrolysis in copper plating, a lead compound containing lead sulfate or lead oxide adheres to the electrode surface of the electrode for electrolysis. During electrolysis, lead contained in the electrolytic solution adheres to the electrode surface as lead oxide, which is a good conductor, but when the electrolysis is stopped, the lead oxide of the conductor changes to lead sulfate, which is a poor conductor. Further, the lead compound (lead sulfate or lead oxide) that is a substance adhering to the surface of the electrode falls off from the surface of the electrode for electrolysis at the time of starting/stopping electrolysis or during electrolysis. As a result, the above-mentioned oxygen generation electrode has a problem that the current distribution becomes non-uniform as an electrode for electrolysis, causes a defective copper foil thickness, and cannot be continuously used as an electrode for electrolysis for a long period of time.
このような場合、上記酸素発生用電極は、電解に使用した電解用電極の表面を物理的に研磨、洗浄することでこすり落とすか、あるいは濃硝酸と過酸化水素水の混合溶液に電解用電極を浸漬する酸処理工程の後、高圧で水洗することにより、鉛化合物を含む電極表面付着物を除去していた（特許文献１）。
しかるに、上記酸素発生用電極は、連続で３ヶ月使用した場合、前記研磨、洗浄処理による電解用電極表面から鉛化合物を含む電極付着物を除去することは困難であった。
また、前記酸処理工程を用いる電解用電極から鉛化合物を含む電極付着物の除去方法は、鉛化合物を含む電極付着物の除去性には優れるが、取扱いにくい過酸化水素水を用いる点、環境負荷が大きい硝酸を用いる点等の問題があった。
In such a case, the electrode for oxygen generation is scraped off by physically polishing and cleaning the surface of the electrode for electrolysis used for electrolysis, or the electrode for electrolysis is added to a mixed solution of concentrated nitric acid and hydrogen peroxide solution. After the acid treatment step of dipping, the electrode surface deposit containing the lead compound was removed by washing with water under high pressure (Patent Document 1).
However, when the oxygen generating electrode is continuously used for 3 months, it is difficult to remove the electrode deposit containing the lead compound from the electrode surface for electrolysis by the polishing and cleaning treatment.
Further, the method for removing electrode deposits containing a lead compound from the electrode for electrolysis using the acid treatment step is excellent in the removability of the electrode deposits containing a lead compound, but it is difficult to handle, and hydrogen peroxide solution is used. There were problems such as using nitric acid, which has a large load.
本発明は、上記の従来法の課題を解消し、電解銅箔製造、または銅メッキ等の工業電解における電解により、表面に鉛化合物を含む電極表面付着物が付着した電解用電極、特に、バルブメタル、またはバルブメタル合金からなる電極基体の表面にタンタル、ニオブ等の金属または金属酸化物、若しくは金属合金を含む層（中間層）を形成し、該層（中間層）の表面に電極触媒層が被覆された電解用電極の表面に付着した、鉛化合物を含む電極表面付着物を効率的に除去することができ、安全且つ環境負荷の低い除去方法を提供することを目的とするものである。 The present invention solves the problems of the conventional methods described above, electrolytic copper foil production, or by electrolysis in industrial electrolysis such as copper plating, an electrode for electrolysis in which an electrode surface deposit containing a lead compound is attached to the surface, in particular, a valve. A layer (intermediate layer) containing a metal such as tantalum or niobium or a metal oxide or a metal alloy is formed on the surface of an electrode substrate made of a metal or a valve metal alloy, and an electrode catalyst layer is formed on the surface of the layer (intermediate layer). It is an object of the present invention to provide a safe and low environmental load removal method capable of efficiently removing electrode surface deposits containing a lead compound, which adheres to the surface of an electrode for electrolysis coated with ..
本発明は、上記目的を達成するために、下記の電解用電極表面からの鉛化合物を含む電極付着物の除去方法を提供することにある。 In order to achieve the above-mentioned object, the present invention provides the following method for removing electrode deposits containing a lead compound from the surface of an electrode for electrolysis.
項１． 表面に鉛化合物を含む電極表面付着物が付着した電解用電極を、
アルカリ水溶液に浸漬するアルカリ浸漬工程と、
有機酸に浸漬する酸処理工程に付することにより、電解用電極表面に付着した鉛化合物を含む電極表面付着物を除去する方法。
項２． アルカリ浸漬工程後、及び／または酸処理工程後に、表面洗浄工程に付することを特徴とする項１に記載の方法。
項３． 有機酸が、カルボン酸、またはスルホン酸である項１または２に記載の方法。
項４． 有機酸が酢酸、ギ酸、シュウ酸、クエン酸、酒石酸から選択される１種以上である項１から３の何れかに記載の方法。
項５． アルカリ水溶液が、アンモニア水、アルカリ金属、またはアルカリ土類金属の水酸化物若しくは炭酸塩の水溶液である項１から４の何れかに記載の方法。
項６． アルカリ水溶液が、水酸化ナトリウム、または水酸化カリウムの水溶液である項１から５の何れかに記載の方法。
項７． 鉛化合物が、硫酸鉛、または酸化鉛である項１から６の何れかに記載の方法。
項８． 電解用電極が、該電極表面に白金族金属、またはその酸化物を含有する電極触媒層が被覆された電解用電極である項１から７の何れかに記載の方法。
項９． 電解用電極が、バルブメタル、またはバルブメタル合金からなる電極基体の表面に金属、または金属酸化物、若しくは金属合金を含む層（中間層）が被覆された電解用電極である項１から８の何れかに記載の方法。
項１０． 前記金属がチタン、タンタル、ニオブ、ジルコニウム及びハフニウムから選択される１種以上の金属または金属酸化物、若しくはその合金である項９に記載の方法。
項１１． 表面に鉛化合物を含む電極表面付着物が付着した電解用電極を、
電解用電極表面にアルカリ水溶液を塗布するアルカリ塗布工程に付することにより、電解用電極表面に付着した鉛化合物を含む電極表面付着物を除去する方法。
項１２． アルカリ塗布工程後に、電解用電極を乾燥工程に付することを特徴とする項１１に記載の方法。
項１３． 乾燥工程後に、表面洗浄工程に付することを特徴とする項１１または項１２に記載の方法。
項１４． アルカリ水溶液が、アンモニア水、アルカリ金属またはアルカリ土類金属の水酸化物、若しくは炭酸塩の水溶液である項１１から１３の何れかに記載の方法。
項１５． アルカリ水溶液が、水酸化ナトリウム、または水酸化カリウムの水溶液である項１１から１４の何れかに記載の方法。
項１６． 鉛化合物が、硫酸鉛、または酸化鉛である項１１から１５の何れかに記載の方法。
項１７． 電解用電極が、該電極表面に白金族金属、またはその酸化物を含有する電極触媒層が被覆された電解用電極である項１１から１６の何れかに記載の方法。
項１８． 電解用電極が、バルブメタルまたはバルブメタル合金からなる電極基体の表面に金属、または金属酸化物、若しくは金属合金を含む層（中間層）が被覆された電解用電極である項１１から１７の何れかに記載の方法。
項１９． 前記金属がチタン、タンタル、ニオブ、ジルコニウム及びハフニウムから選択される１種以上の金属または金属酸化物、若しくはその合金である項１８に記載の方法。
Item 1. An electrode for electrolysis where the electrode surface deposit containing a lead compound is attached to the surface,
An alkali dipping step of dipping in an alkaline aqueous solution,
A method for removing an electrode surface deposit containing a lead compound adhered to the electrode surface for electrolysis by subjecting to an acid treatment step of immersing in an organic acid.
Item 2. Item 2. The method according to Item 1, which is subjected to a surface cleaning step after the alkali immersion step and/or the acid treatment step.
Item 3. Item 3. The method according to Item 1 or 2, wherein the organic acid is carboxylic acid or sulfonic acid.
Item 4. Item 4. The method according to any one of Items 1 to 3, wherein the organic acid is at least one selected from acetic acid, formic acid, oxalic acid, citric acid, and tartaric acid.
Item 5. Item 5. The method according to any one of Items 1 to 4, wherein the alkaline aqueous solution is an aqueous ammonia solution, an aqueous solution of a hydroxide or carbonate of an alkaline metal, or an alkaline earth metal.
