CN116377529A - Blackened copper foil and surface treatment process thereof - Google Patents
Blackened copper foil and surface treatment process thereof Download PDFInfo
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- CN116377529A CN116377529A CN202310504584.5A CN202310504584A CN116377529A CN 116377529 A CN116377529 A CN 116377529A CN 202310504584 A CN202310504584 A CN 202310504584A CN 116377529 A CN116377529 A CN 116377529A
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- copper foil
- curing
- electroplating
- blackening
- surface treatment
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 239000011889 copper foil Substances 0.000 title claims abstract description 100
- 238000000034 method Methods 0.000 title claims abstract description 41
- 238000004381 surface treatment Methods 0.000 title claims abstract description 28
- 230000008569 process Effects 0.000 title claims abstract description 27
- 238000009713 electroplating Methods 0.000 claims abstract description 74
- 239000007788 liquid Substances 0.000 claims abstract description 46
- 238000005507 spraying Methods 0.000 claims abstract description 20
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910000077 silane Inorganic materials 0.000 claims abstract description 15
- 108010010803 Gelatin Proteins 0.000 claims abstract description 13
- 229920000159 gelatin Polymers 0.000 claims abstract description 13
- 239000008273 gelatin Substances 0.000 claims abstract description 13
- 235000019322 gelatine Nutrition 0.000 claims abstract description 13
- 235000011852 gelatine desserts Nutrition 0.000 claims abstract description 13
- 229920002401 polyacrylamide Polymers 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 10
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 10
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 10
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004327 boric acid Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 10
- 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 abstract description 10
- 239000001509 sodium citrate Substances 0.000 claims abstract description 10
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims abstract description 10
- 229910000368 zinc sulfate Inorganic materials 0.000 claims abstract description 10
- 229960001763 zinc sulfate Drugs 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 50
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 18
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 18
- 238000007788 roughening Methods 0.000 claims description 17
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 8
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 6
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 claims description 6
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- 230000009471 action Effects 0.000 abstract description 3
- 230000003287 optical effect Effects 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 238000005554 pickling Methods 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 4
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 4
- 238000007747 plating Methods 0.000 description 4
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- -1 KSCN Chemical compound 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical group [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 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
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/22—Electroplating: Baths therefor from solutions of zinc
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
-
- 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
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
The invention belongs to the technical field of copper foil surface treatment, and discloses a blackened copper foil and a surface treatment process thereof. The surface treatment process of the blackened copper foil comprises the following steps: sequentially carrying out acid washing, coarsening, curing, blackening, silane spraying and drying treatment on the copper foil; the blackening method comprises the steps of placing the copper foil in blackening liquid for electroplating treatment, wherein the electroplating conditions are as follows: the current density is 5-15A/dm 2 The electroplating time is 5-12 s, and the temperature is 30-45 ℃; the blackening liquid comprises the following components: 25-50 g/L of zinc sulfate, 10-25 g/L of sodium citrate, 10-20 g/L of boric acid, 15-25 g/L of ammonium sulfate, 5-15 g/L of polyacrylamide and 4-8 g/L of gelatin. The invention forms an optical trap on the surface of the copper foil under the combined action of the polyacrylamide and the gelatin, and when the light irradiates the surface of the copper foil, the light is reflected and refracted for multiple times, thereby achieving the blackening purposeA kind of electronic device.
Description
Technical Field
The invention relates to the technical field of copper foil surface treatment, in particular to a blackened copper foil and a surface treatment process thereof.
Background
The copper foil is mainly divided into an electrolytic copper foil and a rolled copper foil according to different preparation processes, and can be used for a flexible printed circuit board. In order to meet the requirements of the circuit board on the performances of heat resistance, corrosion resistance and the like of the copper foil, the surface of the copper foil is generally required to be subjected to blackening treatment. Chinese patent CN102618902B discloses a surface treatment process for a copper foil for a flexible copper clad laminate, wherein a blackening agent is added in the blackening step, wherein the blackening agent is selected from ammonium citrate, ammonium sulfate, ammonia water, ammonium thiocyanate and thiourea, and a black ultra-fine plating layer capable of improving corrosion resistance of the copper foil and etching property of the copper foil is formed on the surface of the copper foil.
