CN112226790A - Production method of ultrathin high-strength electronic copper foil - Google Patents
Production method of ultrathin high-strength electronic copper foil Download PDFInfo
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- CN112226790A CN112226790A CN202011116297.XA CN202011116297A CN112226790A CN 112226790 A CN112226790 A CN 112226790A CN 202011116297 A CN202011116297 A CN 202011116297A CN 112226790 A CN112226790 A CN 112226790A
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
- C25D1/04—Wires; Strips; Foils
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- 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
- C25D3/38—Electroplating: Baths therefor from solutions of copper
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- 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
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- 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
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Abstract
The invention discloses a production method of an ultrathin high-strength electronic copper foil, which comprises the following steps: preparing electrolyte, adding mixed additives, manufacturing an isolating layer by using a copper foil with the thickness of 18-35 microns as a cathode carrier, electrodepositing an ultrathin copper foil layer with the thickness of 2.5-5 microns to form a carrier copper foil, carrying out chemical micro-roughening treatment on the rough surface of the carrier copper foil, and carrying out organic film coating to form the ultrathin high-strength electronic copper foil. The copper foil with the thickness of 18-35 microns is used as a cathode carrier, electrochemical deposition is carried out on the surface of the carrier in a mixed solution of electrolyte and an additive to form an ultrathin copper foil layer with the thickness of 2.5-5 microns, and the specific surface area can be improved through micro-roughening; the peeling strength can be improved and the oxidation of the foil can be effectively prevented by coating the organic layer; the isolating layer is prepared on the carrier, so that the bonding force between the ultrathin copper foil and the carrier is reduced, and the ultrathin copper foil and the carrier are easily separated by mechanical force; the process has simple steps, can realize continuous production, and is an efficient production process of the carrier high-strength ultrathin copper foil.
Description
Technical Field
The invention relates to the technical field of copper foil production methods, in particular to a production method of an ultrathin high-strength electronic copper foil.
Background
Electrolytic copper foil is an important raw material in the electronic information industry. With the development of technology, electronic products tend to be multifunctional, light and thin integrated. Therefore, the copper foil substrate for forming the printed circuit is also required to be thinner and have smaller roughness, so that the processing of a fine circuit is facilitated; especially 5G products, require ultra-thin, low roughness copper foil for support.
The traditional electrolytic copper foil is manufactured by adopting a cathode roller as a cathode, in a copper sulfate aqueous solution, electroplating the surface of the cathode roller to form a copper layer, directly stripping to form a rough foil, and carrying out anti-stripping enhancement treatment and anti-oxidation treatment such as coarsening, curing-barrier layer treatment and the like. This process has several disadvantages: 1) the thickness of the copper foil cannot be made very thin; 2) the ultra-thin copper foil is easy to wrinkle when the downstream customer (printed circuit board factory) carries out subsequent processing, and the quality and the yield are influenced; 3) the roughness of the copper foil subjected to electrochemical roughening is increased, so that the influence on high-frequency and high-speed signal transmission is obviously increased; 4) the strength of the copper foil is low and cannot meet the requirement. Along with PCB and IC carrier plate line width is littleer and smaller, and the copper foil is more and more thin, and component calorific capacity increases, and under expend with heat and contract with cold's effect, the tensile property of copper foil is high inadequately, can make the copper foil lines of PCB and IC carrier plate appear chapping, greatly increased cracked risk.
An effective solution to the problems in the related art has not been proposed yet.
Disclosure of Invention
In view of the above technical problems in the related art, an object of the present invention is to provide a method for producing an ultra-thin high-strength electronic copper foil, which overcomes the disadvantages of the prior art.