Item 6. Item 6. The method according to any one of Items 1 to 5, wherein the alkaline aqueous solution is an aqueous solution of sodium hydroxide or potassium hydroxide.
Item 7. Item 7. The method according to any one of Items 1 to 6, wherein the lead compound is lead sulfate or lead oxide.
Item 8. Item 8. The method according to any one of Items 1 to 7, wherein the electrode for electrolysis is an electrode for electrolysis in which an electrode catalyst layer containing a platinum group metal or an oxide thereof is coated on the surface of the electrode.
Item 9. Item 1. The electrolysis electrode is an electrolysis electrode in which the surface of an electrode substrate made of a valve metal or a valve metal alloy is coated with a layer containing metal, metal oxide, or metal alloy (intermediate layer). The method according to any one.
Item 10. Item 10. The method according to Item 9, wherein the metal is at least one metal selected from titanium, tantalum, niobium, zirconium, and hafnium, a metal oxide, or an alloy thereof.
Item 11. An electrode for electrolysis where the electrode surface deposit containing a lead compound is attached to the surface,
A method of removing an electrode surface deposit containing a lead compound adhered to the surface of an electrode for electrolysis by subjecting the surface of the electrode for electrolysis to an alkali application step of applying an alkaline aqueous solution.
Item 12. Item 12. The method according to Item 11, wherein the electrolytic electrode is subjected to a drying step after the alkali coating step.
Item 13. Item 13. The method according to Item 11 or 12, which is subjected to a surface cleaning step after the drying step.
Item 14. Item 14. The method according to any one of Items 11 to 13, wherein the aqueous alkaline solution is aqueous ammonia, an aqueous solution of a hydroxide of an alkali metal or an alkaline earth metal, or a carbonate.
Item 15. Item 15. The method according to any one of Items 11 to 14, wherein the alkaline aqueous solution is an aqueous solution of sodium hydroxide or potassium hydroxide.
Item 16. Item 16. The method according to any one of Items 11 to 15, wherein the lead compound is lead sulfate or lead oxide.
Item 17. Item 17. The method according to any one of Items 11 to 16, wherein the electrode for electrolysis is an electrode for electrolysis in which the electrode surface is covered with an electrode catalyst layer containing a platinum group metal or an oxide thereof.
Item 18. Any of items 11 to 17 wherein the electrode for electrolysis is an electrode for electrolysis in which a layer (intermediate layer) containing a metal, a metal oxide, or a metal alloy is coated on the surface of an electrode substrate made of a valve metal or a valve metal alloy. The method described in crab.
Item 19. Item 19. The method according to Item 18, wherein the metal is at least one metal selected from titanium, tantalum, niobium, zirconium, and hafnium, a metal oxide, or an alloy thereof.
本発明の電解用電極表面から鉛化合物を含む電極付着物の除去方法によれば、電解用電極表面に付着した鉛化合物である硫酸鉛、または酸化鉛を含む電極表面付着物を水酸化ナトリウムまたは炭酸ナトリウム等のアルカリ水溶液に浸漬するアルカリ浸漬工程に付することよって、硫酸鉛または酸化鉛を水酸化鉛または炭酸鉛に変換させ、次いで水酸化鉛または炭酸鉛を含む電極表面付着物を有機酸（例えば、カルボン酸またはスルホン酸等）に浸漬する酸処理工程に付することによって、水酸化鉛または炭酸鉛を除去（溶解）することができる。
また、電解用電極表面に付着した鉛化合物（硫酸鉛または酸化鉛）を含む電極表面付着物に、水酸化ナトリウムまたは炭酸ナトリウム等のアルカリ水溶液を塗布するアルカリ塗布工程によって、硫酸鉛または酸化鉛を水酸化鉛または炭酸鉛に変化させ、水酸化鉛または炭酸鉛を除去可能となる。
According to the method for removing an electrode deposit containing a lead compound from the electrode surface for electrolysis of the present invention, lead sulfate which is a lead compound attached to the electrode surface for electrolysis, or an electrode surface deposit containing lead oxide is treated with sodium hydroxide or Lead sulfate or lead oxide is converted to lead hydroxide or lead carbonate by subjecting it to an alkali dipping step of dipping in an alkaline aqueous solution such as sodium carbonate, and then an electrode surface deposit containing lead hydroxide or lead carbonate is treated with an organic acid. Lead oxide or lead carbonate can be removed (dissolved) by subjecting to an acid treatment step of dipping in (for example, carboxylic acid or sulfonic acid).
In addition, lead sulfate or lead oxide is applied to an electrode surface deposit containing a lead compound (lead sulfate or lead oxide) attached to the electrode surface for electrolysis by an alkali application step of applying an alkaline aqueous solution such as sodium hydroxide or sodium carbonate. Lead hydroxide or lead carbonate can be removed by changing to lead hydroxide or lead carbonate.
更に、アルカリ浸漬工程と酸処理工程、またはアルカリ塗布工程に付した後、電解用電極表面に残存する鉛化合物（水酸化鉛または炭酸鉛）を、ブラシ等を用いたブラッシングによる表面洗浄工程に付することによって、物理的に除去することが出来るため、鉛化合物である電極表面付着物を効果的に除去することが可能となる。 Furthermore, after subjecting to an alkali dipping step and an acid treatment step, or an alkali coating step, the lead compound (lead hydroxide or lead carbonate) remaining on the electrode surface for electrolysis is subjected to a surface cleaning step by brushing with a brush or the like. By doing so, since it can be physically removed, it becomes possible to effectively remove the electrode surface deposits which are lead compounds.
本発明の除去方法は、酸処理工程を用いる場合、用いる酸は、鉱酸等の強酸ではなく、安全且つ環境負荷の低い有機酸を用いるか、または酸処理工程を用いないため、安全且つ環境負荷の低く、電解用電極表面から鉛化合物を含む電極付着物の除去効率に優れる除去方法である。 In the removal method of the present invention, when an acid treatment step is used, the acid used is not a strong acid such as a mineral acid, but an organic acid that is safe and has a low environmental load, or does not use an acid treatment step. The removal method has a low load and is excellent in the removal efficiency of the electrode deposit containing the lead compound from the electrode surface for electrolysis.
以下に、本発明について詳細に説明する。 The present invention will be described in detail below.
（アルカリ浸漬工程）
電解用電極が、金属箔製造用（例えば、銅箔製造用）である場合、電解用電極の表面には、鉛化合物を含む電極表面付着物が付着し、電解用電極の電極性能が阻害される。このような場合、表面に鉛化合物（例えば、硫酸鉛、または酸化鉛等）を含む電極表面付着物が付着した（電極性能が阻害されている）電解用電極を、アルカリ浸漬工程に付することで電解用電極表面に付着した鉛化合物を含む電極表面付着物を除去することができる。
(Alkali immersion process)
When the electrode for electrolysis is for producing metal foil (for example, for producing copper foil), electrode surface deposits containing lead compounds adhere to the surface of the electrode for electrolysis, which hinders the electrode performance of the electrode for electrolysis. It In such a case, the electrode for electrolysis, which has an electrode surface deposit containing a lead compound (for example, lead sulfate, lead oxide, etc.) attached to its surface (inhibited electrode performance), should be subjected to the alkali dipping process. The electrode surface deposits containing the lead compound adhered to the electrode surface for electrolysis can be removed.
具体的には、アンモニア水、アルカリ金属またはアルカリ土類金属の水酸化物、若しくは炭酸塩等のアルカリ水溶液に、電解用電極を数時間程度浸漬することで、鉛化合物を含む電極表面付着物中の硫酸鉛または酸化鉛を水酸化鉛または炭酸鉛へ変換させることができる。 Specifically, by immersing the electrode for electrolysis for about several hours in an aqueous solution of ammonia, an alkali metal or alkaline earth metal hydroxide or carbonate, or the like, an electrode surface deposit containing a lead compound The lead sulfate or lead oxide of the above can be converted into lead hydroxide or lead carbonate.