At present, the blackening treatment of the copper foil surface is mainly performed by electroplating nickel and cobalt, and a blackening agent is added into the electroplating solution for electroplating nickel and cobalt, wherein the blackening agent is generally thiocyanide such as KSCN, NHSCN, SC (NH) 2 And the like as blackening agents to obtain a good black effect, but the thiocyanate causes serious pollution problems.
Therefore, the problem of pollution caused by the use of thiocyanate as a blackening agent in the blackening treatment of copper foil is needed to be solved.
Disclosure of Invention
The invention aims to provide a blackened copper foil and a surface treatment process thereof, which are used for solving the problems in the prior art.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a surface treatment process of a blackened copper foil, which comprises the following steps of:
sequentially carrying out acid washing, coarsening I, coarsening II, curing I, curing II, blackening, silane spraying and drying treatment on the copper foil;
the blackening method comprises the steps of placing copper foil in blackening liquid for electroplating treatment, wherein the electroplating conditions are as follows: the current density is 5-15A/dm 2 The electroplating time is 5-12 s, and the temperature is 30-45 ℃;
the blackening liquid comprises the following components: 25-50 g/L of zinc sulfate, 10-25 g/L of sodium citrate, 10-20 g/L of boric acid, 15-25 g/L of ammonium sulfate, 5-15 g/L of polyacrylamide and 4-8 g/L of gelatin.
Preferably, in the surface treatment process of a blackened copper foil, the method of roughening the first and second copper foils is independently to place the copper foil in a roughening solution for electroplating treatment, and the electroplating conditions in the first and second copper foils are independently as follows: the current density is 15-25A/dm 2 The electroplating time is 5-15 s, and the temperature is 20-30 ℃;
the components of the coarsening liquid in the coarsening I and the coarsening II independently comprise: 50-100 g/L sulfuric acid and 30-50 g/L copper sulfate.
Preferably, in the surface treatment process of a blackened copper foil, the method of curing i and curing ii is independently to place the copper foil in a curing solution for electroplating treatment, and the electroplating conditions in the curing i and curing ii are independently: the current density is 15-25A/dm 2 The electroplating time is 5-15 s, and the temperature is 30-45 ℃;
the components of the curing liquid in the curing I and the curing II independently comprise: 40-80 g/L sulfuric acid and 60-80 g/L copper sulfate.
Preferably, in the surface treatment process of the blackened copper foil, the concentration of the silane coupling agent in the silane spraying is 4-8 g/L, and the temperature of the silane spraying is 20-35 ℃.
Preferably, in the surface treatment process of the blackened copper foil, the silane coupling agent is one or more of gamma- (2, 3-glycidoxy) propyl trimethoxysilane, 3-aminopropyl trimethoxysilane and gamma-aminopropyl triethoxysilane.
The invention also provides a blackened copper foil obtained by the surface treatment process of the blackened copper foil.
Compared with the prior art, the invention has the following beneficial effects:
(1) The polyacrylamide in the blackening liquid has unsaturated bonds, and can be adsorbed on the surface of an electrode to realize cathode polarization, so that reduction of zinc ions is inhibited; gelatin moves to the cathode under the action of an electric field, increases cathode polarization, occupies active sites on the surface of an electrode, reduces nucleation sites of zinc grains while inhibiting zinc ion reduction, and can adjust the height and the spacing of the grains under the combined action of the gelatin and the zinc ions, so that an optical trap is formed on the surface of the copper foil; when light irradiates on the surface of the copper foil, multiple reflection and refraction occur, so that the blackening purpose is achieved.
(2) According to the invention, after roughening and curing treatment are carried out on the surface of the copper foil, a layer of zinc is electroplated to realize blackening treatment on the surface of the copper foil, and substances such as arsenic, lead, mercury and thiocyanate which pollute the environment are not used in the blackening process, so that the environment is protected.
(3) The blackened copper foil prepared by the invention has excellent normal-temperature and high-temperature oxidation resistance.
Detailed Description
The invention provides a surface treatment process of a blackened copper foil, which comprises the following steps of:
and (3) sequentially carrying out acid washing, coarsening I, coarsening II, curing I, curing II, blackening, silane spraying and drying treatment on the copper foil.
In the invention, the pickling method is to use sulfuric acid solution to perform pickling on the copper foil, wherein the pickling time is preferably 5-20 s, more preferably 8-17 s, and even more preferably 10-15 s; the concentration of sulfuric acid is preferably 100 to 150g/L, more preferably 105 to 140g/L, and even more preferably 120 to 132g/L.