In order to achieve the technical purpose, the technical scheme of the invention is realized as follows:
a production method of an ultrathin high-strength electronic copper foil comprises the following steps:
s1, preparing electrolyte from copper pyrophosphate, potassium pyrophosphate and ammonium citrate;
s2, adding the mixed additive, and performing multi-stage filtration;
s3, taking the copper foil with the thickness of 18-35 microns as a cathode carrier, and manufacturing an isolating layer on the cathode carrier by any known method;
s4, adding the cathode carrier with the separating layer into the solution of the step S2 at a concentration of 150-500A/dm2Performing electrodeposition on an ultrathin copper foil layer with the thickness of 2.5-5 microns at the current density to form a carrier copper foil;
s5, using a roughening solution consisting of sulfuric acid, hydrogen peroxide, trisodium phosphate and a wetting agent to carry out chemical micro-roughening treatment on the rough surface of the carrier copper foil;
and S6, carrying out chemical micro-roughening treatment on the rough surface of the carrier copper foil, and then coating an organic film to form the ultrathin high-strength electronic copper foil.
Further, the mixed additive in step S2 includes an agent a, an agent B, an agent C and chloride ions, the agent a at least contains one of thiazolidinethione, fatty amine ethoxy sulfonate, mercapto imidazole propane sulfonic acid and azozine dye, the agent B contains one of polydithio dipropyl sodium sulfonate, mercapto propane sulfonic acid, dimethyl formamide sodium sulfonate and thia imidazone dithio propane sulfonic acid, and the agent C contains one of polyethylene glycol and dodecyl benzene sulfonic acid.
Further, the concentrations of the copper pyrophosphate, the potassium pyrophosphate and the ammonium citrate are respectively 80-120g/L, 300-400g/L and 15-35 g/L.
Further, the concentrations of the agent A, the agent B and the agent C are 3-50mg/L, 3-80mg/L and 1-20mg/L respectively.
Further, the concentrations of sulfuric acid, hydrogen peroxide, trisodium phosphate and a wetting agent in the coarsening liquid are respectively 25-55g/L, 30-60g/L, 50-80g/L and 5-25 mg/L.
Furthermore, the temperature of the coarsening liquid is 35 ℃, and the chemical micro-coarsening treatment time is 38-55 seconds.
Further, the organic film adopts sprayed 3-glycidoxy propyl trimethoxy silane water solution.
Further, the thickness of the isolation layer is 0.05-0.1 micrometer.
The invention also provides an ultrathin high-strength electronic copper foil which is prepared by adopting the production method and comprises a carrier, wherein an isolation layer is arranged on the carrier, an ultrathin copper foil is arranged on the isolation layer, and a coarsening layer and an organic layer are arranged on the ultrathin copper foil; the tensile strength is more than 60-80 Kg/mm2The elongation is more than 3.0 percent, and the anti-stripping strength is more than or equal to 0.7N/mm.
The invention has the beneficial effects that: according to the invention, a copper foil with the thickness of 18-35 microns is used as a cathode carrier, electrochemical deposition is carried out on the surface of the carrier in a mixed solution of copper pyrophosphate, potassium pyrophosphate and an additive to form an ultrathin copper foil layer with the thickness of 2.5-5 microns, and the specific surface area can be improved through micro-roughening; the peeling strength can be improved and the oxidation of the foil can be effectively prevented by coating the organic layer; the isolating layer is prepared on the carrier, so that the bonding force between the ultrathin copper foil and the carrier is reduced, and the ultrathin copper foil and the carrier are easily separated by mechanical force; the process has simple steps, can realize continuous production, and is an efficient production process of the carrier high-strength ultrathin copper foil.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
Fig. 1 is a structural view of an ultra-thin high-strength electronic copper foil manufactured by a method for manufacturing an ultra-thin high-strength electronic copper foil according to an embodiment of the present invention.
In the figure: 1. a carrier; 2. an isolation layer; 3. an ultra-thin copper foil; 4. a roughened layer and an organic layer.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments that can be derived by one of ordinary skill in the art from the embodiments given herein are intended to be within the scope of the present invention.
