CN114959822A - Rolled copper foil blackening electroplating method - Google Patents
Rolled copper foil blackening electroplating method Download PDFInfo
- Publication number
- CN114959822A CN114959822A CN202210770602.XA CN202210770602A CN114959822A CN 114959822 A CN114959822 A CN 114959822A CN 202210770602 A CN202210770602 A CN 202210770602A CN 114959822 A CN114959822 A CN 114959822A
- Authority
- CN
- China
- Prior art keywords
- copper foil
- rolled copper
- blackening
- electroplating
- electroplating method
- 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.)
- Pending
Links
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 239000011889 copper foil Substances 0.000 title claims abstract description 100
- 238000009713 electroplating Methods 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims abstract description 41
- 238000011282 treatment Methods 0.000 claims abstract description 22
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 20
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 17
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 17
- 238000005238 degreasing Methods 0.000 claims abstract description 10
- 239000011248 coating agent Substances 0.000 claims abstract description 7
- 238000000576 coating method Methods 0.000 claims abstract description 7
- 238000005246 galvanizing Methods 0.000 claims abstract description 7
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims description 16
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 12
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 12
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 12
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 12
- 239000004327 boric acid Substances 0.000 claims description 12
- 239000001509 sodium citrate Substances 0.000 claims description 12
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 12
- 229940038773 trisodium citrate Drugs 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 6
- 238000005554 pickling Methods 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 231100000086 high toxicity Toxicity 0.000 abstract description 4
- 239000010865 sewage Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000007747 plating Methods 0.000 description 17
- 230000008569 process Effects 0.000 description 14
- 238000005516 engineering process Methods 0.000 description 9
- 239000011701 zinc Substances 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 206010063385 Intellectualisation Diseases 0.000 description 1
- -1 KSCN Chemical class 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 230000002349 favourable 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
- 238000011221 initial treatment Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
Images
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
- C25D3/22—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
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
The invention relates to a blackening electroplating method of a rolled copper foil, which comprises the following steps: degreasing the reddened rolled copper foil; placing the treated rolled copper foil into an electroplating solution for electrogalvanizing treatment to obtain the electroplated rolled copper foil, wherein the electroplating solution comprises cetyl trimethyl ammonium bromide and polyethylene glycol; and coating a silane coupling agent on the electroplated rolled copper foil, and drying to obtain the blackened rolled copper foil. The rolled copper foil blackening electroplating method provided by the invention adopts cyanide-free electroplating solution, specifically adopts electroplating solution comprising cetyl trimethyl ammonium bromide and polyethylene glycol, realizes surface blackening of the reddened rolled copper foil only through one link of galvanizing, effectively avoids using raw materials with high toxicity, greatly reduces the cost of sewage treatment, reduces the technological link of blackening the rolled copper foil, and improves the production efficiency.
Description
Technical Field
The invention relates to the field of copper electroplating processes, in particular to a blackening electroplating method for rolled copper foil.
Background
With the rapid development of 5G, the Internet of things, automotive electronics, industrial robots, industrial intellectualization and the like, the market puts higher requirements on the quality of the copper foil. The rolled copper foil has good ductility and flexing resistance, and is commonly used in flexible copper clad laminates. Meanwhile, the material has higher density and reduced surface roughness, is favorable for the rapid transmission of high-frequency signals, reduces the loss of the signals, and is also commonly used in high-end products such as high-frequency high-speed transmission, PCBs (printed Circuit boards) of fine circuits and the like.
In order to meet the requirements of a circuit board on the heat resistance, corrosion resistance, weldability and the like of the copper foil, the surface of the rolled copper foil generally needs to be roughened, specifically, blackened and reddened. The method for reddening (copper plating) of the rolled copper foil is basically a method for reddening the electrolytic copper foil, but the flexible copper clad laminate made of the rolled copper foil after pure reddening treatment cannot meet the manufacturing requirements of the flexible printed circuit board in peeling resistance, etching resistance and weldability; meanwhile, high-density and high-precision circuit components (e.g., micro-vias having a diameter of less than 200 m) generally require laser drilling during the manufacturing process of printed circuit boards. However, the ultra-thin copper foil has a bright surface and easily reflects laser light, and thus requires excessive laser processing or many attempts to form micro-holes, resulting in high energy consumption. In order to improve the peel resistance, etching properties, and weldability of a rolled copper foil and to reduce the energy consumption, a surface treatment technique of a rolled copper foil is provided in which a blackening treatment is performed on the surface of a reddened foil.