また、電解用電極が、金属メッキ用（例えば、銅メッキ用）である場合、電解用電極の表面には、鉛化合物である硫酸鉛を含む電極表面付着物が付着し、電解用電極の電極性能が阻害される。このような場合、表面に鉛化合物を含む電極付着物が付着した（電極性能が阻害されている）電解用電極を、アルカリ浸漬工程に付することで、電解用電極表面に付着した鉛化合物を含む電極表面付着物を除去することができる。 Further, when the electrode for electrolysis is for metal plating (for example, for copper plating), an electrode surface deposit containing lead sulfate, which is a lead compound, adheres to the surface of the electrode for electrolysis, and Performance is hindered. In such a case, by subjecting the electrode for electrolysis where the electrode deposit containing the lead compound adheres to the surface (the electrode performance is hindered) to the alkali dipping step, the lead compound attached to the surface of the electrode for electrolysis can be removed. It is possible to remove the deposits on the surface of the electrode.
具体的には、アンモニア水、アルカリ金属またはアルカリ土類金属の水酸化物、若しくは炭酸塩等のアルカリ水溶液に電解用電極を数時間程度浸漬することで、鉛化合物を含む電極表面付着物中の硫酸鉛を水酸化鉛または炭酸鉛へ変換させることができる。 Specifically, by immersing the electrode for electrolysis for about several hours in an aqueous solution of ammonia, an alkali metal or alkaline earth metal hydroxide, or an alkaline aqueous solution such as a carbonate, it is possible to obtain Lead sulfate can be converted to lead hydroxide or lead carbonate.
なお、本発明において、電解用電極の電極性能が阻害されているとは、電解によって生成される金属箔またはメッキの単位面積当たり重量（厚み）公差が、電極表面に鉛化合物を含む電極表面付着物が付着することにより、基準値以上になったものを意味する。例えば、連続的に製造される銅箔の場合、１ｍ２あたりの銅箔重量が基準値より１％以上異なる場合、電解用電極の電極性能が阻害されていると判断する。電解によって生成される金属箔またはメッキの厚み公差が基準値以上になった電解用電極を本発明の除去方法に付することにより、電解用電極表面から鉛化合物を含む電極付着物を効率的に除去することができる。 In the present invention, the fact that the electrode performance of the electrode for electrolysis is impaired means that the weight (thickness) tolerance per unit area of the metal foil or plating produced by electrolysis is the electrode surface containing a lead compound on the electrode surface. It means that a kimono adheres to a standard value or more due to adhesion. For example, in the case of a continuously manufactured copper foil, when the copper foil weight per 1 m 2 differs from the reference value by 1% or more, it is determined that the electrode performance of the electrode for electrolysis is hindered. By subjecting the electrode for electrolysis, which has a thickness tolerance of the metal foil or plating generated by electrolysis to a reference value or more, to the removal method of the present invention, electrode deposits containing a lead compound can be efficiently formed from the surface of the electrode for electrolysis. It can be removed.
本発明のアルカリ浸漬工程に用いることのできるアルカリ水溶液は、電解用電極表面に付着した鉛化合物を含む電極表面付着物を効率的に除去できるものであれば、特に制限なく用いることができる。例えば、アルカリ水溶液としては、アンモニア水、アルカリ金属またはアルカリ土類金属の水酸化物若しくは炭酸塩の水溶液を例示することができる。 The alkaline aqueous solution that can be used in the alkaline dipping step of the present invention can be used without particular limitation as long as it can efficiently remove the electrode surface deposits containing the lead compound that has adhered to the electrode surface for electrolysis. Examples of the alkaline aqueous solution include aqueous ammonia, and aqueous solutions of hydroxides or carbonates of alkali metals or alkaline earth metals.
アルカリ金属、またはアルカリ土類金属の水酸化物としては、水酸化リチウム、水酸化ナトリウム、水酸化カリウム、水酸化ルビジウム、水酸化セシウム、水酸化ベリリウム、水酸化マグネシウム、水酸化カルシウム、水酸化ストロンチウム、水酸化バリウム等を例示することができる。 Examples of hydroxides of alkali metals or alkaline earth metals include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, beryllium hydroxide, magnesium hydroxide, calcium hydroxide and strontium hydroxide. , Barium hydroxide and the like can be exemplified.
アルカリ金属、またはアルカリ土類金属の炭酸塩としては、炭酸リチウム、炭酸ナトリウム、炭酸カリウム、炭酸ルビジウム、炭酸セシウム、炭酸ベリリウム、炭酸マグネシウム、炭酸カルシウム、炭酸ストロンチウム、炭酸バリウム等を例示することができる。上述したものの中でも、アルカリ金属、またはアルカリ土類金属の水酸化物が好ましく、水酸化ナトリウム、または水酸化カリウムがより好ましい。 Examples of the alkali metal or alkaline earth metal carbonates include lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, beryllium carbonate, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate and the like. .. Among the above-mentioned ones, alkali metal or alkaline earth metal hydroxides are preferable, and sodium hydroxide or potassium hydroxide is more preferable.
本発明のアルカリ浸漬工程に用いるアルカリ水溶液の濃度は、目的に応じて適宜選択することができるが、例えば、１質量％から４８質量％（室温２５℃）の範囲のものであれば特に問題なく用いることができる。好ましくは３質量％〜３５質量％（室温２５℃）の範囲であり、より好ましくは４質量％から３０質量％（室温２５℃）の範囲である。なお、アルカリ水溶液の濃度は、４８質量％を超えると、電解用電極の触媒層が剥離する恐れがあり、１質量％未満では、鉛化合物を含む電極表面付着物中の硫酸鉛を水酸化鉛または炭酸鉛に変換する反応が十分におこらず、除去効率の点で不十分となる。 The concentration of the alkaline aqueous solution used in the alkaline dipping step of the present invention can be appropriately selected according to the purpose, but there is no particular problem as long as it is in the range of 1% by mass to 48% by mass (room temperature 25° C.). Can be used. The range is preferably 3% by mass to 35% by mass (room temperature 25°C), and more preferably 4% by mass to 30% by mass (room temperature 25°C). If the concentration of the alkaline aqueous solution exceeds 48% by mass, the catalyst layer of the electrode for electrolysis may peel off, and if it is less than 1% by mass, the lead sulfate in the electrode surface deposit containing the lead compound may be converted into lead hydroxide. Alternatively, the reaction for converting to lead carbonate does not sufficiently occur, and the removal efficiency becomes insufficient.
本発明のアルカリ浸漬工程において、アルカリ水溶液の温度は特に制限されないが、例えば、０〜９０℃程度の範囲であればよく、好ましくは室温（２５℃）〜８０℃程度の範囲であり、より好ましくは５０℃から７０℃程度の範囲である。また、アルカリ浸漬工程における、アルカリ水溶液への電解用電極の浸漬時間については、電解用電極表面に付着した鉛化合物が（硫酸鉛または酸化鉛が水酸化鉛または炭酸鉛等へ）変換する程度の時間であればよく、例えば、電解用電極表面に付着した鉛化合物が硫酸鉛である場合、アルカリ水溶液として、アルカリ金属、またはアルカリ土類金属の水酸化物、若しくは炭酸塩の水溶液を用いた際には、付着した硫酸鉛が水酸化鉛、または炭酸鉛に変換するために十分な時間であればよい。また、電解用電極表面に付着した鉛化合物が酸化鉛である場合、アルカリ水溶液として、アルカリ金属、またはアルカリ土類金属の水酸化物、若しくは炭酸塩の水溶液を用いた際には、付着した酸化鉛が水酸化鉛、または炭酸鉛に変換するために十分な時間であればよい。アルカリ水溶液への浸漬時間は通常、１０分〜１０時間程度であればよく、好ましくは１時間から５時間程度である。 In the alkali dipping step of the present invention, the temperature of the alkaline aqueous solution is not particularly limited, but may be, for example, in the range of 0 to 90°C, preferably room temperature (25°C) to 80°C, and more preferably Is in the range of about 50°C to 70°C. In addition, the immersion time of the electrode for electrolysis in the alkaline aqueous solution in the alkali dipping step is such that the lead compound attached to the surface of the electrode for electrolysis converts lead sulfate or lead oxide to lead hydroxide or lead carbonate. For example, when the lead compound attached to the electrode surface for electrolysis is lead sulfate, when an alkali metal or alkaline earth metal hydroxide or carbonate aqueous solution is used as the alkali aqueous solution, The time required for converting the attached lead sulfate into lead hydroxide or lead carbonate is sufficient. Further, when the lead compound attached to the surface of the electrode for electrolysis is lead oxide, when an aqueous solution of an alkali metal or alkaline earth metal hydroxide or carbonate is used as the alkaline aqueous solution, the adhered oxide is Sufficient time is required to convert lead into lead hydroxide or lead carbonate. The immersion time in the alkaline aqueous solution is usually about 10 minutes to 10 hours, preferably about 1 to 5 hours.