One aspect of the present invention provides a method for producing an ultra-thin high-strength electronic copper foil, comprising the steps of:
s1, preparing electrolyte from copper pyrophosphate, potassium pyrophosphate and ammonium citrate;
s2, adding the mixed additive, and performing multi-stage filtration;
s3, taking the copper foil with the thickness of 18-35 microns as a cathode carrier, and manufacturing an isolating layer on the cathode carrier by any known method, so that the ultra-thin high-tensile copper foil is conveniently separated from the carrier after lamination;
s4, adding the cathode carrier with the isolating layer into the solution obtained in the step S2, and electrodepositing an ultra-thin copper foil layer with the thickness of 2.5-5 microns to form a carrier copper foil;
s5, using a roughening solution consisting of sulfuric acid, hydrogen peroxide, trisodium phosphate and a wetting agent to carry out chemical micro-roughening treatment on the rough surface of the carrier copper foil;
and S6, carrying out chemical micro-roughening treatment on the rough surface of the carrier copper foil, and then coating an organic film to form the ultrathin high-strength electronic copper foil, so that the requirements of the PCB are met.
In a specific embodiment of the present invention, the additive mixture in step S2 includes an agent a, an agent B, an agent C, and chloride ions, the agent a is at least one of thiazolidinethione, fatty amine ethoxy sulfonate, mercaptoimidazolepropanesulfonic acid, and azooxazine dye, the agent B is one of polydithiodipropanesulfonic acid sodium, alkylthiopropanesulfonic acid sodium, dimethylformamidosulfonic acid sodium, and imidazolinyldithiophanasulfonic acid, and the agent C is one of polyethylene glycol and dodecylbenzene sulfonic acid sodium.
In one embodiment of the invention, the concentrations of the copper pyrophosphate, the potassium pyrophosphate and the ammonium citrate are 80-120g/L, 300-400g/L and 15-35g/L respectively.
In one embodiment of the present invention, the concentrations of the agent A, the agent B and the agent C are 3 to 50mg/L, 3 to 80mg/L and 1 to 20mg/L, respectively.
In one embodiment of the invention, the concentrations of the sulfuric acid, the hydrogen peroxide, the trisodium phosphate and the wetting agent in the coarsening liquid are respectively 25-55g/L, 30-60g/L, 50-80g/L and 5-25 mg/L.
In one embodiment of the present invention, the temperature of the roughening solution is 35 ℃ and the chemical micro-roughening treatment time is 38-55 seconds.
In one embodiment of the invention, the organic film is sprayed with an aqueous solution of 3-glycidoxypropyltrimethoxysilane.
In a specific embodiment of the invention, the spacer layer has a thickness of 0.05 to 0.1 μm.
The structure of the ultrathin high-strength electronic copper foil is shown in figure 1, the ultrathin high-strength electronic copper foil comprises a carrier 1, an isolation layer 2 is arranged on the carrier 1, an ultrathin copper foil 3 is arranged on the isolation layer 2, and a coarsening layer and an organic layer 4 are arranged on the ultrathin copper foil 3.
In order to facilitate understanding of the above-described technical aspects of the present invention, the above-described technical aspects of the present invention will be described in detail below in terms of specific usage.
Example 1
Preparing chemical pure copper pyrophosphate, potassium pyrophosphate and ammonium citrate by using pure water according to the concentration of 100g/L, 350g/L and 25g/L, respectively adding 5mg/L of thiazolidinethione A, 8mg/L of 3-mercapto-1-propane sodium sulfonate B and 10mg/L of polyethylene glycol C, filtering by 5 micrometers, 1 micrometer and 0.5 micrometer in multiple stages, electrodepositing a zinc layer with the thickness of 0.01-0.05 micrometer on the smooth surface of a copper foil with the thickness of 18 micrometers at the temperature of 55 ℃ to serve as an isolating layer, and using a titanium anode to ensure that the current density is 300A/dm2And electrodepositing an ultrathin copper foil layer with the thickness of 5 micrometers on the isolation layer.
An ultra-thin copper foil of 5 microns in thickness was attached to a cathode carrier of 18 microns in thickness to form a carrier copper foil.
