CN116288305A - Chromium-free high-temperature anti-oxidation passivating agent for electrolytic copper foil - Google Patents
Chromium-free high-temperature anti-oxidation passivating agent for electrolytic copper foil Download PDFInfo
- Publication number
- CN116288305A CN116288305A CN202211717034.3A CN202211717034A CN116288305A CN 116288305 A CN116288305 A CN 116288305A CN 202211717034 A CN202211717034 A CN 202211717034A CN 116288305 A CN116288305 A CN 116288305A
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- CN
- China
- Prior art keywords
- copper foil
- chromium
- electrolytic copper
- acid
- passivating agent
- 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.)
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000011889 copper foil Substances 0.000 title claims abstract description 52
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 29
- 230000003064 anti-oxidating effect Effects 0.000 title claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 230000007797 corrosion Effects 0.000 claims abstract description 18
- 238000005260 corrosion Methods 0.000 claims abstract description 18
- 239000003112 inhibitor Substances 0.000 claims abstract description 18
- 239000008367 deionised water Substances 0.000 claims abstract description 15
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 15
- 230000003647 oxidation Effects 0.000 claims abstract description 13
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 13
- 239000000080 wetting agent Substances 0.000 claims abstract description 11
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 7
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 7
- 239000008139 complexing agent Substances 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 3
- 238000002161 passivation Methods 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 11
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- ILLHQJIJCRNRCJ-UHFFFAOYSA-N dec-1-yne Chemical compound CCCCCCCCC#C ILLHQJIJCRNRCJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000004593 Epoxy Substances 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 6
- 235000006708 antioxidants Nutrition 0.000 claims description 6
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 6
- APSPVJKFJYTCTN-UHFFFAOYSA-N tetramethylazanium;silicate Chemical compound C[N+](C)(C)C.C[N+](C)(C)C.C[N+](C)(C)C.C[N+](C)(C)C.[O-][Si]([O-])([O-])[O-] APSPVJKFJYTCTN-UHFFFAOYSA-N 0.000 claims description 6
- WXHLLJAMBQLULT-UHFFFAOYSA-N 2-[[6-[4-(2-hydroxyethyl)piperazin-1-yl]-2-methylpyrimidin-4-yl]amino]-n-(2-methyl-6-sulfanylphenyl)-1,3-thiazole-5-carboxamide;hydrate Chemical compound O.C=1C(N2CCN(CCO)CC2)=NC(C)=NC=1NC(S1)=NC=C1C(=O)NC1=C(C)C=CC=C1S WXHLLJAMBQLULT-UHFFFAOYSA-N 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 5
- BJZIJOLEWHWTJO-UHFFFAOYSA-H dipotassium;hexafluorozirconium(2-) Chemical compound [F-].[F-].[F-].[F-].[F-].[F-].[K+].[K+].[Zr+4] BJZIJOLEWHWTJO-UHFFFAOYSA-H 0.000 claims description 5
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 5
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims description 5
- 235000015393 sodium molybdate Nutrition 0.000 claims description 5
- 239000011684 sodium molybdate Substances 0.000 claims description 5
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 5
- 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 claims description 4
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 claims description 4
- 229920002126 Acrylic acid copolymer Polymers 0.000 claims description 4
- 239000002211 L-ascorbic acid Substances 0.000 claims description 4
- 235000000069 L-ascorbic acid Nutrition 0.000 claims description 4
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 229960005070 ascorbic acid Drugs 0.000 claims description 4
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 4
- 239000012964 benzotriazole Substances 0.000 claims description 4
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 4
- 229920000570 polyether Polymers 0.000 claims description 4
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 4
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 4
- 229910000077 silane Inorganic materials 0.000 claims description 4
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 4
- 229940061605 tetrasodium glutamate diacetate Drugs 0.000 claims description 4
- UZVUJVFQFNHRSY-OUTKXMMCSA-J tetrasodium;(2s)-2-[bis(carboxylatomethyl)amino]pentanedioate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CC[C@@H](C([O-])=O)N(CC([O-])=O)CC([O-])=O UZVUJVFQFNHRSY-OUTKXMMCSA-J 0.000 claims description 4
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 3