The blackening treatment technology of the rolled copper foil abroad is early researched, has a certain research history and thick foundation, and the high-end blackening rolled copper foil production technology is monopolized abroad at present. However, in the prior art, the rolled copper foil blackening technology is not available in 2011, and in recent years, along with the advanced technology development of domestic enterprises, some rolled copper foil blackening technologies gradually appear, but at present, cyanides such as KSCN, NHSCN, SC (NH2)2 and the like are mostly used as blackening agents to obtain black color in the domestic copper foil surface blackening technology, and the use of cyanogen-containing blackening agents can cause serious pollution problems. In addition, cobalt is added into the plating solution of some enterprises, and because cobalt belongs to a strategic material element and is high in price, the use of a cobalt-containing compound can increase the production cost of copper foil treatment.
Disclosure of Invention
In view of the above, it is necessary to provide a rolled copper foil blackening electroplating method in view of at least one of the problems mentioned above.
The invention provides a rolled copper foil blackening electroplating method, which comprises the following steps:
carrying out oil removal treatment on the reddened rolled copper foil;
putting the treated rolled copper foil into an electroplating solution to carry out electro-galvanizing treatment to obtain the electroplated rolled copper foil, wherein the electroplating solution comprises cetyl trimethyl ammonium bromide and polyethylene glycol;
and coating a silane coupling agent on the electroplated rolled copper foil, and drying to obtain the blackened rolled copper foil.
In one embodiment, the plating solution further comprises zinc ions, trisodium citrate, boric acid, and ammonium sulfate.
In one embodiment, the concentration of the zinc ions is 46-80g/L, the concentration of the trisodium citrate is 20-30g/L, the concentration of the boric acid is 30-40g/L, and the concentration of the ammonium sulfate is 5-15 g/L.
In one embodiment, the concentration of the hexadecyl trimethyl ammonium bromide is 0.6-1g/L, and the concentration of the polyethylene glycol is 1-2 g/L.
In one embodiment, in the step of subjecting the rolled copper foil after the treatment to electrogalvanizing treatment in an electroplating solution, the current density of electroplating is 0.1 to 0.18A/cm 2 The electroplating time is 6-14s, and the electroplating temperature is 20-25 ℃.
In one embodiment, the step of degreasing the reddened rolled copper foil specifically includes: and cleaning the rolled copper foil by adopting absolute ethyl alcohol to remove oil stains on the surface of the rolled copper foil.
In one embodiment, the step of performing degreasing treatment on the reddened rolled copper foil further includes: and then carrying out water washing, acid washing and water washing on the rolled copper foil, wherein acid washing liquid adopted by the acid washing is dilute sulfuric acid with the mass fraction of 10%.
In one embodiment, the time for degreasing and the time for pickling are both controlled to be 10-15 s.
The technical scheme provided by the embodiment of the invention has the following beneficial technical effects:
the rolled copper foil blackening electroplating method provided by the invention adopts cyanide-free electroplating solution, specifically adopts electroplating solution comprising cetyl trimethyl ammonium bromide and polyethylene glycol, realizes surface blackening of the reddened rolled copper foil only through one link of galvanizing, effectively avoids using raw materials with high toxicity, greatly reduces the cost of sewage treatment, reduces the technological link of blackening the rolled copper foil, and improves the production efficiency.
Additional aspects and advantages of the present invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
FIG. 1 is a schematic flow chart of a method for blackening and electroplating a rolled copper foil according to an embodiment of the present invention.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Possible embodiments of the invention are given in the figures. The invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein by the accompanying drawings. The embodiments described by way of reference to the drawings are illustrative for the purpose of providing a more thorough understanding of the present disclosure and are not to be construed as limiting the present invention. In addition, if a detailed description of known technologies is not necessary for the features of the present invention shown, such technical details may be omitted.
It will be understood by those skilled in the relevant art that, unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
As used herein, the singular forms "a", "an", "the" and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be further understood that the terms "comprises" and/or "comprising," when used in this specification, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof. It is to be understood that the term "and/or" as used herein is intended to include all or any and all combinations of one or more of the associated listed items.