The carrier copper foil is subjected to chemical micro-roughening in roughening solution prepared by pure water so as to improve the specific surface area of the ultrathin super-strong electronic copper foil, wherein the roughening solution consists of sulfuric acid, hydrogen peroxide, trisodium phosphate and wetting agents, and the concentrations of the roughening solution are 25g/L, 30g/L, 50g/L and 5mg/L respectively. The temperature of the roughing solution was 35 ℃ and the treatment time was 55 seconds.
After micro-roughening, carrying out peel strength enhancement and oxidation resistance treatment, and spraying 3-glycidol ether oxypropyl trimethoxy silane aqueous solution with the concentration of 0.5% on the surface of the ultrathin high-tensile carrier copper foil to form an organic film.
Example 2
In the embodiment, the ultra-thin copper foil with the thickness of 4 microns is electrodeposited by using mercaptoimidazole sodium propyl sulfonate, sodium mercaptopropane sulfonate and sodium dodecyl benzene sulfonate as additives.
Preparing chemical pure copper pyrophosphate, potassium pyrophosphate and ammonium citrate by using pure water according to the concentration of 100g/L, 350g/L and 25g/L, respectively adding 8mg/L of mercaptoimidazole propanesulfonic acid sodium salt A, 10mg/L of mercaptopropanesulfonic acid sodium salt B and 15mg/L of dodecylbenzene sulfonic acid sodium salt C, filtering by 5-micron, 1-micron and 0.5-micron multistage filtration, electro-depositing a zinc layer with the thickness of 0.01-0.05 micron on the smooth surface of 18-micron copper foil at the temperature of 55 ℃, using a titanium anode and the current density of 280A/dm2And electrodepositing an ultrathin copper foil layer with the thickness of 4 microns on the isolation layer.
An ultra-thin copper foil having a thickness of 4 microns was attached to a cathode carrier having a thickness of 18 microns to form a carrier copper foil.
The carrier copper foil is chemically roughened in a roughening solution prepared by pure water to improve the specific surface area of the ultrathin super-strong copper foil, the roughening solution consists of sulfuric acid, hydrogen peroxide, trisodium phosphate and a wetting agent, the concentrations of the roughening solution are respectively 25/L, 30g/L, 50g/L and 5mg/L, the temperature of the roughening solution is 35 ℃, and the treatment time is 50 seconds.
After micro-roughening, carrying out peel strength enhancement and oxidation resistance treatment, and spraying 3-glycidol ether oxypropyl trimethoxy silane aqueous solution with the concentration of 0.5% on the surface of the ultrathin high-tensile carrier copper foil to form an organic film.
Example 3
Chemical pure copper pyrophosphate, potassium pyrophosphate and ammonium citrate are respectively prepared by pure water according to the concentration of 100g/L, 350g/L and 25g/L, and the A agent of thiazolidine sulfur is respectively added5mg/l of ketone, 8mg/l of 3-mercapto-1-propane sodium sulfonate B and 10mg/l of polyethylene glycol C, performing multistage filtration of 5 microns, 1 micron and 0.5 micron, electrodepositing a zinc layer with the thickness of 0.01-0.05 micron on the smooth surface of 18 micron copper foil at the temperature of 55 ℃ to serve as an isolating layer, and performing titanium anode treatment at the current density of 280A/dm2And electrodepositing an ultrathin copper foil layer with the thickness of 2.5 microns on the isolation layer.
An ultra-thin copper foil having a thickness of 2.5 micrometers was attached to a cathode carrier having a thickness of 18 micrometers to form a carrier copper foil.
The carrier copper foil is chemically roughened in a roughening solution prepared by pure water to improve the specific surface area of the ultrathin super-strong copper foil, the roughening solution consists of sulfuric acid, hydrogen peroxide, trisodium phosphate and a wetting agent, the concentrations of the roughening solution are respectively 25g/L, 30g/L, 50g/L and 5mg/L, the temperature of the roughening solution is 35 ℃, and the treatment time is 45 seconds.
After micro-roughening, carrying out peel strength enhancement and oxidation resistance treatment, and spraying 3-glycidol ether oxypropyl trimethoxy silane aqueous solution with the concentration of 0.5% on the surface of the ultrathin high-tensile carrier copper foil to form an organic film.
Example 4
Preparing chemical pure copper pyrophosphate, potassium pyrophosphate and ammonium citrate respectively by using pure water according to the concentration of 100g/L, 350g/L and 25g/L, adding 8mg/L of mercaptoimidazole propanesulfonic acid sodium, 10mg/L of alcohol thiopropane sulfonic acid sodium and 15mg/L of dodecyl benzene sulfonic acid sodium as additives, filtering by 5 microns, 1 micron and 0.5 micron multistage filtration, electrodepositing a zinc layer with the thickness of 0.01-0.05 micron on the smooth surface of 18 micron copper foil at the temperature of 55 ℃ as an isolating layer, and using a titanium anode with the current density of 220A/dm2And electrodepositing an ultrathin copper foil layer with the thickness of 2.5 microns on the isolation layer.
An ultra-thin copper foil having a thickness of 2.5 micrometers was attached to a cathode carrier having a thickness of 18 micrometers to form a carrier copper foil.
The carrier copper foil is chemically roughened in a roughening solution prepared by pure water to improve the specific surface area of the ultrathin super-strong copper foil, the roughening solution consists of sulfuric acid, hydrogen peroxide, trisodium phosphate and a wetting agent, the concentrations of the roughening solution are respectively 25/L, 30g/L, 50g/L and 5mg/L, the temperature of the roughening solution is 35 ℃, and the treatment time is 45 seconds.
After micro-roughening, carrying out peel strength enhancement and oxidation resistance treatment, and spraying 3-glycidol ether oxypropyl trimethoxy silane aqueous solution with the concentration of 0.5% on the surface of the ultrathin high-tensile carrier copper foil to form an organic film.
Example 5
The concentrations of copper pyrophosphate, potassium pyrophosphate and ammonium citrate in the electrodeposition solution are respectively 120g/L, 380g/L and 35g/L, 5mg/L of thiazolidinethione, 8mg/L of 3-mercapto-1-propane sodium sulfonate and 10mg/L of polyethylene glycol are added, multistage filtration of 5 microns, 1 micron and 0.5 micron is carried out, a zinc layer with the thickness of 0.01-0.05 micron is electrodeposited on the smooth surface of 18 micron copper foil at the temperature of 55 ℃ as an isolating layer, a titanium anode is used, and the current density is 250A/dm2And electrodepositing a copper foil layer with the thickness of 2.5 microns on the isolation layer.
An ultra-thin copper foil having a thickness of 2.5 micrometers was attached to a cathode carrier having a thickness of 18 micrometers to form a carrier copper foil.
The carrier copper foil is chemically roughened in a roughening solution prepared by pure water, wherein the concentrations of the roughening solution are 25/L, 30g/L, 50g/L and 5mg/L respectively, the temperature of the roughening solution is 35 ℃, and the treatment time is 45 seconds.
After micro-roughening, carrying out peel strength enhancement and oxidation resistance treatment, and spraying 3-glycidol ether oxypropyl trimethoxy silane aqueous solution with the concentration of 0.5% on the surface of the ultrathin high-tensile carrier copper foil to form an organic film.
Example 6
The concentrations of copper pyrophosphate, potassium pyrophosphate and ammonium citrate in the electrodeposition solution are respectively 120g/L, 380g/L and 35g/L, 5mg/L of thiazolidinethione, 8mg/L of 3-mercapto-1-propane sodium sulfonate and 10mg/L of polyethylene glycol are added, multistage filtration of 5 microns, 1 micron and 0.5 micron is carried out, a zinc layer with the thickness of 0.01-0.05 micron is electrodeposited on the smooth surface of 18 micron copper foil at the temperature of 55 ℃ as an isolating layer, a titanium anode is used, and the current density is 250A/dm2And electrodepositing a copper foil layer with the thickness of 2.5 microns on the isolation layer.
An ultra-thin copper foil having a thickness of 2.5 micrometers was attached to a cathode carrier having a thickness of 18 micrometers to form a carrier copper foil.
The carrier copper foil is chemically roughened in a roughening solution prepared by pure water, wherein the concentrations of the roughening solution are 35/L, 40g/L, 60g/L and 10mg/L respectively, the roughening solution temperature is 35 ℃, and the treatment time is 38 seconds.
After micro-roughening, carrying out peel strength enhancement and oxidation resistance treatment, and spraying 3-glycidol ether oxypropyl trimethoxy silane aqueous solution with the concentration of 0.5% on the surface of the ultrathin high-tensile carrier copper foil to form an organic film.
The properties of the ultra-thin high-strength electronic copper foil of the above embodiments 1-6 are shown in Table 1, and the tensile strength thereof is greater than 60-80 Kg/mm2The elongation is more than 3.0 percent, and the anti-stripping strength is more than or equal to 0.7N/mm.
TABLE 1 ultra-thin high-strength electronic copper foil
The peel strength of the ultra-thin high strength electronic copper foil is related to the insulating substrate, and the result of the FR-4 test is shown in the above examples. For the same F-4 substrate, the peel strength data will be slightly different depending on the resin formulation of each PCB manufacturer.
The ultrathin high-strength electronic copper foil provided by the invention is provided for PCB or CCL users in a coiled manner, can be directly cut into required sizes, and is laminated with an insulating material according to a normal copper foil. After lamination, the ultra-thin high-strength copper foil is firmly bonded with the insulating base material, a zinc layer between the ultra-thin high-strength copper foil and the carrier is heated and diffused during lamination, so that the bonding force between the ultra-thin copper foil and the carrier is reduced, and the ultra-thin high-strength copper foil and the carrier are easily separated by mechanical force.
In summary, according to the technical scheme of the invention, 18-35 micron copper foil is used as a cathode carrier, electrochemical deposition is carried out on the surface of the carrier in mixed solution of copper pyrophosphate, potassium pyrophosphate and an additive to form an ultra-thin copper foil layer with the thickness of 2.5-5 microns, and the specific surface area can be increased through micro-roughening; the peeling strength can be improved and the oxidation of the foil can be effectively prevented by coating the organic layer; the isolating layer is prepared on the carrier, so that the bonding force between the ultrathin copper foil and the carrier is reduced, and the ultrathin copper foil and the carrier are easily separated by mechanical force; the process has simple steps, can realize continuous production, and is an efficient production process of the carrier high-strength ultrathin copper foil.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (9)
1. The production method of the ultrathin high-strength electronic copper foil is characterized by comprising the following steps of:
s1, preparing electrolyte from copper pyrophosphate, potassium pyrophosphate and ammonium citrate;
s2, adding the mixed additive, and performing multi-stage filtration;
s3, taking the copper foil with the thickness of 18-35 microns as a cathode carrier, and manufacturing an isolating layer on the cathode carrier by any known method;
s4, adding the cathode carrier with the separating layer into the solution of the step S2 at a concentration of 150-500A/dm2Performing electrodeposition on an ultrathin copper foil layer with the thickness of 2.5-5 microns at the current density to form a carrier copper foil;
s5, using a roughening solution consisting of sulfuric acid, hydrogen peroxide, trisodium phosphate and a wetting agent to carry out chemical micro-roughening treatment on the rough surface of the carrier copper foil;
and S6, carrying out chemical micro-roughening treatment on the rough surface of the carrier copper foil, and then coating an organic film to form the ultrathin high-strength electronic copper foil.
2. The method of claim 1, wherein the additive mixture in step S2 comprises an agent a, an agent B, an agent C and chloride ions, wherein the agent a is at least one of thiazolidinethione, fatty amine ethoxylate sulfonate, sodium mercaptoimidazolepropanesulfonate and azoazine dye, the agent B is one of sodium polydithio dipropanesulfonate, sodium thiolpropanate, sodium dimethylformamidosulfonate and thiamidazolinyl dithiopropanesulfonic acid, and the agent C is one of polyethylene glycol and sodium dodecylbenzenesulfonate.
3. The method as claimed in claim 1, wherein the concentrations of copper pyrophosphate, potassium pyrophosphate and ammonium citrate are 80-120g/L, 300-400g/L and 15-35g/L, respectively.
4. The method for manufacturing an ultra-thin high-strength electronic copper foil as claimed in claim 2, wherein the concentrations of the agent a, the agent B and the agent C are 3 to 50mg/L, 3 to 80mg/L and 1 to 20mg/L, respectively.
5. The method for manufacturing an ultra-thin high-strength electronic copper foil as claimed in claim 1, wherein the concentrations of sulfuric acid, hydrogen peroxide, trisodium phosphate and wetting agent in the roughening solution are 25-55g/L, 30-60g/L, 50-80g/L and 5-25mg/L, respectively.
6. The method for manufacturing an ultra-thin high-strength electronic copper foil as claimed in claim 1, wherein the roughening solution temperature is 35 ℃ and the chemical micro-roughening treatment time is 38-55 seconds.
7. The method for manufacturing an ultra-thin high-strength electronic copper foil according to claim 1, wherein the organic film is a sprayed 3-glycidoxypropyltrimethoxysilane aqueous solution.
8. The method for manufacturing an ultra-thin high-strength electronic copper foil as claimed in claim 1, wherein the thickness of the separator is 0.05-0.1 μm.
9. AAn ultra-thin high-strength electronic copper foil, characterized by being produced by the production method according to any one of claims 1 to 8, comprising a carrier (1), wherein an isolation layer (2) is provided on the carrier (1), an ultra-thin copper foil (3) is provided on the isolation layer (2), and a roughened layer and an organic layer (4) are provided on the ultra-thin copper foil (3); the tensile strength of the ultrathin high-strength electronic copper foil is more than 60-80 Kg/mm2The elongation is more than 3.0 percent, and the anti-stripping strength is more than or equal to 0.7N/mm.
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| CN202011116297.XA CN112226790B (en) | 2020-10-19 | 2020-10-19 | Production method of ultrathin high-strength electronic copper foil |
| PCT/CN2020/132527 WO2022082933A1 (en) | 2020-10-19 | 2020-11-28 | Production method for ultrathin high-strength electronic copper foil |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| US20220267954A1 (en) * | 2021-02-25 | 2022-08-25 | Sixring Inc. | Modified sulfuric acid and uses thereof |
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| CN112725847A (en) * | 2021-01-16 | 2021-04-30 | 九江德福科技股份有限公司 | High-modulus lithium battery copper foil electrolyte and method for preparing copper foil by using same |
| CN112981481A (en) * | 2021-02-05 | 2021-06-18 | 广东嘉元科技股份有限公司 | Ultrathin copper foil and preparation method thereof |
| US20220267954A1 (en) * | 2021-02-25 | 2022-08-25 | Sixring Inc. | Modified sulfuric acid and uses thereof |
| US11965289B2 (en) * | 2021-02-25 | 2024-04-23 | Sixring Inc. | Modified sulfuric acid and uses thereof |
| CN113176188A (en) * | 2021-04-08 | 2021-07-27 | 九江德福科技股份有限公司 | Method for measuring specific surface area of electrolytic copper foil |
| CN113265685A (en) * | 2021-05-27 | 2021-08-17 | 益阳市菲美特新材料有限公司 | Porous copper foil and preparation method thereof |
| CN113265685B (en) * | 2021-05-27 | 2024-01-23 | 益阳市菲美特新材料有限公司 | Porous copper foil and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112226790B (en) | 2022-04-22 |
| WO2022082933A1 (en) | 2022-04-28 |
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