In the invention, the method for coarsening I and coarsening II is independently to place the copper foil into coarsening liquid for electroplating treatment, and the electroplating conditions in coarsening I and coarsening II are independently as follows: the current density is preferably 15 to 25A/dm 2 Further preferably 17 to 22A/dm 2 More preferably 19 to 21A/dm 2 The method comprises the steps of carrying out a first treatment on the surface of the The plating time is preferably 5 to 15 seconds, more preferably 7 to 13 seconds, and still more preferably 9 to 10 seconds; the temperature is preferably 20 to 30 ℃, more preferably 21 to 27 ℃, still more preferably 23 to 25 ℃;
the components of the coarsening liquid in the coarsening I and the coarsening II independently comprise: 50-100 g/L sulfuric acid and 30-50 g/L copper sulfate;
in the coarsening solution of coarsening I and coarsening II, the content of sulfuric acid is independently preferably 50-100 g/L, more preferably 65-90 g/L, and even more preferably 70-82 g/L;
in the roughening solutions of the coarsening I and the coarsening II, the content of copper sulfate is independently preferably 30 to 50g/L, more preferably 35 to 47g/L, and even more preferably 39 to 43g/L.
In the invention, the method for curing I and curing II independently comprises the steps of placing copper foil in a curing liquid for electroplating treatment, wherein the electroplating conditions in the curing I and curing II independently comprise: the current density is preferably 15 to 25A/dm 2 Further preferably 17 to 22A/dm 2 More preferably 19 to 21A/dm 2 The method comprises the steps of carrying out a first treatment on the surface of the The plating time is preferably 5 to 15 seconds, more preferably 7 to 13 seconds, and still more preferably 9 to 10 seconds; the temperature is preferably 30 to 45 ℃, more preferably 32 to 43 ℃, still more preferably 35 to 40 ℃;
the components of the curing liquid in the curing I and the curing II independently comprise: 40-80 g/L of sulfuric acid and 60-80 g/L of copper sulfate;
in the curing liquid for curing I and curing II, the independent content of sulfuric acid is preferably 40-80 g/L, more preferably 48-72 g/L, and even more preferably 55-67 g/L;
the content of copper sulfate in the curing liquid for curing I and curing II is preferably 60 to 80g/L, more preferably 63 to 76g/L, and even more preferably 65 to 72g/L.
In the invention, the blackening method is that the copper foil is placed in blackening liquid for electroplating treatment, and the electroplating conditions are as follows: the current density is preferably 5 to 15A/dm 2 More preferably 8 to 13A/dm 2 More preferably 9 to 11A/dm 2 The method comprises the steps of carrying out a first treatment on the surface of the The plating time is preferably 5 to 12 seconds, more preferably 6 to 10 seconds, and still more preferably 7 to 9 seconds; the temperature is preferably 30 to 45 ℃, more preferably 32 to 41 ℃, and even more preferably 35 to 38 ℃.
The blackening liquid comprises the following components: 25-50 g/L of zinc sulfate, 10-25 g/L of sodium citrate, 10-20 g/L of boric acid, 15-25 g/L of ammonium sulfate, 5-15 g/L of polyacrylamide and 4-8 g/L of gelatin;
the content of zinc sulfate in the blackening liquid is preferably 25 to 50g/L, more preferably 28 to 45g/L, and even more preferably 31 to 38g/L;
the content of sodium citrate in the blackening liquid is preferably 10 to 25g/L, more preferably 12 to 23g/L, and even more preferably 15 to 19g/L;
the boric acid content in the blackening liquid is preferably 10 to 20g/L, more preferably 12 to 18g/L, and even more preferably 14 to 17g/L;
the content of ammonium sulfate in the blackening liquid is preferably 15 to 25g/L, more preferably 17 to 23g/L, and even more preferably 19 to 21g/L;
the content of polyacrylamide in the blackening liquid is preferably 5 to 15g/L, more preferably 7 to 13g/L, and even more preferably 9 to 11g/L;
the content of gelatin in the blackening liquid is preferably 4 to 8g/L, more preferably 4.5 to 7g/L, and even more preferably 5 to 6g/L.
In the present invention, the concentration of the silane coupling agent in the silane spraying is preferably 4 to 8g/L, more preferably 4.5 to 7g/L, and still more preferably 5 to 6g/L; the silane spraying temperature is preferably 20 to 35 ℃, more preferably 23 to 31 ℃, and even more preferably 25 to 28 ℃.
In the present invention, the silane coupling agent is preferably one or more of gamma- (2, 3-glycidoxy) propyl trimethoxysilane, 3-aminopropyl trimethoxysilane and gamma-aminopropyl triethoxysilane, more preferably one or two of gamma- (2, 3-glycidoxy) propyl trimethoxysilane and 3-aminopropyl trimethoxysilane, and still more preferably gamma- (2, 3-glycidoxy) propyl trimethoxysilane.
In the present invention, the temperature of the drying is preferably 180 to 250 ℃, more preferably 195 to 230 ℃, and even more preferably 200 to 220 ℃.
The invention also provides a blackened copper foil obtained by the surface treatment process of the blackened copper foil.
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
A surface treatment process of a blackened copper foil comprises the following steps:
(1) Acid washing: pickling the copper foil by using a sulfuric acid solution with the concentration of 100g/L for 10s;
(2) Coarsening I: placing the acid-washed copper foil into a roughening solution for electroplating treatment; wherein, the components of the roughening liquid comprise: 60g/L sulfuric acid and 40g/L copper sulfate; conditions of electroplating: current density 15A/dm 2 Electroplating time is 8s, and the temperature is 20 ℃; repeating the steps to carry out coarsening II treatment;
(3) Curing I: placing the coarsened copper foil in a curing solution for electroplating treatment; wherein, the components of the curing liquid comprise: 75g/L sulfuric acid and 70g/L copper sulfate; conditions of electroplating: current density 15A/dm 2 Electroplating time is 8s, and the temperature is 35 ℃; repeating the steps to carry out curing II treatment;
(5) Blackening: placing the solidified copper foil into blackening liquid for electroplating treatment; wherein, the blackening liquid comprises the following components: 30g/L of zinc sulfate, 16g/L of sodium citrate, 13g/L of boric acid, 20g/L of ammonium sulfate, 14g/L of polyacrylamide and 7g/L of gelatin; conditions of electroplating: current density 10A/dm 2 Electroplating time is 8s, and the temperature is 35 ℃;
(6) And (3) silane spraying: spraying the copper foil at 25 ℃ by adopting 3-aminopropyl trimethoxysilane with the concentration of 4 g/L; and then drying at 200 ℃ to obtain the blackened copper foil.
Example 2
A surface treatment process of a blackened copper foil comprises the following steps:
(1) Acid washing: pickling the copper foil by using a sulfuric acid solution with the concentration of 130g/L for 13s;
(2) Coarsening I: placing the acid-washed copper foil into a roughening solution for electroplating treatment; wherein, the components of the roughening liquid comprise: 100g/L of sulfuric acid and 35g/L of copper sulfate; conditions of electroplating: current density 18A/dm 2 Electroplating time is 10s, and temperature is 20 ℃; repeating the steps to carry out coarsening II treatment;
(3) Curing I: placing the coarsened copper foil in a curing solution for electroplating treatment; wherein, the components of the curing liquid comprise: 80g/L sulfuric acid and 65g/L copper sulfate; conditions of electroplating: current density 15A/dm 2 Electroplating time is 10s, and temperature is 35 ℃; repeating the steps to carry out curing II treatment;
(5) Blackening: placing the solidified copper foil into blackening liquid for electroplating treatment; wherein, the blackening liquid comprises the following components: 45g/L of zinc sulfate, 10g/L of sodium citrate, 16g/L of boric acid, 23g/L of ammonium sulfate, 7g/L of polyacrylamide and 7g/L of gelatin; conditions of electroplating: current density 15A/dm 2 Electroplating time is 12s, and the temperature is 38 ℃;
(6) And (3) silane spraying: spraying the copper foil at 25 ℃ by adopting 3-aminopropyl trimethoxysilane with the concentration of 5.5 g/L; and then drying at 200 ℃ to obtain the blackened copper foil.
Example 3
A surface treatment process of a blackened copper foil comprises the following steps:
(1) Acid washing: pickling the copper foil by using a sulfuric acid solution with the concentration of 100g/L for 10s;
(2) Coarsening I: placing the acid-washed copper foil into a roughening solution for electroplating treatment; wherein, the components of the roughening liquid comprise: 95g/L sulfuric acid and 35g/L copper sulfate; conditions of electroplating: current density 15A/dm 2 Electroplating time is 8s, and the temperature is 25 ℃; repeating the steps to carry out coarsening II treatment;
(3) Curing I: placing the coarsened copper foil in a curing solution for electroplating treatment; wherein, the components of the curing liquid comprise: 80g/L sulfuric acid and 65g/L copper sulfate; conditions of electroplating: current density 15A/dm 2 Electroplating time is 8s, and the temperature is 35 ℃; repeating the steps to carry out curing II treatment;
(5) Blackening: placing the solidified copper foil into blackening liquid for electroplating treatment; wherein, the blackening liquid comprises the following components: 47g/L zinc sulfate, 20g/L sodium citrate, 17g/L boric acid and sulfur18g/L of ammonium acid, 10g/L of polyacrylamide and 6g/L of gelatin; conditions of electroplating: current density 8A/dm 2 Electroplating time is 8s, and the temperature is 35 ℃;
(6) And (3) silane spraying: spraying the copper foil at 25 ℃ by adopting gamma- (2, 3-glycidoxy) propyl trimethoxysilane with the concentration of 5g/L; and then drying at 200 ℃ to obtain the blackened copper foil.
Example 4
A surface treatment process of a blackened copper foil comprises the following steps:
(1) Acid washing: pickling the copper foil by using a sulfuric acid solution with the concentration of 100g/L for 10s;
(2) Coarsening I: placing the acid-washed copper foil into a roughening solution for electroplating treatment; wherein, the components of the roughening liquid comprise: 60g/L sulfuric acid and 40g/L copper sulfate; conditions of electroplating: current density 18A/dm 2 Electroplating time is 8s, and the temperature is 20 ℃; repeating the steps to carry out coarsening II treatment;
(3) Curing I: placing the coarsened copper foil in a curing solution for electroplating treatment; wherein, the components of the curing liquid comprise: 80g/L sulfuric acid and 75g/L copper sulfate; conditions of electroplating: current density 18A/dm 2 Electroplating time is 8s, and the temperature is 35 ℃; repeating the steps to carry out curing II treatment;
(5) Blackening: placing the solidified copper foil into blackening liquid for electroplating treatment; wherein, the blackening liquid comprises the following components: 30g/L of zinc sulfate, 12g/L of sodium citrate, 16g/L of boric acid, 23g/L of ammonium sulfate, 9g/L of polyacrylamide and 4.5g/L of gelatin; conditions of electroplating: current density 10A/dm 2 Electroplating time is 8s, and the temperature is 35 ℃;
(6) And (3) silane spraying: spraying the copper foil at 25 ℃ by adopting 3-aminopropyl trimethoxysilane with the concentration of 4 g/L; and then drying at 200 ℃ to obtain the blackened copper foil.
Example 5
A surface treatment process of a blackened copper foil comprises the following steps:
(1) Acid washing: pickling the copper foil by using a sulfuric acid solution with the concentration of 100g/L for 10s;
(2) Coarsening I: placing the acid-washed copper foil into a roughening solution for electroplating treatment; wherein, the components of the roughening liquid comprise: 90g/L of sulfuric acid and 40g/L of copper sulfate; conditions of electroplating: current density 15A/dm 2 Electroplating time is 8s, and the temperature is 20 ℃; repeating the steps to carry out coarsening II treatment;
(3) Curing I: placing the coarsened copper foil in a curing solution for electroplating treatment; wherein, the components of the curing liquid comprise: 75g/L sulfuric acid and 65g/L copper sulfate; conditions of electroplating: current density 15A/dm 2 Electroplating time is 8s, and the temperature is 35 ℃; repeating the steps to carry out curing II treatment;
(5) Blackening: placing the solidified copper foil into blackening liquid for electroplating treatment; wherein, the blackening liquid comprises the following components: 27g/L of zinc sulfate, 25g/L of sodium citrate, 16g/L of boric acid, 21g/L of ammonium sulfate, 13g/L of polyacrylamide and 6g/L of gelatin; conditions of electroplating: current density 10A/dm 2 Electroplating time is 8s, and the temperature is 35 ℃;
(6) And (3) silane spraying: spraying the copper foil at 25 ℃ by adopting 3-aminopropyl trimethoxysilane with the concentration of 4 g/L; and then drying at 200 ℃ to obtain the blackened copper foil.