- 239000004471 Glycine Substances 0.000 claims description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 239000004310 lactic acid Substances 0.000 claims description 3
- 235000014655 lactic acid Nutrition 0.000 claims description 3
- 239000001630 malic acid Substances 0.000 claims description 3
- 235000011090 malic acid Nutrition 0.000 claims description 3
- 229940099596 manganese sulfate Drugs 0.000 claims description 3
- 235000007079 manganese sulphate Nutrition 0.000 claims description 3
- 239000011702 manganese sulphate Substances 0.000 claims description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- DGSDBJMBHCQYGN-UHFFFAOYSA-M sodium;2-ethylhexyl sulfate Chemical compound [Na+].CCCCC(CC)COS([O-])(=O)=O DGSDBJMBHCQYGN-UHFFFAOYSA-M 0.000 claims description 3
- XYRAEZLPSATLHH-UHFFFAOYSA-N trisodium methoxy(trioxido)silane Chemical compound [Na+].[Na+].[Na+].CO[Si]([O-])([O-])[O-] XYRAEZLPSATLHH-UHFFFAOYSA-N 0.000 claims description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- 238000007865 diluting Methods 0.000 claims description 2
- 150000002191 fatty alcohols Chemical class 0.000 claims description 2
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 239000011651 chromium Substances 0.000 abstract description 6
- 238000004065 wastewater treatment Methods 0.000 abstract description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052804 chromium Inorganic materials 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 230000008859 change Effects 0.000 description 16
- 238000005406 washing Methods 0.000 description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 230000008569 process Effects 0.000 description 7
- 230000006872 improvement Effects 0.000 description 6
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 3
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 3
- 235000019796 monopotassium phosphate Nutrition 0.000 description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 3
- BAERPNBPLZWCES-UHFFFAOYSA-N (2-hydroxy-1-phosphonoethyl)phosphonic acid Chemical compound OCC(P(O)(O)=O)P(O)(O)=O BAERPNBPLZWCES-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 2
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 description 2
- 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 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 2
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical group [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229940099690 malic acid Drugs 0.000 description 2
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000001384 succinic acid Substances 0.000 description 2
- CAQWNKXTMBFBGI-UHFFFAOYSA-N C.[Na] Chemical compound C.[Na] CAQWNKXTMBFBGI-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- -1 decyne diol Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229960001484 edetic acid Drugs 0.000 description 1
- 238000001978 electrochemical passivation Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229960002449 glycine Drugs 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229940116298 l- malic acid Drugs 0.000 description 1
- 229960000448 lactic acid Drugs 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
- C23C22/08—Orthophosphates
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
- C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
- C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
- C23C22/361—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing titanium, zirconium or hafnium compounds
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
- C23C22/42—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates containing also phosphates
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
- C23C22/44—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates containing also fluorides or complex fluorides
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/20—Use of solutions containing silanes
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Abstract
The invention discloses an electrolytic copper foil chromium-free high-temperature anti-oxidation passivating agent, which comprises the following components: complexing agent 10-22g/L; 2-6g/L of corrosion inhibitor; 1-3g/L of auxiliary corrosion inhibitor; 8-300g/L of antioxidant; 0.1-0.5g/L of wetting agent; the solvent is deionized water. The passivating agent does not contain chromium, meets the environmental protection requirement, saves the wastewater treatment cost, and further improves the high-temperature oxidation resistance of the electrolytic copper foil.
Description
Technical Field
The invention relates to the technical field of metal surface treatment, in particular to an electrolytic copper foil chromium-free high-temperature oxidation-resistant passivating agent and a passivation process thereof.
Background
In order to protect the electrolytic copper foil from oxidation during the application processes of transportation, storage, copper-clad plates, printed circuit boards, lithium ion batteries and the like, and further influence the adhesiveness, weldability, resistance and the like, the copper foil needs to be subjected to anti-oxidation treatment during the production process of the electrolytic copper foil. Currently, the commonly used oxidation protection treatment is hexavalent chromium passivation, i.e. immersion passivation in chromic acid solution or electrolytic passivation in chromate solution. Both methods require the use of Cr (VI). Cr (VI) is a high-toxicity and cancerogenic substance, seriously harms the environment and human health, and has high wastewater treatment cost. The European Union WEES and RoHS directives severely limit the use of Cr (VI). Therefore, in order to meet the increasingly severe environmental requirements and further improve the oxidation resistance of passivation films, a need exists for a chromium-free passivation agent that replaces the existing chromic acid and chromate passivation processes.
Disclosure of Invention
Based on the defects of the prior art, the technical problem solved by the invention is to provide the chromium-free high-temperature oxidation-resistant passivating agent and the passivation process thereof, wherein the passivating agent does not contain chromium, meets the environmental protection requirement, saves the wastewater treatment cost, and further improves the high-temperature oxidation resistance of the electrolytic copper foil.
In order to solve the technical problems, the invention provides an electrolytic copper foil chromium-free high-temperature oxidation-resistant passivating agent which is characterized by comprising the following components in parts by weight:
complexing agent 10-22g/L;
1-6g/L of corrosion inhibitor;
1-3g/L of auxiliary corrosion inhibitor;
8-300g/L of antioxidant;
0.1-0.5g/L of wetting agent;
the solvent is deionized water.
As the optimization of the technical scheme, the electrolytic copper foil chromium-free high-temperature oxidation-resistant passivating agent provided by the invention further comprises part or all of the following technical characteristics:
as an improvement of the technical scheme, the pH value of the passivating agent is 1-3.
As improvement of the technical scheme, the complexing agent is one or two of hydroxyethylidene diphosphonic acid, lactic acid, L-ascorbic acid, malic acid, succinic acid, tetrasodium glutamate diacetate, ethylenediamine tetraacetic acid, glycine, sulfosalicylic acid, sulfamic acid, citric acid, fluoroboric acid, fluorozirconic acid and phosphoric acid.
As improvement of the technical scheme, the corrosion inhibitor is one or two of sodium molybdate, ammonium molybdate, sodium tungstate, titanyl sulfate, nickel chloride, cobalt sulfate and cobalt nitrate.
As improvement of the technical scheme, the auxiliary corrosion inhibitor is one or two of lanthanum nitrate, cerium nitrate, sodium metavanadate, potassium fluorozirconate, manganese sulfate and potassium dihydrogen phosphate.
As an improvement of the technical scheme, the antioxidant is as follows: acidic silica sol (25% of effective content), epoxy functional oligosiloxane, benzotriazole, methylbenzotriazole, tetramethylammonium silicate, sodium methyl silicate.
As an improvement of the technical scheme, the wetting agent is as follows: one or two of decyne glycol polyoxyethylene ether, fatty alcohol block polyether, 2-ethylhexyl sulfate sodium salt, gemini silane organic wetting agent JC-7000 and maleic acid-acrylic acid copolymer
The preparation method of the chromium-free high-temperature anti-oxidation passivating agent for electrolytic copper foil, which is any one of the above, comprises the following steps:
(1) adding a calculated amount of deionized water into a preparation container;
(2) adding the calculated amount of complexing agent in sequence, and fully stirring;
(3) sequentially adding a calculated amount of corrosion inhibitor and an auxiliary corrosion inhibitor, and stirring at normal temperature until the corrosion inhibitor and the auxiliary corrosion inhibitor are completely dissolved;
(4) slowly adding a calculated amount of antioxidant, and fully stirring;
(5) adding the calculated amount of wetting agent, and fully stirring to obtain the electrolytic copper foil chromium-free high-temperature oxidation-resistant passivating agent.
