CN109208050B - Surface treatment method for improving corrosion resistance of electrolytic copper foil - Google Patents
Surface treatment method for improving corrosion resistance of electrolytic copper foil Download PDFInfo
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 239000011889 copper foil Substances 0.000 title claims abstract description 64
- 238000000034 method Methods 0.000 title claims abstract description 33
- 238000005260 corrosion Methods 0.000 title claims abstract description 21
- 230000007797 corrosion Effects 0.000 title claims abstract description 21
- 238000004381 surface treatment Methods 0.000 title claims abstract description 19
- 238000007747 plating Methods 0.000 claims abstract description 20
- 239000011888 foil Substances 0.000 claims abstract description 12
- 238000002161 passivation Methods 0.000 claims abstract description 11
- 238000005507 spraying Methods 0.000 claims abstract description 11
- 239000007822 coupling agent Substances 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 15
- HDUMBHAAKGUHAR-UHFFFAOYSA-J titanium(4+);disulfate Chemical class [Ti+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O HDUMBHAAKGUHAR-UHFFFAOYSA-J 0.000 claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 239000000654 additive Substances 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- 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 8
- 235000019270 ammonium chloride Nutrition 0.000 claims description 8
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 8
- 239000004327 boric acid Substances 0.000 claims description 8
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 8
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 8
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 8
- 239000001509 sodium citrate Substances 0.000 claims description 8
- 239000011975 tartaric acid Substances 0.000 claims description 8
- 235000002906 tartaric acid Nutrition 0.000 claims description 8
- WVWURCPXADTHPI-UHFFFAOYSA-J tetrapotassium 2,2-diphosphonatoethanol Chemical group [K+].[K+].[K+].[K+].OCC(P([O-])([O-])=O)P([O-])([O-])=O WVWURCPXADTHPI-UHFFFAOYSA-J 0.000 claims description 8
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 8
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 8
- 229960001763 zinc sulfate Drugs 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 6
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 6
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 5
- 239000013065 commercial product Substances 0.000 claims description 5
- 238000007796 conventional method Methods 0.000 claims description 5
- 238000007788 roughening Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000009736 wetting Methods 0.000 claims description 5
- 239000008139 complexing agent Substances 0.000 claims description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 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 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 238000012360 testing method Methods 0.000 abstract description 14
- 230000003647 oxidation Effects 0.000 abstract description 13
- 238000007254 oxidation reaction Methods 0.000 abstract description 13
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000007711 solidification Methods 0.000 abstract 1
- 230000008023 solidification Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 20
- 238000002845 discoloration Methods 0.000 description 5
- 229910052761 rare earth metal Inorganic materials 0.000 description 5
- 239000011973 solid acid Substances 0.000 description 5
- 150000002910 rare earth metals Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910000348 titanium sulfate Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- -1 La2O3 modified titanium sulfate Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006388 chemical passivation reaction Methods 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004649 discoloration prevention Methods 0.000 description 1
- 238000001978 electrochemical passivation Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 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 1
- 238000009776 industrial production Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 150000003071 polychlorinated biphenyls Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003860 storage 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
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0614—Strips or foils
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating Methods And Accessories (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
The invention discloses a surface treatment method for improving corrosion resistance of an electrolytic copper foil, and belongs to the technical field of electrolytic copper foil production. The treatment method comprises the steps of raw foil pretreatment, plating solution solidification, passivation treatment, coupling agent spraying and the like. Tests show that the 12-micron copper foil product prepared by the process disclosed by the invention has the performances of oxidation resistance, corrosion resistance, peeling strength resistance and the like which meet the application requirements, and shows good prospects and application values.
Description
Technical Field
The invention belongs to the technical field of electrolytic copper foil surface treatment, and particularly relates to a surface treatment method for improving the corrosion resistance of an electrolytic copper foil.
Background
The electrolytic copper foil is one of basic materials in the electronic industry, has wide application in the electronic industry and plays an important role in the development of the whole electronic industry. The electrolytic copper foil is a metal copper deposition layer obtained by an electrodeposition technology under the action of a certain current density by using a proper electrolyte solution, and is widely used for producing copper clad laminates (CCLs for short) and printed circuit boards (PCBs for short).
The quality of the electrolytic copper foil is not only related to the green foil substrate but also to the surface treatment technique of the copper foil [ 1 ]. After the electrolytic copper foil is treated by a proper surface treatment process, the quality and the performance of the product can be effectively improved, so that the electrolytic copper foil has excellent heat resistance, corrosion resistance and higher peel strength, and meets higher requirements of industrial production.
In order to meet the functional requirements of miniaturization and light weight of electronic equipment, thin copper foils or ultrathin copper foils with the thickness of less than 12 microns are increasingly applied, and the traditional copper foil surface treatment technology cannot meet the requirements of better elongation, flatness, high temperature resistance, oxidation resistance and the like for ensuring the copper foil to have high performance. Since copper foil is subject to oxidation, corrosion, etc. during storage, transportation, etc., it is often necessary to surface-treat the copper foil to prevent oxidation of the copper foil. At present, the traditional oxidation-resistant treatment method for the surface of the copper foil is a passivation method, namely chemical passivation in chromic acid solution or electrolytic passivation under chromate, and the main purpose of the oxidation-resistant treatment method is to form a chromized layer on the surface of the copper foil to isolate the copper foil from air so as to achieve the effects of rust prevention, spot prevention and discoloration prevention. However, with respect to the technical level of the currently used surface treatment additives and treatment processes, the treated copper foil still cannot fully meet the actual production requirements in terms of oxidation resistance and corrosion resistance.
Disclosure of Invention
The invention mainly aims to provide a surface treatment method for improving the corrosion resistance of an electrolytic copper foil, and the corrosion resistance and the oxidation resistance of the copper foil are obviously improved after the surface treatment method.
The above object of the present invention is achieved by the following technical solution, a surface treatment method for improving corrosion resistance of an electrolytic copper foil, comprising the steps of:
(1) pretreatment of raw foil: removing oil from a copper foil raw foil by using absolute ethyl alcohol according to a conventional method, washing with water, removing an oxide film by using sulfuric acid, washing with water again, roughening, and washing with water again.
(2) Solidifying the plating solution: and (3) carrying out a curing plating solution on the pretreated copper foil, wherein the curing solution comprises zinc sulfate, nickel sulfate, an additive and a complexing agent.
Further, the curing liquid also comprises catalyst modified titanium sulfate.
Further, the additives comprise sodium citrate, tartaric acid, N', N-dimethylformamide, boric acid and ammonium chloride.
Further, the complexing agent is hydroxyethylidene diphosphonic acid potassium salt.
Further, the curing liquid comprises the following components: 80-110 g/L of zinc sulfate, 60-90 g/L of nickel sulfate, 20-50 g/L of sodium hypophosphite, 5-10 g/L of modified titanium sulfate, 3-9 g/L of sodium citrate, 2-5 g/L of tartaric acid, 10-15 g/L of N', N-dimethylformamide, 15 m L g/L of boric acid, 2-6 g/L of ammonium chloride and 2-10 g/L of hydroxyethylidene diphosphonic acid potassium salt.
The preparation method of the modified titanium sulfate comprises the following steps: weighing a certain amount of Ti (SO4)2, dissolving in deionized water, dissolving a certain amount of La2O3 in the deionized water, drying at 100 ℃, roasting the solid in a muffle furnace at 400-500 ℃ for 4 hours, cooling, grinding and storing in a dry environment for later use.
The curing process condition is that the cathode current density is 2-3A/dm2The temperature is normal temperature, the anode is a lead plate, and the plating time is 16-20 s.
(3) Passivating, wherein the passivation solution is a commercial product, and is passivated under the conditions of pH value of 8.0-11.0 and temperature of 40-50 ℃, and the passivation treatment is preferably carried out for 5 s;
(4) and (3) spraying a coupling agent, namely spraying and wetting the surface of the electrolytic copper foil by adopting a KBE-903 silane coupling agent.
The titanium sulfate is doped with La2O3 and then is roasted at high temperature to prepare rare earth modified solid acid, rare earth elements are introduced into the solid acid, and the modified solid acid not only has the advantages of better acid catalytic activity, less rare earth content, quick settlement after reaction, easy separation and recovery, repeated use, easy regeneration and the like, but also greatly simplifies the post-treatment process of the reaction, and the product is colorless, clear and transparent. The rare earth modified solid acid is an environment-friendly catalyst.
To further verify the effect of modified titanium sulfate as a curing solution additive in improving the corrosion resistance of the electrolytic copper foil, the company made the following tests:
for the test, a 12 μm high-purity electrolytic copper foil manufactured by this company was used, and a copper foil was cut into two pieces in a size of 5 cm × 10cm, and surface-treated with a test curing liquid and a control curing liquid, respectively, to study the corrosion resistance of the matte side of the copper foil.
Test groups: the curing liquid comprises 100 g/L of zinc sulfate, 80 g/L of nickel sulfate, 35 g/L of sodium hypophosphite, 8 g/L of modified titanium sulfate, 6g/L of sodium citrate, 3 g/L of tartaric acid, 12 m L/L of N', N-dimethylformamide, 15 g/L of boric acid, 4 g/L of ammonium chloride and 6g/L of hydroxyethylidene diphosphonic acid potassium salt.
Control group: the other components of the curing liquid are completely in accordance with the test groups, except that the modified titanium sulfate, which is one of the additives, is replaced by titanium sulfate.
At a cathode current density of 3A/dm2The temperature is normal temperature, the anode is a lead plate, and the plating time is 20 s.
And (3) test results: the copper foils subjected to surface treatment of the test group and the control group are simultaneously placed in a constant temperature and humidity box, and corrosion performance tests are carried out under the conditions of 100 ℃ and 80% humidity, and the results show that the copper foils of the test group do not show oxidation discoloration phenomenon for 48 hours; the control group was clearly subject to oxidative discoloration. Meanwhile, an Instron 3343 type universal testing machine is adopted to detect the anti-peeling strength of the electrolytic copper foil, the test group has the result of 1.18N/mm, the control group has the result of 1.06N/mm, and the test group shows better anti-peeling strength performance.
The invention has the beneficial effects that: the surface treatment of electrolytic copper foil by using titanium sulfate modified as an additive of a curing solution is not reported, and particularly, the corrosion resistance of the copper foil is improved by using rare earth modified solid acid prepared by using La2O3 modified titanium sulfate and roasting at high temperature. Compared with the prior art, the electrolytic copper foil surface treatment of the invention adopts the modified titanium sulfate as the additive, can enhance the deep plating capability of the electrolytic copper foil, and can plate a uniform fine alloy particle coarsening layer on both the profile peak height and the profile valley, so that the produced very-low profile electrolytic copper foil achieves the microcrystal effect, the peeling strength of the copper foil on the substrate is enhanced, the plating layer is crystallized and compact, and the corrosion resistance of the plating layer is enhanced. Meanwhile, the process does not contain harmful elements such As Pb, As and the like, and has good environmental protection characteristic. Tests show that the 12-micron copper foil product prepared by the process disclosed by the invention has the performances of oxidation resistance, corrosion resistance, peeling strength resistance and the like which meet the application requirements, and shows good prospects and application values.
Detailed Description
The first embodiment is as follows: a surface treatment method for improving the corrosion resistance of an electrolytic copper foil comprises the following steps:
(1) pretreatment of raw foil: removing oil from a copper foil raw foil by using absolute ethyl alcohol according to a conventional method, washing with water, removing an oxide film by using sulfuric acid, washing with water again, roughening, and washing with water again.
(2) Solidifying the plating solution: carrying out curing plating solution on the pretreated copper foil, wherein the curing solution comprises the following components: 100 g/L of zinc sulfate, 80 g/L of nickel sulfate, 35 g/L of sodium hypophosphite, 8 g/L of modified titanium sulfate, 6g/L of sodium citrate, 3 g/L of tartaric acid, 12 m L/L of N', N-dimethylformamide, 15 g/L of boric acid, 4 g/L of ammonium chloride and 6g/L of hydroxyethylidene diphosphonic acid potassium salt.
The curing process condition is that the cathode current density is 2A/dm2The temperature is normal temperature, the anode is a lead plate, and the plating time is 16 s.
(3) Passivating, wherein the passivation solution is a commercial product, and is passivated under the conditions of pH value of 8.0-11.0 and 45 ℃, and the passivation treatment is preferably carried out for 5 s;
(4) and (3) spraying a coupling agent, namely spraying and wetting the surface of the electrolytic copper foil by adopting a KBE-903 silane coupling agent.
The electrolytic copper foil obtained by the treatment method is placed in a constant temperature and humidity box, and does not show oxidation discoloration phenomenon within 48 hours under the conditions of 70 ℃ and 80% of humidity.
Example two: a surface treatment method for improving the corrosion resistance of an electrolytic copper foil comprises the following steps:
(1) pretreatment of raw foil: removing oil from a copper foil raw foil by using absolute ethyl alcohol according to a conventional method, washing with water, removing an oxide film by using sulfuric acid, washing with water again, roughening, and washing with water again.
(2) Solidifying the plating solution: carrying out curing plating solution on the pretreated copper foil, wherein the curing solution comprises the following components: 80 g/L of zinc sulfate, 60 g/L of nickel sulfate, 20g/L of sodium hypophosphite, 10g/L of modified titanium sulfate, 9g/L of sodium citrate, 2g/L of tartaric acid, 10 m L/L of N', N-dimethylformamide, 20g/L of boric acid, 2g/L of ammonium chloride and 10g/L of hydroxyethylidene diphosphonic acid potassium salt.
The curing process condition is that the cathode current density is 3A/dm2At normal temperature, the anodeIs a lead plate, wherein the plating time is 20 s.
(3) Passivating, wherein the passivation solution is a commercial product, and is passivated under the conditions of pH value of 8.0-11.0 and 40 ℃, and the passivation treatment is preferably carried out for 5 s;
(4) and (3) spraying a coupling agent, namely spraying and wetting the surface of the electrolytic copper foil by adopting a KBE-903 silane coupling agent.
The electrolytic copper foil obtained by the treatment method is placed in a constant temperature and humidity box, and does not show oxidation discoloration phenomenon within 48 hours under the conditions of 120 ℃ and 80% humidity.
Example three: a surface treatment method for improving the corrosion resistance of an electrolytic copper foil comprises the following steps:
(1) pretreatment of raw foil: removing oil from a copper foil raw foil by using absolute ethyl alcohol according to a conventional method, washing with water, removing an oxide film by using sulfuric acid, washing with water again, roughening, and washing with water again.
(2) Solidifying the plating solution: carrying out curing plating solution on the pretreated copper foil, wherein the curing solution comprises the following components: 110g/L of zinc sulfate, 90g/L of nickel sulfate, 50g/L of sodium hypophosphite, 5 g/L of modified titanium sulfate, 3 g/L of sodium citrate, 5 g/L of tartaric acid, 15 m L/L of N', N-dimethylformamide, 10g/L of boric acid, 6g/L of ammonium chloride and 2g/L of hydroxyethylidene diphosphonic acid potassium salt.
The curing process condition is that the cathode current density is 3A/dm2The temperature is normal temperature, the anode is a lead plate, and the plating time is 20 s.
(3) Passivating, wherein the passivation solution is a commercial product, and is passivated under the conditions of pH value of 8.0-11.0 and 40 ℃, and the passivation treatment is preferably carried out for 5 s;
(4) and (3) spraying a coupling agent, namely spraying and wetting the surface of the electrolytic copper foil by adopting a KBE-903 silane coupling agent.
The electrolytic copper foil obtained by the treatment method has the following performance indexes through tests:
the electrolytic copper foil obtained by the treatment method is placed in a constant temperature and humidity box, and does not show oxidation discoloration phenomenon within 48 hours under the conditions of 150 ℃ and 80% of humidity.
Claims (1)
1. A surface treatment method for improving corrosion resistance of an electrolytic copper foil, the treatment method comprising the steps of: (1) pretreatment of raw foil: removing oil from a copper foil raw foil by using absolute ethyl alcohol according to a conventional method, washing with water, removing an oxide film by using sulfuric acid, washing with water again, roughening, and washing with water again; (2) solidifying the plating solution: carrying out a curing plating solution on the pretreated copper foil, wherein the curing solution comprises zinc sulfate, nickel sulfate, an additive and a complexing agent; (3) passivating, wherein the passivation solution is a commercial product, and is passivated for 5s at the conditions of pH value of 8.0-11.0 and temperature of 40-50 ℃; (4) spraying a coupling agent, namely spraying and wetting the surface of the electrolytic copper foil by adopting a KBE-903 silane coupling agent; the additive comprises sodium citrate, tartaric acid, N', N-dimethylformamide, boric acid and ammonium chloride; the complexing agent is hydroxyl ethylidene diphosphonic acid potassium salt; the curing liquid comprises the following components: 80-110 g/L of zinc sulfate, 60-90 g/L of nickel sulfate, 20-50 g/L of sodium hypophosphite, 5-10 g/L of modified titanium sulfate, 3-9 g/L of sodium citrate, 2-5 g/L of tartaric acid, 10-15 mL/L of N', N-dimethylformamide, 10-20 g/L of boric acid, 2-6 g/L of ammonium chloride and 2-10 g/L of hydroxyethylidene diphosphonic acid potassium salt; the curing process conditions comprise that the cathode current density is 2-3A/dm 2, the temperature is normal temperature, the anode is a lead plate, and the plating time is 16-20 s; the method is characterized in that the curing solution also comprises catalyst modified titanium sulfate, and the preparation method of the modified titanium sulfate comprises the following steps: weighing a certain amount of Ti (SO)4)2Dissolving with deionized water, and adding a certain amount of La2O3Dissolving the solid into the solution, drying the solid at 100 ℃, roasting the solid in a muffle furnace at 400-500 ℃ for 4 hours, cooling, grinding and storing the solid in a dry environment for later use.
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| CN109518237B (en) * | 2019-01-24 | 2020-12-08 | 合鸿新材科技有限公司 | Zinc-nickel-phosphorus electroplating solution, preparation method thereof and electroplating method |
| CN110079840A (en) * | 2019-04-26 | 2019-08-02 | 山东金宝电子股份有限公司 | A kind of surface treatment additive package improving copper foil high-temp antioxidizing performance |
| CN111005045A (en) * | 2019-12-31 | 2020-04-14 | 西安西工大超晶科技发展有限责任公司 | Preparation method of titanium and titanium alloy surface coating |
| CN113943954B (en) * | 2021-12-01 | 2023-06-30 | 青海诺德新材料有限公司 | Preparation method of 2-3 micron pinhole-free carrier electrolytic copper foil |
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