At present, cyanide is mostly used as a blackening agent to obtain black color in the domestic copper foil surface blackening technology, but the use of the cyanide-containing blackening agent can cause serious pollution problems, and the cyanide-containing blackening agent has high toxicity and great harm to human bodies or animals and plants. In the previous researches, there are also process technologies for realizing blackening by galvanizing, but the blackening mechanism is realized by chromic acid passivation, so that the sewage treatment cost is high, and the popularization of industrial production is not facilitated.
The technical solution of the present invention and how to solve the above technical problems will be described in detail with specific examples.
The invention provides a rolled copper foil blackening electroplating method, which comprises the following steps as shown in figure 1:
s100: the reddened rolled copper foil is subjected to degreasing treatment. The initial treatment of electroplating can adopt specific technical means commonly used in the electroplating field, and mainly comprises the steps of water washing, acid washing and the like, wherein oil removal is one loop which must be carried out.
S200: and (3) putting the treated rolled copper foil into an electroplating solution to carry out electro-galvanizing treatment to obtain the electroplated rolled copper foil, wherein the electroplating solution comprises cetyl trimethyl ammonium bromide and polyethylene glycol. Cetyl trimethyl ammonium bromide is used as a surfactant, and polyethylene glycol is used as an inhibitor.
S300: and coating a silane coupling agent on the electroplated rolled copper foil, and drying to obtain the blackened rolled copper foil.
The rolled copper foil blackening electroplating method provided by the invention adopts cyanide-free electroplating solution, specifically adopts electroplating solution comprising cetyl trimethyl ammonium bromide and polyethylene glycol, realizes surface blackening of the reddened rolled copper foil only through one link of galvanizing, effectively avoids using raw materials with high toxicity, greatly reduces the cost of sewage treatment, reduces the technological link of blackening the rolled copper foil, and improves the production efficiency.
Specifically, in the step of subjecting the treated rolled copper foil to electrogalvanizing treatment in the plating solution in S200, the plating solution used further includes zinc ions, trisodium citrate, boric acid, and ammonium sulfate. Optionally, the concentration of zinc ions is 46-80g/L, the concentration of trisodium citrate is 20-30g/L, the concentration of boric acid is 30-40g/L, and the concentration of ammonium sulfate is 5-15 g/L. Optionally, the concentration of cetyl trimethyl ammonium bromide is 0.6-1g/L, and the concentration of polyethylene glycol is 1-2 g/L.
Optionally, in one embodiment of the present application, in the step of subjecting the treated rolled copper foil to electrogalvanizing treatment in an electroplating bath, the current density of electroplating is 0.1 to 0.18A/cm 2 The electroplating time is 6-14s, and the electroplating temperature is 20-25 ℃.
Optionally, the step of performing degreasing treatment on the reddened rolled copper foil in S100 specifically includes: and cleaning the rolled copper foil by adopting absolute ethyl alcohol to remove oil stains on the surface of the rolled copper foil. Optionally, the step further includes: and (3) washing, pickling and washing the rolled copper foil after removing the oil stain on the surface of the rolled copper foil, wherein the pickling solution adopted by pickling is dilute sulfuric acid with the mass fraction of 10%. Optionally, the time for oil removal and acid washing is controlled to be 10-15 s.
The following are specific examples:
example 1:
the method adopts the technical scheme in the prior art, and obtains the reddened rolled copper foil through coarsening and curing of the rolled copper foil. Then the reddened rolled copper foil is degreased → washed with water → acid washed with water → electrogalvanized → coated with silane coupling agent → dried.
The first round of oil removal can be realized by cleaning the reddened rolled copper foil with absolute ethyl alcohol to remove oil stains on the surface of the copper foil. After the deoiled rolled copper foil is washed by water, 10% dilute sulfuric acid is selected for pickling the deoiled rolled copper foil, and an oxidation film on the surface of the deoiled rolled copper foil is removed. The time for oil removal and acid washing is controlled to be 10-15 s.
The plating solution formula in the step of electrogalvanizing is as follows:
Zn 2+ : 46g/L, trisodium citrate: 20g/L, boric acid: 30g/L, ammonium sulfate: 5g/L, cetyl trimethylammonium bromide: 0.6g/L, polyethylene glycol: 1 g/L.