アルカリ浸漬工程に付した電解用電極は、そのまま後述する酸処理工程に付してもよく、また、後述する表面洗浄工程に付した後、酸処理工程に付してもよい。アルカリ浸漬工程に付した後にどの工程に付すかは、電解用電極表面に付着した鉛化合物を含む電極表面付着物の付着量に応じて、適宜検討することができる。 The electrode for electrolysis that has been subjected to the alkali immersion step may be directly subjected to the acid treatment step described later, or may be subjected to the surface cleaning step described later and then subjected to the acid treatment step. Which step is performed after the alkali immersion step can be appropriately examined according to the amount of the electrode surface deposit containing the lead compound attached to the electrode surface for electrolysis.
（酸処理工程）
本発明の除法方法において、アルカリ浸漬工程に次いで、電解用電極を酸処理工程に付することで、電解用電極表面に付着した鉛化合物を含む電極表面付着物を効率的に除去することができる。
(Acid treatment step)
In the removal method of the present invention, the electrode for electrolysis is subjected to an acid treatment step after the step of dipping the alkali, whereby the electrode surface deposit containing the lead compound attached to the surface of the electrode for electrolysis can be efficiently removed. ..
具体的には、電解用電極を有機酸に数時間程度浸漬し、アルカリ浸漬工程で変換した水酸化鉛または炭酸鉛を溶解させることで、電解用電極表面から鉛化合物を含む電極付着物を除去することができる Specifically, the electrode for electrolysis is immersed in an organic acid for about several hours, and the lead hydroxide or lead carbonate converted in the alkali immersion step is dissolved to remove electrode deposits containing lead compounds from the surface of the electrode for electrolysis. can do
本発明の酸処理工程に用いることのできる有機酸は、特に限定されないが、例えば、カルボン酸、またはスルホン酸を用いることができる。 The organic acid that can be used in the acid treatment step of the present invention is not particularly limited, but for example, carboxylic acid or sulfonic acid can be used.
具体的ものとしては、シュウ酸、マロン酸、コハク酸、アジピン酸、セバシン酸、クエン酸、フマル酸、マレイン酸、蟻酸、酢酸、酒石酸等のカルボン酸、ｐ−トルエンスルホン酸、メタンスルホン酸、トリフルオロ酢酸、ジクロロ酢酸、トリクロロ酢酸、トリフルオロメタンスルホン酸、ベンゼンスルホン酸、ナフタレンスルホン酸、ナフタレンジスルホン酸等のスルホン酸等を例示することができる。 Specifically, oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, citric acid, fumaric acid, maleic acid, formic acid, acetic acid, carboxylic acids such as tartaric acid, p-toluenesulfonic acid, methanesulfonic acid, Examples thereof include sulfonic acids such as trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid and naphthalenedisulfonic acid.
中でも、酢酸、ギ酸、シュウ酸、クエン酸、酒石酸が好ましく、酢酸またはギ酸がより好ましい。用いる有機酸の濃度は特に限定されないが、５０質量％以上（室温２５℃）であればよく、７５質量％以上（室温２５℃）が好ましく、９０質量％以上（室温２５℃）がより好ましい。 Among them, acetic acid, formic acid, oxalic acid, citric acid and tartaric acid are preferable, and acetic acid or formic acid is more preferable. The concentration of the organic acid used is not particularly limited, but may be 50% by mass or more (room temperature 25° C.), preferably 75% by mass or more (room temperature 25° C.), and more preferably 90% by mass or more (room temperature 25° C.).
本発明の酸処理工程において、有機酸の温度は特に制限されないが、例えば、０〜９０℃程度の範囲であればよく、好ましくは室温（２５℃）〜８０℃程度の範囲であり、より好ましくは５０℃から７０℃程度の範囲である。また、酸処理工程における、有機酸への電解用電極の浸漬時間については、電解用電極表面に付着した鉛化合物が溶解する程度の時間であればよく、例えば、電解用電極表面に付着した鉛化合物が水酸化鉛または炭酸鉛である場合、水酸化鉛、または炭酸鉛が溶解するために十分な時間であればよい。有機酸への浸漬時間は通常、１０分〜１０時間程度であればよく、好ましくは１時間から５時間程度である。 In the acid treatment step of the present invention, the temperature of the organic acid is not particularly limited, but may be, for example, in the range of 0 to 90°C, preferably room temperature (25°C) to 80°C, and more preferably Is in the range of about 50°C to 70°C. In the acid treatment step, the immersion time of the electrode for electrolysis in the organic acid may be a time such that the lead compound attached to the surface of the electrode for electrolysis is dissolved, and for example, lead attached to the surface of the electrode for electrolysis is used. When the compound is lead hydroxide or lead carbonate, it may have sufficient time for the lead hydroxide or lead carbonate to dissolve. The immersion time in the organic acid is usually about 10 minutes to 10 hours, preferably about 1 to 5 hours.
酸処理工程に付した電解用電極は、そのまま後述する表面洗浄工程に付してもよい。また、再度アルカリ浸漬工程に付することで効率的に電解用電極表面から鉛化合物を含む電極付着物を除去することができる。 The electrode for electrolysis that has been subjected to the acid treatment step may be directly subjected to the surface cleaning step described later. In addition, it is possible to efficiently remove the electrode deposit containing the lead compound from the surface of the electrode for electrolysis by subjecting it to the alkali dipping step again.
（アルカリ塗布工程）
本発明における除去方法として、上述したアルカリ浸漬工程と酸処理工程に付する以外の態様として、電解用電極表面にアルカリ溶液を塗布するアルカリ塗布工程に付することにより、電解用電極表面に付着した鉛化合物を含む電極表面付着物を除去することができる。
(Alkali coating process)
As a removal method in the present invention, as an aspect other than the above-mentioned alkali dipping step and acid treatment step, by applying an alkaline coating step of applying an alkaline solution to the electrode surface for electrolysis, the electrode surface for electrolysis is attached. Electrode surface deposits containing lead compounds can be removed.
具体的には、表面に鉛化合物を含む電極表面付着物が付着した電解用電極の表面に、アンモニア水、アルカリ金属またはアルカリ土類金属の水酸化物、若しくは炭酸塩等のアルカリ水溶液を塗布することで、鉛化合物を含む電極表面付着物中の硫酸鉛、または酸化鉛を水酸化鉛または炭酸鉛へ変換させ、電極表面付着物を除去することができる。 Specifically, an aqueous alkaline solution such as ammonia water, a hydroxide of an alkali metal or an alkaline earth metal, or a carbonate is applied to the surface of the electrode for electrolysis on which the electrode surface deposit containing a lead compound is attached. Thus, lead sulfate or lead oxide in the electrode surface deposit containing the lead compound can be converted into lead hydroxide or lead carbonate, and the electrode surface deposit can be removed.
アルカリ塗布工程における電解用電極表面へのアルカリ水溶液を塗布する方法としては、特に制限されず、刷毛・ローラー等によって塗布する方法、スプレー法、ディップコート法等公知の方法を採用することができる。 The method of applying the alkaline aqueous solution to the surface of the electrode for electrolysis in the alkali applying step is not particularly limited, and a known method such as a method of applying with a brush or a roller, a spray method, a dip coating method can be adopted.
本発明のアルカリ塗布工程に用いることのできるアルカリ水溶液は、電解用電極表面に付着した鉛化合物を含む電極表面付着物を効率的に除去できるものであれば、特に制限なく用いることができる。例えば、アルカリ水溶液としては、アンモニア水、アルカリ金属、またはアルカリ土類金属の水酸化物、または炭酸塩の水溶液を例示することができる。 The alkaline aqueous solution that can be used in the alkali coating step of the present invention can be used without particular limitation as long as it can efficiently remove the electrode surface deposits including the lead compound that has adhered to the electrode surface for electrolysis. Examples of the alkaline aqueous solution include aqueous ammonia, aqueous solutions of alkali metal or alkaline earth metal hydroxides or carbonates.