The method for using the chromium-free high-temperature anti-oxidation passivating agent for electrolytic copper foil, which is characterized by comprising the following steps of:
diluting the passivating agent by 5% -20%, and adjusting the pH value: 1-3, the passivation temperature is room temperature, and the passivation mode is soaking; the passivation time is 6-10s.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
1. the passivating agent disclosed by the invention does not contain carcinogens such as hexavalent chromium and trivalent chromium, so that the risk of harm of the passivating solution to the environment and human bodies is reduced, the wastewater treatment cost is reduced, and the environment-friendly and environment-friendly requirements are met.
2. According to the invention, by referring to the electrolytic copper foil for the lithium ion battery of the electrolytic copper foil industry standard SJ/T11483-2014, the high-temperature baking test is carried out, the passivation film can reach the requirements of no color change when baked for 1 hour at 180-200 ℃, and the appearance is uniform, and is far more than the standard of no color change when baked for 15 minutes at 140 ℃.
The foregoing description is only an overview of the present invention, and is intended to be implemented in accordance with the teachings of the present invention in order that the same may be more clearly understood and appreciated, as well as the other objects, features and advantages of the present invention, as described in detail below in connection with the preferred embodiments.
Drawings
In order to more clearly illustrate the technical solution of the embodiments of the present invention, the drawings of the embodiments will be briefly described below.
FIG. 1 is a graph comparing color change before and after baking at 180℃for 60 minutes of unpassivated copper foil;
FIG. 2 is a graph showing a comparison of color change after the copper foil is passivated with the passivation solution prepared in example 1, before and after baking at 180℃for 60 minutes;
FIG. 3 is a graph showing the color change of a copper foil after passivation using the passivation solution prepared in example 2, before and after baking at 180℃for 60 minutes;
FIG. 4 is a graph showing the color change of a copper foil after passivation using the passivation solution prepared in example 3, before and after baking at 180℃for 60 minutes;
FIG. 5 is a graph showing the color change of a copper foil after passivation using the passivation solution prepared in example 4, before and after baking at 180℃for 60 minutes;
FIG. 6 is a graph showing the color change of a copper foil after passivation using the passivation solution prepared in example 5, before and after baking at 180℃for 60 minutes;
FIG. 7 is a graph showing the color change of a copper foil after passivation using the passivation solution prepared in example 6, before and after baking at 180℃for 60 minutes;
FIG. 8 is a graph showing the color change of a copper foil after passivation using the passivation solution prepared in example 7, before and after baking at 180℃for 60 minutes;
FIG. 9 is a graph showing the color change of a copper foil after passivation using the passivation solution prepared in example 8, before and after baking at 180℃for 60 minutes;
FIG. 10 is a graph showing the color change of a copper foil after passivation using the passivation solution prepared in example 9, before and after baking at 180℃for 60 minutes;
figure 11 is a graph comparing color change after passivation of copper foil using the passivation solution prepared in example 10 before and after baking at 180 c for 60 minutes.
Detailed Description
The following detailed description of the invention, which is a part of this specification, illustrates the principles of the invention by way of example, and other aspects, features, and advantages of the invention will become apparent from the detailed description.
In an embodiment, the passivation process flow is as follows:
copper foil polishing, pure water flushing, activation (10% dilute sulfuric acid), pure water flushing, sealing (normal temperature), water squeezing, hot air drying and high temperature baking test.
Example 1
15g/L of lactic acid, 1.5g/L of L-ascorbic acid, 5g/L of sodium molybdate, 1g/L of cerium nitrate, 200g/L of acidic silica sol (effective content 25%), 0.1g/L of decyne glycol polyoxyethylene ether and the balance of deionized water. The prepared solution is concentrated solution, when in use, the concentrated solution is diluted according to 3% -20%, the pH value is 1-3, the copper foil is soaked and passivated for 6-10s at room temperature, and the concentrated solution is dried by hot air after water washing.
Example 2
12g/L of sulfosalicylic acid, 2g/L of fluoroboric acid, 3g/L of sodium molybdate, 1g/L of manganese sulfate, 5g/L of epoxy functional oligosiloxane, 3.6g/L of benzotriazole, 0.3g/L of gemini silane organic wetting agent JC-7000 and the balance of deionized water. The prepared solution is concentrated solution, when in use, the concentrated solution is diluted according to 3% -20%, the pH value is 1-3, the copper foil is soaked and passivated for 6-10s at room temperature, and the concentrated solution is dried by hot air after water washing.
Example 3
Tetra sodium glutamate diacetate 10g/L, phosphoric acid 5g/L, sodium tungstate 6g/L, potassium fluorozirconate 2g/L, epoxy functional oligosiloxane 10g/L, methyl sodium silicate 1.5g/L, aliphatic alcohol block polyether 0.5g/L, and deionized water the rest. The prepared solution is concentrated solution, when in use, the concentrated solution is diluted according to 3% -20%, the pH value is 1-3, the copper foil is soaked and passivated for 6-10s at room temperature, and the concentrated solution is dried by hot air after water washing.
Example 4
8g/L of hydroxyethylidene diphosphonic acid, 6g/L of citric acid, 6g/L of ammonium molybdate, 2g/L of lanthanum nitrate, 10g/L of epoxy functional oligosiloxane, 1.5g/L of tetramethyl ammonium silicate, 0.5g/L of maleic acid-acrylic acid copolymer and the balance of deionized water. The prepared solution is concentrated solution, when in use, the concentrated solution is diluted according to 3% -20%, the pH value is 1-3, the copper foil is soaked and passivated for 6-10s at room temperature, and the concentrated solution is dried by hot air after water washing.
Example 5
8g/L malic acid, 6g/L ethylenediamine tetraacetic acid, 6g/L nickel sulfate, 1g/L sodium metavanadate, 8g/L tetramethyl ammonium silicate, 2g/L methylbenzotriazole, 0.5 g/L2-ethylhexyl sulfate sodium salt and the balance deionized water. The prepared solution is concentrated solution, when in use, the concentrated solution is diluted according to 3% -20%, the pH value is 1-3, the copper foil is soaked and passivated for 6-10s at room temperature, and the concentrated solution is dried by hot air after water washing.
Example 6
8g/L of citric acid, 8g/L of sulfosalicylic acid, 3g/L of titanyl sulfate, 2g/L of monopotassium phosphate, 12g/L of sodium methyl silicate, 8g/L of benzotriazole, 0.5g/L of decyne diol polyoxyethylene ether and the balance of deionized water. The prepared solution is concentrated solution, when in use, the concentrated solution is diluted according to 3% -20%, the pH value is 1-3, the copper foil is soaked and passivated for 6-10s at room temperature, and the concentrated solution is dried by hot air after water washing.
Example 7
Succinic acid 10g/L, fluorozirconic acid 5g/L, sodium tungstate 6g/L, potassium fluorozirconate 2g/L, acidic silica sol (effective content 25%) 250g/L, gemini silane organic wetting agent JC-7000 0.3g/L, and deionized water the rest. The prepared solution is concentrated solution, when in use, the concentrated solution is diluted according to 5% -20%, the pH value is 1-3, the copper foil is soaked and passivated for 6-10s at room temperature, and the concentrated solution is dried by hot air after water washing.
Example 8
15g/L of sulfosalicylic acid, 5g/L of glycine, 3g/L of sodium molybdate, 3g/L of nickel chloride, 2g/L of sodium metavanadate, 10g/L of epoxy functional oligosiloxane, 5g/L of tetramethyl ammonium silicate, 0.5g/L of aliphatic alcohol block polyether and the balance of deionized water. The prepared solution is concentrated solution, when in use, the concentrated solution is diluted according to 3% -20%, the pH value is 1-3, the copper foil is soaked and passivated for 6-10s at room temperature, and the concentrated solution is dried by hot air after water washing.
Example 9
8g/L of malic acid, 8g/L of L-ascorbic acid, 6g/L of titanyl sulfate, 0.5g/L of lanthanum nitrate, 2g/L of monopotassium phosphate, 300g/L of acidic silica sol (effective content of 25%), 0.3g/L of 2-ethylhexyl sulfate sodium salt and the balance of deionized water. The prepared solution is concentrated solution, when in use, the concentrated solution is diluted according to 3% -20%, the pH value is 1-3, the copper foil is soaked and passivated for 6-10s at room temperature, and the concentrated solution is dried by hot air after water washing.
Example 10
Tetra sodium glutamate diacetate 10g/L, succinic acid 10g/L, nickel chloride 3g/L, cobalt nitrate 3g/L, potassium fluorozirconate 1g/L, sodium metavanadate 1g/L, methylbenzotriazole 8g/L, tetramethyl ammonium silicate 5g/L, maleic acid-acrylic acid copolymer 0.1g/L, and deionized water as the rest. The prepared solution is concentrated solution, when in use, the concentrated solution is diluted according to 3% -20%, the pH value is 1-3, the copper foil is soaked and passivated for 6-10s at room temperature, and the concentrated solution is dried by hot air after water washing.
TABLE 1 passivation film baking test conditions and evaluation criteria
FIG. 1 is a graph comparing color change before and after baking at 180℃for 60 minutes of unpassivated copper foil; FIGS. 2 to 11 show the color changes of the passivation films obtained by the same passivation process using the passivation solutions prepared in examples 1 to 10, respectively, before and after baking at 180℃for 60 minutes. As can be seen from the comparison of figures 1-11, the copper foil passivated by the chromium-free high-temperature oxidation-resistant passivating agent for electrolytic copper foil has greatly improved oxidation resistance, can be baked at 180 ℃ for 60 minutes without color change, has uniform appearance, and exceeds the requirement of baking at 140 ℃ for 15 minutes without color change specified by the electrolytic copper foil industry standard SJ/T11483-2014.
The present invention can be realized by the respective raw materials listed in the present invention, and the upper and lower limits and interval values of the respective raw materials, and the upper and lower limits and interval values of the process parameters (such as temperature, time, etc.), and examples are not listed here.
While the invention has been described with respect to the preferred embodiments, it will be understood that the invention is not limited thereto, but is capable of modification and variation without departing from the spirit of the invention, as will be apparent to those skilled in the art.
Claims (9)
1. The chromium-free high-temperature anti-oxidation passivating agent for the electrolytic copper foil is characterized by comprising the following components in parts by weight:
complexing agent 10-22g/L;
2-6g/L of corrosion inhibitor;
1-3g/L of auxiliary corrosion inhibitor;
8-300g/L of antioxidant;
0.1-0.5g/L of wetting agent;
the solvent is deionized water.
2. The electrolytic copper foil chromium-free high temperature oxidation-preventing passivating agent according to claim 1, wherein: the pH value of the passivating agent is 1-3.
3. The electrolytic copper foil chromium-free high temperature oxidation-preventing passivating agent according to claim 1, wherein: the complexing agent is one or two of lactic acid, L-ascorbic acid, malic acid, succinic acid, tetra sodium glutamate diacetate, glycine, sulfosalicylic acid, sulfamic acid, fluoboric acid, fluozirconic acid and phosphoric acid.
4. The electrolytic copper foil chromium-free high temperature oxidation-preventing passivating agent according to claim 1, wherein: the corrosion inhibitor is one or two of sodium molybdate, sodium tungstate and titanyl sulfate.
5. The electrolytic copper foil chromium-free high temperature oxidation-preventing passivating agent according to claim 1, wherein: the auxiliary corrosion inhibitor is one or two of lanthanum nitrate, cerium nitrate, sodium metavanadate, potassium fluorozirconate and manganese sulfate.
6. The electrolytic copper foil chromium-free high temperature oxidation-preventing passivating agent according to claim 1, wherein: the antioxidant is as follows: acidic silica sol (25% of effective content), epoxy functional oligosiloxane, benzotriazole, methylbenzotriazole, tetramethylammonium silicate, sodium methyl silicate.
7. The electrolytic copper foil chromium-free high temperature oxidation-preventing passivating agent according to claim 1, wherein: the wetting agent is as follows: one or two of decyne glycol polyoxyethylene ether, fatty alcohol block polyether, 2-ethylhexyl sulfate sodium salt, gemini silane organic wetting agent JC-7000 and maleic acid-acrylic acid copolymer.
8. A method for preparing the chromium-free high-temperature oxidation-preventing passivating agent for electrolytic copper foil according to any one of claims 1-7, comprising the following steps:
(1) adding a calculated amount of deionized water into a preparation container;
(2) adding the calculated amount of complexing agent in sequence, and fully stirring;
(3) sequentially adding a calculated amount of corrosion inhibitor and an auxiliary corrosion inhibitor, and stirring at normal temperature until the corrosion inhibitor and the auxiliary corrosion inhibitor are completely dissolved;
(4) slowly adding a calculated amount of antioxidant, and fully stirring;
(5) adding the calculated amount of wetting agent, and fully stirring to obtain the electrolytic copper foil chromium-free high-temperature oxidation-resistant passivating agent.
9. A method of using the chromium-free high temperature oxidation-preventing passivating agent for electrolytic copper foil according to any one of claims 1-8, comprising the steps of:
diluting the passivating agent by 5% -20%, and adjusting the pH value: 1-3, the passivation temperature is room temperature, and the passivation mode is soaking; the passivation time is 6-10s.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005068683A1 (en) * | 2004-01-08 | 2005-07-28 | China International Marine Containers(Group) Co., Ltd. | Chrome-free passivating solution |
| CN105695977A (en) * | 2016-02-04 | 2016-06-22 | 南昌大学 | Method for carrying out surface treatment on electrolytic copper foil by virtue of high-heat-resistance organosiloxane film-forming material |
| CN109183018A (en) * | 2018-10-18 | 2019-01-11 | 苏州吉之美表面处理材料有限公司 | A kind of copper foil chromium-free passivation liquid and preparation method thereof |
| CN111575693A (en) * | 2020-06-15 | 2020-08-25 | 武汉迪赛环保新材料股份有限公司 | Chromium-free pre-passivation solution for hot-dip galvanized steel pipe |
| CN112144049A (en) * | 2019-07-26 | 2020-12-29 | 佛山市顺德区新琪洗涤用品有限公司 | Copper material chromium-free passivator and preparation method and use method thereof |
-
2022
- 2022-12-29 CN CN202211717034.3A patent/CN116288305A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005068683A1 (en) * | 2004-01-08 | 2005-07-28 | China International Marine Containers(Group) Co., Ltd. | Chrome-free passivating solution |
| CN105695977A (en) * | 2016-02-04 | 2016-06-22 | 南昌大学 | Method for carrying out surface treatment on electrolytic copper foil by virtue of high-heat-resistance organosiloxane film-forming material |
| CN109183018A (en) * | 2018-10-18 | 2019-01-11 | 苏州吉之美表面处理材料有限公司 | A kind of copper foil chromium-free passivation liquid and preparation method thereof |
| CN112144049A (en) * | 2019-07-26 | 2020-12-29 | 佛山市顺德区新琪洗涤用品有限公司 | Copper material chromium-free passivator and preparation method and use method thereof |
| CN111575693A (en) * | 2020-06-15 | 2020-08-25 | 武汉迪赛环保新材料股份有限公司 | Chromium-free pre-passivation solution for hot-dip galvanized steel pipe |
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