The parameters of the electroplating process are as follows:
current density: 0.18A/cm 2
Electroplating time: 14s
Temperature: 25 deg.C
And (3) electroplating results: a black plating layer was formed on the rolled copper foil.
Example 2:
the overall process is the same as in example 1.
The plating solution formula in the step of electrogalvanizing is as follows:
Zn 2+ : 70g/L, trisodium citrate: 26g/L, boric acid: 37g/L, ammonium sulfate: 12 g-L, cetyltrimethylammonium bromide: 0.8g/L, polyethylene glycol: 1.6 g/L.
Electroplating process parameters:
current density: 0.15A/cm 2
Electroplating time: 13s
Temperature: 23 deg.C
And (3) electroplating results: a black plating layer is formed on the rolled copper foil.
Example 3:
the overall process is the same as example 1, and the plating solution formula in the electrogalvanizing step is as follows:
Zn 2+ : 60g/L, trisodium citrate: 22g/L, boric acid: 32g/L, ammonium sulfate: 7g/L, hexadecyl trimethyl ammonium bromide: 0.7g/L, polyethylene glycol: 1.2 g/L.
The parameters of the electroplating process are as follows:
current density: 0.16A/cm 2
Electroplating time: 10s
Temperature: at 22 ℃.
And (3) electroplating results: a black plating layer is formed on the rolled copper foil.
Example 4:
the overall process is the same as example 1, and the plating solution formula in the electrogalvanizing step is as follows:
Zn 2+ : 80g/L, trisodium citrate: 30g/L, boric acid: 40g/L, ammonium sulfate: 15g/L, cetyltrimethylammonium bromide: 1g/L, polyethylene glycol: 2 g/L.
The parameters of the electroplating process are as follows:
current density: 0.1A/cm 2
Electroplating time: 6s
Temperature: at 20 ℃.
And (3) electroplating results: a black plating layer is formed on the rolled copper foil.
Example 5:
the overall process is the same as example 1, and the plating solution formula in the electrogalvanizing step is as follows:
Zn 2+ : 70g/L, trisodium citrate: 26g/L, boric acid: 37g/L, ammonium sulfate: 12g/L, additive cetyl trimethyl ammonium bromide:0.8g/L。
the parameters of the electroplating process are as follows:
current density: 0.15A/cm 2
Electroplating time: 13s
Temperature: 23 deg.C
And (3) electroplating results: a grey plating layer was formed on the rolled copper foil.
Example 6:
the overall process is the same as example 5, and the plating solution formula in the electrogalvanizing step is as follows:
Zn 2+ : 70g/L, trisodium citrate: 26g/L, boric acid: 37g/L, ammonium sulfate: 12g/L, additive polyethylene glycol: 1.6 g/L.
The parameters of the electroplating process are as follows:
current density: 0.15A/cm 2
Electroplating time: 13s
Temperature: 23 deg.C
And (3) electroplating results: a grey plating layer was formed on the rolled copper foil.
In the electrodeposition process, cetyl trimethyl ammonium bromide (CTAB for short) can slow down the speed of metal ions reaching the surface of a cathode through the directional arrangement and adsorption on the interface of metal and solution, and can block the reduction of the metal ions, thereby achieving the effect of cathode polarization. Polyethylene glycol, such as PEG-4000, as an inhibitor, can be adsorbed on the surface of the cathode like CTAB to inhibit Zn 2+ The deposition and diffusion can also occupy active sites and reduce the nucleation points of Zn atoms. CTAB and PEG-4000 act together to regulate and control the crystal grain structure, and finally a dense columnar crystal grain structure is formed on the surface of the copper foil, and the structure has stronger capturing capability on incident light and can realize the blackening treatment of the copper foil.
TABLE 1 calendered copper foil L with different additive additions
In the table, L represents brightness and is the most important parameter for representing the blackening effect of the coating, and the smaller L is, the darker the coating color is, and the larger L is, the whiter the coating color is. Generally, a copper foil with L × less than 30 is regarded as a blackened foil. It can be seen from table 1 that the blackened rolled copper foils obtained in examples 1 to 4 all meet the product requirements.