The blackened copper foil prepared in examples 1 to 5 was subjected to performance test, and the results are shown in Table 1.
TABLE 1 results of Performance test of blackened copper foil in examples 1 to 5
| 80℃90％RH24h | 200℃30min | Brightness of light | |
| Example 1 | No oxidation point | Unoxidized | 27.2 |
| Example 2 | No oxidation point | Unoxidized | 29.3 |
| Example 3 | No oxidation point | Unoxidized | 28.5 |
| Example 4 | No oxidation point | Unoxidized | 27.5 |
| Example 5 | No oxidation point | Unoxidized | 28.3 |
The smaller the brightness value, the darker the coating color, the larger the brightness value, and the whiter the coating color. As can be seen from Table 1, the blackened copper foil provided by the invention has a brightness value of less than 30, meets the requirements of blackened copper foil products, has no obvious oxidation point when being stored for 24 hours under the conditions of 80 ℃ and 90% of humidity, and has no oxidation phenomenon when being stored for 30 minutes at 200 ℃.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (6)
1. The surface treatment process of the blackened copper foil is characterized by comprising the following steps of:
sequentially carrying out acid washing, coarsening I, coarsening II, curing I, curing II, blackening, silane spraying and drying treatment on the copper foil;
the blackening method comprises the steps of placing copper foil in blackening liquid for electroplating treatment, wherein the electroplating conditions are as follows: the current density is 5-15A/dm 2 The electroplating time is 5-12 s, and the temperature is 30-45 ℃;
the blackening liquid comprises the following components: 25-50 g/L of zinc sulfate, 10-25 g/L of sodium citrate, 10-20 g/L of boric acid, 15-25 g/L of ammonium sulfate, 5-15 g/L of polyacrylamide and 4-8 g/L of gelatin.
2. The surface treatment process of the blackened copper foil according to claim 1, wherein the method of roughening the copper foil is independently to electroplate the copper foil in a roughening solution, and the electroplating conditions in the roughening solution are independently: the current density is 15-25A/dm 2 The electroplating time is 5-15 s, and the temperature is 20-30 ℃;
the components of the coarsening liquid in the coarsening I and the coarsening II independently comprise: 50-100 g/L sulfuric acid and 30-50 g/L copper sulfate.
3. The surface treatment process of the blackened copper foil according to claim 1 or 2, wherein the method of curing i and curing ii is independently to place the copper foil in a curing liquid for electroplating treatment, and the conditions of electroplating in curing i and curing ii are independently: the current density is 15-25A/dm 2 The electroplating time is 5-15 s, and the temperature is 30-45 ℃;
the components of the curing liquid in the curing I and the curing II independently comprise: 40-80 g/L sulfuric acid and 60-80 g/L copper sulfate.
4. The surface treatment process of a blackened copper foil according to claim 3, wherein the concentration of the silane coupling agent in the silane spraying is 4 to 8g/L, and the temperature of the silane spraying is 20 to 35 ℃.
5. The surface treatment process of the blackened copper foil according to claim 4, wherein the silane coupling agent is one or more of gamma- (2, 3-glycidoxy) propyl trimethoxysilane, 3-aminopropyl trimethoxysilane and gamma-aminopropyl triethoxysilane.
6. A blackened copper foil which is obtained by the surface treatment process of a blackened copper foil according to any one of claims 1 to 5.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114959822A (en) * | 2022-06-30 | 2022-08-30 | 中铜华中铜业有限公司 | Rolled copper foil blackening electroplating method |
| CN116970934A (en) * | 2023-08-03 | 2023-10-31 | 广东盈华电子科技有限公司 | Double-sided blackening surface treatment process for electrolytic copper foil |
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2023
- 2023-05-06 CN CN202310504584.5A patent/CN116377529A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114959822A (en) * | 2022-06-30 | 2022-08-30 | 中铜华中铜业有限公司 | Rolled copper foil blackening electroplating method |
| CN116970934A (en) * | 2023-08-03 | 2023-10-31 | 广东盈华电子科技有限公司 | Double-sided blackening surface treatment process for electrolytic copper foil |
| CN116970934B (en) * | 2023-08-03 | 2024-02-06 | 广东盈华电子科技有限公司 | Double-sided blackening surface treatment process for electrolytic copper foil |
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