アルカリ金属、またはアルカリ土類金属の水酸化物としては、水酸化リチウム、水酸化ナトリウム、水酸化カリウム、水酸化ルビジウム、水酸化セシウム、水酸化ベリリウム、水酸化マグネシウム、水酸化カルシウム、水酸化ストロンチウム、水酸化バリウム等を例示することができる。 Examples of hydroxides of alkali metals or alkaline earth metals include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, beryllium hydroxide, magnesium hydroxide, calcium hydroxide and strontium hydroxide. , Barium hydroxide and the like can be exemplified.
アルカリ金属、またはアルカリ土類金属の炭酸塩としては、炭酸リチウム、炭酸ナトリウム、炭酸カリウム、炭酸ルビジウム、炭酸セシウム、炭酸ベリリウム、炭酸マグネシウム、炭酸カルシウム、炭酸ストロンチウム、炭酸バリウム等を例示することができる。上述したものの中でも、アルカリ金属、またはアルカリ土類金属の水酸化物が好ましく、水酸化ナトリウムまたは水酸化カリウムがより好ましい。 Examples of the alkali metal or alkaline earth metal carbonates include lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, beryllium carbonate, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate and the like. .. Among the above, alkali metal or alkaline earth metal hydroxides are preferable, and sodium hydroxide or potassium hydroxide is more preferable.
本発明のアルカリ塗布工程に用いるアルカリ水溶液は、１質量％から飽和濃度（例えば、２０度では、５２．２質量％等のように、各温度での最大溶解濃度を意味する）の範囲のものであれば特に問題なく用いることができる。好ましくは２０質量％〜４８質量％（室温：２５℃）の範囲であり、より好ましくは３２％質量％〜４８質量％（室温：２５℃）の範囲である。なお、１質量％未満では、鉛化合物を含む電極表面付着物中の硫酸鉛を水酸化鉛または炭酸鉛に変換する反応が十分におこらず、除去効率の点で不十分となる。 The alkaline aqueous solution used in the alkali coating step of the present invention has a range of 1% by mass to a saturated concentration (for example, at 20 degrees, it means the maximum dissolved concentration at each temperature, such as 52.2% by mass). If so, it can be used without any particular problems. The range is preferably 20% by mass to 48% by mass (room temperature: 25°C), and more preferably 32% by mass to 48% by mass (room temperature: 25°C). If it is less than 1% by mass, the reaction of converting lead sulfate in the electrode surface deposit containing a lead compound into lead hydroxide or lead carbonate does not sufficiently occur, resulting in insufficient removal efficiency.
アルカリ塗布工程におけるアルカリ水溶液の塗布量は、電解用電極表面に付着した鉛化合物を含む電極表面付着物を十分に変換できる量であればよく、具体的には、硫酸鉛または酸化鉛等の鉛化合物を水酸化鉛または炭酸鉛等へ変換することができる量であればよく、例えば、１００ｍｌ/ｍ２〜１０００ｍｌ/ｍ２の範囲であればよく、好ましくは２００ｍｌ/ｍ２〜８００ｍｌ/ｍ２の範囲である。 The coating amount of the alkaline aqueous solution in the alkali coating step may be an amount that can sufficiently convert the electrode surface deposit containing the lead compound attached to the electrode surface for electrolysis, and specifically, lead sulfate or lead oxide or the like. compound may be an amount that can be converted into lead hydroxide or lead carbonate and the like, for example, may be in the range of 100ml / m 2 ~1000ml / m 2 , preferably 200ml / m 2 ~800ml / m 2 The range is.
アルカリ塗布工程に付した電解用電極は、乾燥工程に付して電解用電極を乾燥させてもよい。乾燥工程は、塗布したアルカリ水溶液が蒸発する程度の条件で行えばよく、例えば、室温で１０分から２４時間程度乾燥すればよく、室温以上２００℃以下の温度で５分から１０数時間程度行うことが好ましい。 The electrode for electrolysis subjected to the alkali coating step may be subjected to a drying step to dry the electrode for electrolysis. The drying step may be performed under conditions such that the applied alkaline aqueous solution evaporates. For example, the drying step may be performed at room temperature for about 10 minutes to 24 hours, and may be performed at room temperature or more and 200° C. or less for about 5 minutes to several tens of hours. preferable.
アルカリ塗布工程に付した電解用電極は、そのまま後述する表面洗浄工程に付してもよく、乾燥工程に付した後、表面洗浄工程に付してもよい。また、表面処理工程に付した後、電解用電極を再度アルカリ塗布工程と表面洗浄工程に繰り返し付することでより、効率的に電解用電極表面から鉛化合物を含む電極付着物を除去することができる。 The electrode for electrolysis that has been subjected to the alkali coating step may be subjected to the surface cleaning step described below as it is, or may be subjected to the surface cleaning step after being subjected to the drying step. Further, after the surface treatment step, the electrode for electrolysis is repeatedly subjected to the alkali coating step and the surface cleaning step again, whereby the electrode deposit containing the lead compound can be efficiently removed from the electrode surface for electrolysis. it can.
（表面洗浄工程）
本発明の除去方法においては、アルカリ浸漬工程後、及び/または酸処理工程後、若しくはアルカリ塗布工程後に、表面洗浄工程に付することにより、電解用電極表面の鉛化合物を含む電極表面付着物を物理的に除去することができる。
(Surface cleaning process)
In the removal method of the present invention, after the alkali dipping step, and / or after the acid treatment step, or after the alkali coating step, by subjecting the surface cleaning step, the electrode surface deposits containing lead compounds on the electrode surface for electrolysis It can be physically removed.
表面洗浄工程としては、通常電極表面の表面洗浄に用いることのできる手法を用いることができる。例えば、５〜１００メガパスカル程度の圧力の高圧水を電極表面に吹き付けて表面洗浄を行う方法でもよく、ブラシや刷毛等を用いて研磨（ブラッシング）を行うことで表面洗浄を行う手法でもよい。電解用電極について、表面洗浄処理を行うことで、電解用電極表面に残存する鉛化合物を物理的に除去することによって、電解用電極表面からの鉛化合物を含む電極付着物の除去することができる。
なお、研磨（ブラッシング）により表面洗浄を行う際に、水（例えば、イオン交換水、蒸留水、純水、水道水等）を用いながらブラッシングを行ってもよい。
As the surface cleaning step, a method that can be usually used for surface cleaning of the electrode surface can be used. For example, a method of spraying high-pressure water having a pressure of about 5 to 100 megapascals onto the electrode surface to clean the surface may be used, or a method of cleaning the surface by polishing (brushing) with a brush or a brush may be used. By performing a surface cleaning treatment on the electrode for electrolysis, it is possible to physically remove the lead compound remaining on the surface of the electrode for electrolysis, thereby removing the electrode deposit containing the lead compound from the surface of the electrode for electrolysis. ..
When the surface is cleaned by polishing (brushing), the brushing may be performed using water (for example, ion-exchanged water, distilled water, pure water, tap water, etc.).
（電解用電極）
本発明の除去方法を適用することのできる電解用電極は、電解用電極の表面に付着する鉛化合物を含む電極表面付着物が付着しているものであり、鉛化合物を含む電極表面付着物は、電解めっきや金属箔製造電解によって、電解用電極表面に硫酸鉛または酸化鉛等を含む鉛化合物が付着しているものである。
(Electrode for electrolysis)
The electrode for electrolysis to which the removing method of the present invention can be applied is one in which an electrode surface deposit containing a lead compound attached to the surface of the electrode for electrolysis is attached, and an electrode surface deposit containing a lead compound is The lead compound containing lead sulfate or lead oxide is attached to the surface of the electrode for electrolysis by electrolytic plating or electrolysis for producing metal foil.
電極表面付着物中の鉛化合物としては、硫酸鉛、または酸化鉛を含んでいれば、その含有量は特に制限されないが、少なくとも電極表面付着物中の５０％以上が、鉛化合物である場合、本発明の除去方法を好適に適用することできる。また、電極表面付着物には、鉛化合物以外に各種の金属不純物を含んでいてもよい。即ち、本発明の除去方法は、電解めっきや金属箔製造電解に用いる電解用電極表面に酸化鉛、または硫酸鉛等の鉛化合物を含む電極表面付着物が付着することで電解用電極の電極性能が阻害されている電解用電極へ用いることができる。 The lead compound in the electrode surface deposit is not particularly limited as long as it contains lead sulfate or lead oxide, but at least 50% or more of the electrode surface deposit is a lead compound, The removal method of the present invention can be preferably applied. Further, the electrode surface deposit may contain various metal impurities in addition to the lead compound. That is, the removal method of the present invention, the electrode performance of the electrode for electrolysis by adhering electrode surface deposits containing lead compounds such as lead oxide or lead sulfate to the electrode surface for electrolysis used for electroplating or metal foil manufacturing electrolysis. It can be used for an electrode for electrolysis in which is inhibited.
電解用電極に付着した電極表面付着物中の鉛化合物の除去量は、実施例に記載する方法により測定することができる。具体的には、電極表面を、蛍光Ｘ線分析装置を用いて鉛のピーク強度を測定し、除去方法に付する前の電極表面の鉛のピーク強度（初期強度）と除去方法に付した後の電極表面の鉛のピーク強度から求めることができる。 The amount of the lead compound removed from the electrode surface deposit attached to the electrode for electrolysis can be measured by the method described in Examples. Specifically, after measuring the lead intensity on the electrode surface using a fluorescent X-ray analyzer and applying the lead intensity on the electrode surface before the removal method (initial intensity) and the removal method. It can be obtained from the peak intensity of lead on the electrode surface.
電解用電極の電極基体は、金属性材料が用いられ、導電性や適当な剛性を有するものであれば材質や形状は特に制限なく用いることができる。例えば、耐食性の良いチタン、タンタル、ニオブ、ジルコニウム等のバルブメタル、またはバルブメタルの合金が好ましい。また、電極基体は必要ならば予め焼鈍、ブラスト等による表面粗化、酸洗等による表面清浄化等の物理的、化学的前処理を適宜行ったものであってもよい。 A metal material is used for the electrode substrate of the electrode for electrolysis, and the material and shape can be used without particular limitation as long as it has conductivity and appropriate rigidity. For example, a valve metal such as titanium, tantalum, niobium, zirconium or the like, or an alloy of valve metals, which has good corrosion resistance, is preferable. If necessary, the electrode substrate may be preliminarily subjected to physical or chemical pretreatment such as surface roughening by annealing, blasting or the like, surface cleaning by pickling or the like.
更に、電解用電極は、該電極基体の表面には、金属、または金属酸化物、若しくは金属合金を含む層（中間層）で被覆されていることが好ましい。該層（中間層）を形成する金属は、導電性や耐食性に優れ、基体や電極触媒層との密着が良好なものであれば特に限定されない。中間層に用いる代表的な金属として、耐食性に優れたチタン、タンタル、ニオブ、ジルコニウム、ハフニウム等、及びこれらの酸化物、若しくはこれらの合金等が挙げられ、これらはチタン等のバルブメタルからなる電極基体との密着性に優れる。なお、金属、または金属酸化物、若しくは金属合金を含む層（中間層）における金属は１種類のみでもよく、複数の金属を組み合わせたものでもよい。複数を組み合わせて用いる場合の比率は適宜調整することが可能である。中でも、タンタル、チタン、またはこれらの酸化物、若しくはこれらの合金が好ましい。 Further, the electrode for electrolysis is preferably coated on the surface of the electrode substrate with a layer (intermediate layer) containing a metal, a metal oxide, or a metal alloy. The metal forming the layer (intermediate layer) is not particularly limited as long as it has excellent conductivity and corrosion resistance and has good adhesion to the substrate and the electrode catalyst layer. Typical metals used for the intermediate layer include titanium, tantalum, niobium, zirconium, hafnium, etc., which are excellent in corrosion resistance, and oxides thereof, or alloys thereof, etc. These are electrodes made of valve metals such as titanium. Excellent adhesion to the substrate. Note that the metal in the layer (intermediate layer) containing the metal, the metal oxide, or the metal alloy may be only one kind, or may be a combination of a plurality of metals. The ratio in the case of using a plurality of combinations can be appropriately adjusted. Among them, tantalum, titanium, oxides thereof, or alloys thereof are preferable.
電極基体上に層（中間層）を被覆させる方法としては、真空スパッタリングによる層形成方法が挙げられる。真空スパッタリングとしては、例えば、直流スパッタリング、高周波スパッタリング、アークイオンプレーティング、イオンビームプレーティング、クラスターイオンビーム法等、種々の装置を適用することが可能であり、真空度、基板温度、ターゲット板の組成や純度、析出速度（投入電力）等の条件を適宜設定することにより所望の物性の層（中間層）を形成することができる。該層（中間層）の厚さは、通常０．１〜１０μｍの範囲でよく、耐食性や生産性等の実用的見地から適宜選定すればよい。かくして、表面が被覆された電極基体は、その表面の熱的酸化に対する優れた特性、即ち酸化皮膜の成長挙動に顕著な特色を有する。 Examples of the method for coating the layer (intermediate layer) on the electrode substrate include a layer forming method by vacuum sputtering. As the vacuum sputtering, for example, various devices such as direct current sputtering, high frequency sputtering, arc ion plating, ion beam plating, cluster ion beam method, etc. can be applied, and the degree of vacuum, substrate temperature, target plate A layer (intermediate layer) having desired physical properties can be formed by appropriately setting conditions such as composition, purity, and deposition rate (input power). The thickness of the layer (intermediate layer) may be usually in the range of 0.1 to 10 μm, and may be appropriately selected from the practical viewpoints such as corrosion resistance and productivity. Thus, the surface-coated electrode substrate has excellent properties for thermal oxidation of its surface, i.e. a distinctive feature in the growth behavior of the oxide film.
電解用電極は、上述した手法により電極基体上に層（中間層）で被覆され、さらに電極触媒層で被覆されたものが好ましい。該電極触媒層は、用途に応じて既知の種々のものを適用することが可能であり、特に限定されないが、例えば、耐久性を特に要求される酸素発生反応用においては、イリジウム酸化物等の白金族金属酸化物を含むものが好ましい。 The electrode for electrolysis is preferably coated with a layer (intermediate layer) on the electrode substrate by the above-mentioned method, and further coated with an electrode catalyst layer. As the electrode catalyst layer, various known ones can be applied depending on the application and are not particularly limited. For example, in the case of oxygen generation reaction where durability is particularly required, iridium oxide or the like is used. Those containing a platinum group metal oxide are preferred.
電解用電極に電極触媒層を被覆させる方法として、種々の方法が知られおり、目的に応じて適宜の選択することができる。例えば、熱分解法等を例示することができ、触媒層成分金属の塩化物、硝酸塩、アルコキシド、レジネート等の原料塩を塩酸、硝酸、アルコール、有機溶媒等の溶剤に溶解して被覆液とし、前記電極基体表面に塗布し、乾燥後空気中等の酸化性雰囲気で焼成炉中にて加熱処理することによって、電極触媒層を形成されることができる。なお、電極触媒層の厚みは通常０．１〜３０μｍの範囲である。また、電極触媒層中における金属は１種のみでもよく、複数を組み合わせて用いてもよい。複数を組み合わせて用いる場合は各種金属の比率は適宜調整することができる。 Various methods are known as methods for coating the electrode for electrolysis with the electrode catalyst layer, and can be appropriately selected depending on the purpose. For example, it is possible to exemplify a thermal decomposition method or the like, and chloride of the catalyst layer component metal, nitrate, alkoxide, raw material salt such as resinate is dissolved in a solvent such as hydrochloric acid, nitric acid, alcohol, an organic solvent to obtain a coating liquid, The electrode catalyst layer can be formed by applying it on the surface of the electrode substrate, drying and then heat-treating it in a firing furnace in an oxidizing atmosphere such as air. The thickness of the electrode catalyst layer is usually in the range of 0.1 to 30 μm. Further, the metal in the electrode catalyst layer may be only one kind or a combination of plural kinds. When a plurality of metals are used in combination, the ratio of various metals can be adjusted appropriately.
また、予め金属酸化物を作製し、適当な有機バインダー、有機溶媒を加えてペースト状とし、電極基体上に印刷し焼成を行う厚膜法、或いはＣＶＤ法を用いて、電極基体上に電極触媒層を形成させることも可能である。 In addition, a metal oxide is prepared in advance, a suitable organic binder and an organic solvent are added to form a paste, and a thick film method in which printing is performed on an electrode substrate and firing is performed, or a CVD method is used to form an electrode catalyst on the electrode substrate. It is also possible to form layers.
更に、本発明の除去方法において、電極表面付着物を除去した電解用電極に上述した手法により、電極触媒層を形成させることも可能である。 Furthermore, in the removal method of the present invention, it is possible to form the electrode catalyst layer on the electrode for electrolysis from which the electrode surface deposit has been removed, by the above-described method.
本発明の除去方法に用いる電解用電極は、金属箔製造用電極、または金属メッキ用電極に用いるものであればよく。具体的には、金属箔製造用電極（例えば、銅箔製造用電極）は、円筒状の陰極上に銅をめっきし、それを剥離することによって銅箔を連続的に製造に用いられる電極のことである。また、金属メッキ用電極（例えば、銅めっき用電極）は、電解質中に含まれる任意の金属成分（例えば銅）を還元し、被めっき物上に電析させることによって薄膜層を形成させる電解に用いられる電極のことである。 The electrode for electrolysis used in the removing method of the present invention may be any one used for a metal foil production electrode or a metal plating electrode. Specifically, a metal foil manufacturing electrode (for example, a copper foil manufacturing electrode) is an electrode used for continuously manufacturing a copper foil by plating copper on a cylindrical cathode and peeling it off. That is. Further, a metal plating electrode (for example, a copper plating electrode) is used for electrolysis to form a thin film layer by reducing an arbitrary metal component (for example, copper) contained in an electrolyte and depositing it on an object to be plated. It is the electrode used.
次に、実施例により本発明を具体的に説明するが、本発明はこれに限定されるものではない。 Next, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.
＜実施例１＞
下記試験電極を電解条件において、銅箔製造電解の模擬電解試験に使用した電解用電極を用いた。なお、電極表面付着物中の鉛化合物の除去量は後述する蛍光Ｘ線分析装置を用いて測定した。
<Example 1>
The following test electrodes were used under electrolysis conditions, and the electrolysis electrodes used in the simulated electrolysis test of copper foil production electrolysis were used. The amount of the lead compound removed from the deposits on the electrode surface was measured using a fluorescent X-ray analyzer described later.
市販の金属箔製造用の電解用電極（ダイソーエンジニアリング株式会社製 品番：ＭＤ−２２０、基体：チタン、電極触媒層：イリジウム酸化物、中間層；チタンとタンタルの合金） Electrolytic electrode for manufacturing commercially available metal foil (manufactured by Daiso Engineering Co., Ltd., product number: MD-220, substrate: titanium, electrode catalyst layer: iridium oxide, intermediate layer; alloy of titanium and tantalum)
電解条件
・対極（陰極）：Ｐｔ板
・電流密度：１００Ａ／ｄｍ２
・電解温度：８０℃
・電解液：５０ｐｐｍのＰｂ（ＮＯ３）２を添加した ２０重量％ Ｈ２ＳＯ４と １０重量％ Ｎａ２ＳＯ４の溶液
・電解時間：１６８時間
Electrolysis conditions -Counter electrode (cathode): Pt plate-Current density: 100 A/dm 2
・Electrolysis temperature: 80℃
Electrolyte solution: a solution of 20 wt% H 2 SO 4 and 10 wt% Na 2 SO 4 with 50 ppm of Pb(NO 3 ) 2 added ・Electrolysis time: 168 hours
蛍光Ｘ線分析条件
測定機器：(株)リガク製、３２７０
ターゲット：Ｒｈ（ロジウム）
出力設定：２０ｋＶ、３０ｍＡ
測定時間：３０秒
測定雰囲気：大気下
試料の調製：試験電極を縦１０ｍｍ×横１０ｍｍ×厚み１ｍｍの大きさに切断した切片
X-ray fluorescence analysis conditions Measuring instrument: 3270, manufactured by Rigaku Corporation
Target: Rh (Rhodium)
Output setting: 20kV, 30mA
Measurement time: 30 seconds Measurement atmosphere: Under air Preparation of sample: Test electrode cut into a size of 10 mm length × 10 mm width × 1 mm thickness
上記電解条件で硫酸鉛を含む電極表面付着物が付着した電解用電極の切片（縦１０ｍｍ×横１０ｍｍ×厚み１ｍｍ）を２４質量％の水酸化ナトリウム水溶液（東京化成工業株式会社製）に浸漬し、６０℃で２時間浸漬し、電解用電極表面に付着した電極表面付着物中の硫酸鉛を水酸化鉛へ変換するアルカリ浸漬工程に付した。その後、電解用電極表面にイオン交換水を吹きかけながらブラシでブラッシングすることにより、アルカリ浸漬工程によって除去可能となった鉛化合物（主に水酸化鉛）の一部を物理的に除去し、表面洗浄工程を行った。次いで、電解用電極の切片を９９．５質量％の酢酸（東京化成工業株式会社製）に浸漬し、６０℃で１時間浸漬し、酸処理工程付し、水酸化鉛を溶解させた。更に、電解用電極表面にイオン交換水を吹きかけながらブラシでブラッシングし、残存する鉛化合物（主に水酸化鉛）を物理的に除去し、表面洗浄工程を行った。表面から鉛化合物を含む電極付着物の除去した電解用電極について、電極表面を、蛍光Ｘ線分析装置を用いて鉛のピーク強度を測定した。初期強度のピーク強度（表面から鉛化合物を含む電極付着物の除去前の電極表面における鉛のピーク強度を１００とする）と比較して、鉛化合物が９４．４％減少していた。 Under the above electrolysis conditions, a piece of an electrode for electrolysis to which an electrode surface deposit containing lead sulfate was attached (length 10 mm x width 10 mm x thickness 1 mm) was immersed in a 24 mass% sodium hydroxide aqueous solution (manufactured by Tokyo Chemical Industry Co., Ltd.). It was immersed at 60° C. for 2 hours and then subjected to an alkali immersion step of converting the lead sulfate in the electrode surface deposit adhered to the electrode surface for electrolysis to lead hydroxide. After that, by brushing with a brush while spraying ion-exchanged water on the surface of the electrode for electrolysis, some of the lead compounds (mainly lead hydroxide) that could be removed by the alkali dipping process are physically removed, and the surface is cleaned. The process was carried out. Then, the piece of the electrode for electrolysis was immersed in 99.5% by mass of acetic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), immersed at 60° C. for 1 hour, and subjected to an acid treatment step to dissolve lead hydroxide. Further, the surface of the electrode for electrolysis was brushed with a brush while spraying ion-exchanged water to physically remove the residual lead compound (mainly lead hydroxide), and a surface cleaning step was performed. The peak intensity of lead was measured on the electrode surface of the electrode for electrolysis in which the electrode deposit containing the lead compound was removed from the surface using a fluorescent X-ray analyzer. Compared with the peak intensity of the initial intensity (the peak intensity of lead on the electrode surface before removal of the electrode deposit containing the lead compound from the surface is 100), the lead compound was reduced by 94.4%.
＜実施例２＞
実験に用いた水酸化ナトリウムを１２質量％に変更した以外は、実施例１と同様に試験を行った。表面から鉛化合物を含む電極付着物の除去した電解用電極について、電極表面を、蛍光Ｘ線分析装置を用いて鉛のピーク強度を測定した。初期強度のピーク強度と比較して、鉛化合物が８５．６％減少していた。
<Example 2>
The test was performed in the same manner as in Example 1 except that the sodium hydroxide used in the experiment was changed to 12% by mass. Regarding the electrode for electrolysis in which the electrode deposit containing the lead compound was removed from the surface, the peak intensity of lead was measured on the electrode surface using a fluorescent X-ray analyzer. Compared to the peak intensity of the initial intensity, the lead compound was reduced by 85.6%.
＜実施例３＞
実験に用いた水酸化ナトリウムを６質量％に変更した以外は、実施例１と同様に試験を行った。表面から鉛化合物を含む電極付着物の除去した電解用電極について、電極表面を、蛍光Ｘ線分析装置を用いて鉛のピーク強度を測定した。初期強度のピーク強度と比較して、鉛化合物が７８．１％減少していた。
<Example 3>
The test was performed in the same manner as in Example 1 except that the sodium hydroxide used in the experiment was changed to 6% by mass. Regarding the electrode for electrolysis in which the electrode deposit containing the lead compound was removed from the surface, the peak intensity of lead was measured on the electrode surface using a fluorescent X-ray analyzer. The lead compound was reduced by 78.1% as compared with the peak intensity of the initial intensity.
＜実施例４＞
上記電解条件で硫酸鉛を含む電極表面付着物が付着した電解用電極の切片上（縦１０ｍｍ×横１０ｍｍ×厚み１ｍｍ）に４８質量％の水酸化ナトリウム水溶液（東京化成工業株式会社製）を４００ｍｌ／ｍ２となるように刷毛を用いて塗布し、電解用電極表面に付着した電極表面付着物中の硫酸鉛を水酸化鉛へ変換するアルカリ塗布工程に付した。その後、室温（２５℃）で一晩自然乾燥し、乾燥工程に付した。更に、電解用電極表面にイオン交換水を吹きかけながらブラシでブラッシングし、鉛化合物（主に水酸化鉛）を物理的に除去し、表面洗浄工程を行った。表面から鉛化合物を含む電極付着物の除去した電解用電極について、電極表面を、蛍光Ｘ線分析装置を用いて鉛のピーク強度を測定した。初期強度のピーク強度（表面から鉛化合物を含む電極付着物の除去前の電極表面における鉛のピーク強度を１００とする）と比較して、鉛化合物が６５．６％減少していた。さらに、同様の手順で、アルカリ塗布工程、乾燥工程、表面洗浄工程に繰り返し行い、電極表面の鉛化合物の除去率を測定したところ、２サイクル後は、鉛化合物が初期強度のピーク強度と比較して８１．５％減少しており、３サイクル後は、鉛化合物が初期強度のピーク強度と比較して９４．４％減少していた。
<Example 4>
400 ml of 48 mass% sodium hydroxide aqueous solution (manufactured by Tokyo Kasei Kogyo Co., Ltd.) on the section of the electrode for electrolysis (10 mm in length×10 mm in width×1 mm in thickness) to which the electrode surface deposit containing lead sulfate is attached under the above electrolysis conditions. /M 2 was applied by using a brush, and an alkali application step of converting lead sulfate in the electrode surface deposit adhered to the electrode surface for electrolysis to lead hydroxide was performed. Then, it was naturally dried overnight at room temperature (25° C.) and subjected to a drying step. Further, the surface of the electrode for electrolysis was brushed with a brush while spraying ion-exchanged water to physically remove the lead compound (mainly lead hydroxide), and a surface cleaning step was performed. Regarding the electrode for electrolysis in which the electrode deposit containing the lead compound was removed from the surface, the peak intensity of lead was measured on the electrode surface using a fluorescent X-ray analyzer. The lead compound was reduced by 65.6% as compared with the peak intensity of the initial intensity (the peak intensity of lead on the electrode surface before removing the electrode deposit containing the lead compound from the surface is 100). Furthermore, the same procedure was repeated for the alkali coating step, the drying step, and the surface cleaning step, and the removal rate of the lead compound on the electrode surface was measured. After two cycles, the lead compound was compared with the peak strength of the initial strength. 81.5%, and after 3 cycles, the lead compound decreased 94.4% compared to the peak intensity of the initial intensity.
＜比較例１＞
＜実施例１＞で用いたものと同様の電解試験に用いた電解用電極の切片（縦１０ｍｍ×横１０ｍｍ×厚み１ｍｍ）を、６質量％の水酸化ナトリウム水溶液に浸漬し、６０℃で２時間浸漬し、電解用電極表面に付着した電極表面付着物中の硫酸鉛を水酸化鉛へ変換するアルカリ浸漬工程に付した。その後、電解用電極表面にイオン交換水を吹きかけながら（ブラシで）ブラッシングすることにより、アルカリ浸漬工程によって除去可能となった鉛化合物（主に水酸化鉛）の一部を物理的に除去し表面洗浄工程を行った。表面から鉛化合物を含む電極付着物の除去した電解用電極について、電極表面を、蛍光Ｘ線分析装置を用いて鉛のピーク強度を測定した。初期強度のピーク強度と比較して、鉛化合物が３１．７％減少していた。
<Comparative Example 1>
A piece of an electrode for electrolysis used in the same electrolysis test as that used in <Example 1> (length 10 mm x width 10 mm x thickness 1 mm) was immersed in a 6 mass% sodium hydroxide aqueous solution, and the temperature was adjusted to 2 at 60°C. It was immersed for a period of time, and then subjected to an alkali immersion step of converting lead sulfate in the electrode surface deposit adhered to the electrode surface for electrolysis to lead hydroxide. After that, by brushing (using a brush) while spraying ion-exchanged water on the surface of the electrode for electrolysis, some of the lead compound (mainly lead hydroxide) that could be removed by the alkali immersion process was physically removed. A washing process was performed. Regarding the electrode for electrolysis in which the electrode deposit containing the lead compound was removed from the surface, the peak intensity of lead was measured on the electrode surface using a fluorescent X-ray analyzer. The lead compound was reduced by 31.7% as compared with the peak intensity of the initial intensity.
＜比較例２＞
＜実施例１＞で用いたものと同様の電解試験に用いた電解用電極の切片（縦１０ｍｍ×横１０ｍｍ×厚み１ｍｍ）を、９８質量％の酢酸に浸漬し、９０℃で３時間浸漬し、酸処理工程に付した。その後、電解用電極表面にイオン交換水を吹きかけながら（ブラシで）ブラッシングすることにより、酸処理工程によって除去可能となった鉛化合物の一部を物理的に除去し表面洗浄工程を行った。表面から鉛化合物を含む電極付着物の除去した電解用電極について、電極表面を、蛍光Ｘ線分析装置を用いて鉛のピーク強度を測定した。初期強度のピーク強度と比較して、鉛化合物が２９．３％減少していた。
<Comparative example 2>
A section of an electrode for electrolysis used in the same electrolysis test as that used in <Example 1> (10 mm in length×10 mm in width×1 mm in thickness) was dipped in 98% by mass of acetic acid and dipped at 90° C. for 3 hours. , Acid treatment step. Then, the surface of the electrode for electrolysis was brushed (by a brush) while being sprayed with ion-exchanged water to physically remove a part of the lead compound that could be removed by the acid treatment step, and a surface washing step was performed. Regarding the electrode for electrolysis in which the electrode deposit containing the lead compound was removed from the surface, the peak intensity of lead was measured on the electrode surface using a fluorescent X-ray analyzer. The lead compound was reduced by 29.3% as compared with the peak intensity of the initial intensity.
本発明の除去方法は、電解銅粉、電解銅箔の製造または銅メッキだけでなく、各種の電解用電極表面から鉛化合物を含む電極付着物の除去することが可能である。
INDUSTRIAL APPLICABILITY The removal method of the present invention can remove not only electrolytic copper powder, electrolytic copper foil or copper plating, but also electrode deposits containing lead compounds from various electrolytic electrode surfaces.
Claims (19)
アルカリ水溶液に浸漬するアルカリ浸漬工程と、
有機酸に浸漬する酸処理工程に付することにより、電解用電極表面に付着した鉛化合物を含む電極表面付着物を除去する方法。 An electrode for electrolysis where the electrode surface deposit containing a lead compound is attached to the surface,
An alkaline dipping step of dipping in an alkaline aqueous solution,
A method for removing an electrode surface deposit containing a lead compound adhered to the electrode surface for electrolysis by subjecting to an acid treatment step of immersing in an organic acid.
電解用電極表面にアルカリ水溶液を塗布するアルカリ塗布工程に付することにより、電解用電極表面に付着した鉛化合物を含む電極表面付着物を除去する方法。 An electrode for electrolysis where the electrode surface deposit containing a lead compound is attached to the surface,
A method of removing an electrode surface deposit containing a lead compound adhered to the surface of an electrode for electrolysis by subjecting the surface of the electrode for electrolysis to an alkali application step of applying an alkaline aqueous solution.
19. The method of claim 18, wherein the metal is one or more metals or metal oxides selected from titanium, tantalum, niobium, zirconium and hafnium, or alloys thereof.
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