Those of skill in the art will understand that various operations, methods, steps in the flow, measures, schemes discussed in this application can be alternated, modified, combined, or deleted. Further, other steps, measures, or schemes in various operations, methods, or flows that have been discussed in this application can be alternated, altered, rearranged, broken down, combined, or deleted. Further, steps, measures, schemes in the prior art having various operations, methods, procedures disclosed in the present application may also be alternated, modified, rearranged, decomposed, combined, or deleted.
In the description herein, particular features, structures, materials, or characteristics may be combined in any suitable manner in any one or more embodiments or examples.
It should be understood that, although the steps in the flowcharts of the figures are shown in order as indicated by the arrows, the steps are not necessarily performed in order as indicated by the arrows. The steps are not performed in the exact order shown and may be performed in other orders unless explicitly stated herein. Moreover, at least a portion of the steps in the flow chart of the figure may include multiple sub-steps or multiple stages, which are not necessarily performed at the same time, but may be performed at different times, which are not necessarily performed in sequence, but may be performed alternately or alternately with other steps or at least a portion of the sub-steps or stages of other steps.
The foregoing is only a partial embodiment of the present application, and it should be noted that, for those skilled in the art, several modifications and decorations can be made without departing from the principle of the present application, and these modifications and decorations should also be regarded as the protection scope of the present application.
Claims (8)
1. The rolled copper foil blackening electroplating method is characterized by comprising the following steps of:
degreasing the reddened rolled copper foil;
putting the treated rolled copper foil into an electroplating solution to carry out electro-galvanizing treatment to obtain the electroplated rolled copper foil, wherein the electroplating solution comprises cetyl trimethyl ammonium bromide and polyethylene glycol;
and coating a silane coupling agent on the electroplated rolled copper foil, and drying to obtain the blackened rolled copper foil.
2. The blackening electroplating method for rolled copper foil according to claim 1, wherein the electroplating solution further comprises zinc ions, trisodium citrate, boric acid and ammonium sulfate.
3. The blackening electroplating method for rolled copper foil according to claim 2, wherein the concentration of zinc ions is 46-80g/L, the concentration of trisodium citrate is 20-30g/L, the concentration of boric acid is 30-40g/L, and the concentration of ammonium sulfate is 5-15 g/L.
4. The rolled copper foil blackening electroplating method of claim 1, wherein the concentration of the cetyltrimethylammonium bromide is 0.6-1g/L, and the concentration of the polyethylene glycol is 1-2 g/L.
5. The blackening electroplating method for rolled copper foil according to claim 1, wherein in the step of subjecting the treated rolled copper foil to the electrogalvanizing treatment in an electroplating solution, the current density of electroplating is 0.1 to 0.18A/cm 2 The electroplating time is 6-14s, and the electroplating temperature is 20-25 ℃.
6. The blackening electroplating method for rolled copper foil according to claim 1, wherein the step of degreasing the reddened rolled copper foil specifically comprises: and cleaning the rolled copper foil by adopting absolute ethyl alcohol to remove oil stains on the surface of the rolled copper foil.
7. The blackening electroplating method for rolled copper foil according to claim 1, wherein the step of degreasing the reddened rolled copper foil further comprises: and then carrying out water washing, acid washing and water washing on the rolled copper foil, wherein acid washing liquid adopted by the acid washing is dilute sulfuric acid with the mass fraction of 10%.
8. The blackening electroplating method for rolled copper foil according to claim 7, wherein the time for degreasing and pickling is controlled to 10 to 15 seconds.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210770602.XA CN114959822A (en) | 2022-06-30 | 2022-06-30 | Rolled copper foil blackening electroplating method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210770602.XA CN114959822A (en) | 2022-06-30 | 2022-06-30 | Rolled copper foil blackening electroplating method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114959822A true CN114959822A (en) | 2022-08-30 |
Family
ID=82967915
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210770602.XA Pending CN114959822A (en) | 2022-06-30 | 2022-06-30 | Rolled copper foil blackening electroplating method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114959822A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110012222A1 (en) * | 2009-07-17 | 2011-01-20 | Cho Hans S | Method of making light trapping crystalline structures |
| CN112609217A (en) * | 2020-11-11 | 2021-04-06 | 中铜华中铜业有限公司 | Blackening solution and cyanide-free zinc-plating cadmium-free electroplating blackening process |
| CN116083984A (en) * | 2023-03-22 | 2023-05-09 | 江苏铭丰电子材料科技有限公司 | Blackening electroplating method for rolled copper foil |
| CN116377529A (en) * | 2023-05-06 | 2023-07-04 | 江苏铭丰电子材料科技有限公司 | Blackened copper foil and surface treatment process thereof |
-
2022
- 2022-06-30 CN CN202210770602.XA patent/CN114959822A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110012222A1 (en) * | 2009-07-17 | 2011-01-20 | Cho Hans S | Method of making light trapping crystalline structures |
| CN112609217A (en) * | 2020-11-11 | 2021-04-06 | 中铜华中铜业有限公司 | Blackening solution and cyanide-free zinc-plating cadmium-free electroplating blackening process |
| CN116083984A (en) * | 2023-03-22 | 2023-05-09 | 江苏铭丰电子材料科技有限公司 | Blackening electroplating method for rolled copper foil |
| CN116377529A (en) * | 2023-05-06 | 2023-07-04 | 江苏铭丰电子材料科技有限公司 | Blackened copper foil and surface treatment process thereof |
Non-Patent Citations (4)
| Title |
|---|
| 伍玉琴 等: "三种添加剂对纳米晶锌镀层电沉积行为及结构的影响", 化学学报, no. 06, 28 March 2010 (2010-03-28), pages 31 - 34 * |
| 伍玉琴 等: "三种添加剂对纳米晶锌镀层电沉积行为及结构的影响", 化学学报, no. 06, pages 42 - 45 * |
| 邬明钰 等: "硫酸盐体系中直流电沉积参数对纳米晶锌镀层的影响", 材料保护, no. 08, pages 42 - 45 * |
| 饶翔 等: "压延铜箔的无氰电镀锌黑化处理工艺", 材料保护, vol. 55, no. 5, 15 May 2022 (2022-05-15), pages 123 - 128 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1303250C (en) | Magnesium alloy non cyanogen plating copper chemical plating nickle and its plating process | |
| CN103668359B (en) | A kind of electroplate liquid of multilayer non-cyanide copper electroplating-tin alloy coat, electroplating technology and coin thereof | |
| CN104962965B (en) | The environment-friendly type ashing handling process of rolled copper foil | |
| CA2866786C (en) | Process for metallizing nonconductive plastic surfaces | |
| CN107245742B (en) | A kind of aluminium alloy with no cyanogen sinks zinc agent and aluminium alloy sinks zinc method | |
| BR112014021969B1 (en) | PROCESS FOR METALIZING NON-CONDUCTIVE PLASTIC SURFACES | |
| WO2012114737A1 (en) | Method for producing trivalent chromium-plated molded article and trivalent chromium-plated molded article | |
| CN106835088A (en) | A kind of chemical nickel and gold production line and production technology | |
| JP2022120813A (en) | Ultrathin copper foil, and method of producing the same | |
| CN101724871B (en) | Double-pulse cyanide-free alkali silver electroplating method | |
| KR20070014721A (en) | A double nickel plating method of a permanent magnet with nd-fe-b | |
| CN1144670C (en) | Copper film for TAB band carrier and TAB carried band and TAB band carrier | |
| CN114959822A (en) | Rolled copper foil blackening electroplating method | |
| JP7456578B2 (en) | Copper surface processing equipment | |
| CN111394765A (en) | Electrolytic copper foil surface treatment process | |
| CN114016098A (en) | Copper-clad plate electroplating Ni-Co-Ce film plating solution for PCB and film preparation method | |
| CN106544707B (en) | The acid cuprous stannous plating ladder of steel core imitates gold bronze | |
| CN104087985A (en) | Copper coating method of metal part | |
| CN104164684A (en) | Method for plating nickel on surface of oxygen-free copper | |
| JPH04318997A (en) | Copper foil for printed circuit and manufacture thereof | |
| JP3709142B2 (en) | Copper foil for printed wiring board and method for producing the same | |
| CN114752973B (en) | Cyanide-free bright silver plating solution and electroplating method | |
| JPS63297577A (en) | Surface structure of steel material strengthened in physical property and its production | |
| CN1473961A (en) | Non-cyanide electroplating process for zinc alloy die casting | |
| KR101443085B1 (en) | Method for manufacturing brass plating steel sheet |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |