CN109576718B - Surface treatment process of rolled copper foil - Google Patents

Surface treatment process of rolled copper foil Download PDF

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Publication number
CN109576718B
CN109576718B CN201910077181.0A CN201910077181A CN109576718B CN 109576718 B CN109576718 B CN 109576718B CN 201910077181 A CN201910077181 A CN 201910077181A CN 109576718 B CN109576718 B CN 109576718B
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copper foil
rolled copper
solution
electroplating
rolled
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CN109576718A (en
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张运东
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Jiangxi Province Hangyu New Material Co ltd
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Jiangxi Province Hangyu New Material Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/10—Other heavy metals
    • C23G1/103—Other heavy metals copper or alloys of copper
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • C23C22/10—Orthophosphates containing oxidants
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
    • 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
    • C25D5/38—Pretreatment of metallic surfaces to be electroplated of refractory metals or nickel
    • 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
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
    • C23C2222/20—Use of solutions containing silanes

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Electroplating Methods And Accessories (AREA)

Abstract

The invention relates to the technical field of copper foil production processes, in particular to a surface treatment process of rolled copper foil, which optimizes and improves various procedures of surface treatment of the rolled copper foil according to the characteristics of the rolled copper foil, does not introduce harmful elements such as chromium, arsenic and the like in the whole process, is completely environment-friendly and conforms to the ROHS regulation of European Union; the rolled copper foil obtained after the procedures of cleaning, primary roughening, primary curing, secondary roughening, secondary curing, nickel-lanthanum alloy plated heat-resistant layer, tungsten-zinc alloy plated heat-resistant layer, passivation, drying, silane coupling agent treatment and the like has low surface roughness, excellent heat resistance, corrosion resistance and higher peel strength, and can meet higher requirements of industrial production.

Description

Surface treatment process of rolled copper foil
Technical Field
The invention relates to the technical field of copper foil production processes, in particular to a surface treatment process of rolled copper foil.
Background
Copper foil is one of the important materials for manufacturing printed circuit boards, and the quality of copper foil has an important influence on the performance of printed circuit boards. According to the difference of the production process, the copper foil mainly comprises two types of electrolytic copper foil and rolled copper foil, and the rolled copper foil has better bending performance than the electrolytic copper foil, so that the copper foil is more suitable for the application of the flexible printed circuit board.
Before the copper foil is used, the copper foil is usually pressed with a resin substrate to form a copper-clad plate, and then the copper foil can be applied to a circuit board, so that the copper foil and the substrate have enough binding force, certain heat resistance, corrosion resistance, oxidation resistance and other characteristics, the performance of the printed circuit board is guaranteed, and the copper foil is subjected to surface treatment before pressing. At present, the surface treatment process of the copper foil mainly comprises degreasing, coarsening, curing, heat-resistant layer plating, oxidation resistance plating and the like. However, the copper foil prepared by adopting the traditional copper foil surface treatment process has small peeling strength and poor heat resistance and corrosion resistance, and harmful elements such as chromium, arsenic and the like can be introduced, so that the copper foil is not environment-friendly enough and does not meet ROHS regulations of European Union.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a surface treatment process of rolled copper foil, which is completely environment-friendly and meets the ROHS regulation of European Union, does not contain harmful elements such as chromium, arsenic and the like, has low surface roughness, excellent heat resistance, corrosion resistance and higher peel strength, and meets higher requirements of industrial production.
In order to achieve the purpose, the invention adopts the technical scheme that:
a surface treatment process of rolled copper foil comprises the following steps:
s1, cleaning: soaking the rolled copper foil in a cleaning solution for cleaning, taking out the rolled copper foil, cleaning the rolled copper foil for three times by using hot water at the temperature of 50-80 ℃, and airing for later use;
the cleaning solution comprises the following components in percentage by weight:
15-20% of anionic surfactant, 10-15% of nonionic surfactant, 8-12% of sulfuric acid, 1-3% of solubilizer, 1-3% of builder and 47-65% of pure water;
s2, first coarsening: adding a roughening solution into the electroplating rectifier at a current density of 15-20A/dm2Electroplating 12-18S on the rolled copper foil at the temperature of 30-40 ℃;
the coarsening liquid comprises 15-25g/L copper sulfate, 60-80 g/L sulfuric acid, 3-5g/L ferric sulfite and 1-3g/L nickel sulfate;
s3, first curing: adding a curing liquid into the electroplating rectifier at a current density of 15-20A/dm2Electroplating the rolled copper foil for 8-15S at the temperature of 45-55 ℃;
the curing liquid comprises 60-70g/L copper sulfate, 90-100 g/L sulfuric acid and 2-3g/L lecithin;
s4, secondary coarsening: adding the roughening solution in the first roughening step into an electroplating rectifier, wherein the current density is 8-12A/dm2Electroplating the rolled copper foil for 7-10S at the temperature of 20-30 ℃;
s5, secondary curing: adding the curing liquid in the first curing step into an electroplating rectifier, wherein the current density is 12-15A/dm2Electroplating the rolled copper foil for 5-10S at the temperature of 35-40 ℃;
s6, nickel-lanthanum alloy plating: adding a nickel-lanthanum alloy plating solution into an electroplating rectifier at a current density of 10-20A/dm2Electroplating 30-50S on the rolled copper foil at the temperature of 50-65 ℃;
the nickel-lanthanum alloy plating solution comprises 35-45g/L nickel sulfamate, 20-30g/L lanthanum chloride, 3-5g/L urea and 2-3g/L stabilizer, and the pH value of the plating solution is adjusted to 3-6 by using citric acid;
s7 tungsten platingZinc alloy: adding a tungsten-zinc alloy plating solution into an electroplating rectifier at a current density of 5-10A/dm2Electroplating 15-25S on the rolled copper foil at the temperature of 40-50 ℃;
the tungsten-zinc alloy plating solution comprises 20-30g/L of sodium tungstate, 10-15g/L of zinc nitrate, 1-2g/L of sodium dodecyl sulfate and 2-3g/L of stabilizer, and the pH value is adjusted to 3-5 by using boric acid solution;
s8, passivation: firstly heating the passivation solution to 40-50 ℃, and then soaking the rolled copper foil in the passivation solution for passivation for 25-35 s;
the passivation solution comprises 6-10g/L of titanium trichloride, 8-12g/L of phytic acid, 8-15mL/L of hydrogen peroxide and 10-18g/L of sodium hexametaphosphate, and the pH of the passivation solution is adjusted to 1-3 by nitric acid;
s9, drying: placing the passivated rolled copper foil in an oven at 50-60 ℃ to dry for 8-10 h;
s10, silane coupling agent treatment: preparing 3-5% of silane coupling agent alcohol solution by using absolute ethyl alcohol, then soaking the dried rolled aluminum foil into the silane coupling agent alcohol solution, taking out the rolled aluminum foil after 10-15s, and finally curing the rolled aluminum foil for 1-3h at the temperature of 70-80 ℃ to finish the surface treatment work of the rolled copper foil.
Preferably, in the step S1, the rolled copper foil is soaked in the cleaning solution for three times to be cleaned, each soaking time is 1-2min, and after each soaking time, the rolled copper foil needs to be cleaned with hot water at 50-80 ℃ for three times.
Preferably, the anionic surfactant is any one of sodium dodecyl benzene sulfonate, sodium stearate, lauryl alcohol, vinyl ether and glyceride.
Preferably, the nonionic surfactant is any one of fatty alcohol-polyoxyethylene ether, coconut oil fatty acid diethanolamide, alkylphenol ethoxylate and fatty acid-polyoxyethylene ester.
Preferably, the solubilizer is any one of ethanol, isopropanol and butanol.
Preferably, the builder is any one of potassium pyrophosphate, sodium nitrite, sodium benzoate and sodium sulfate.
Preferably, the stabilizer in the S6 step is sodium pyrophosphate.
Preferably, the stabilizer in the S7 step is sodium citrate.
Preferably, the rolled copper foil plated with the wolfram-zinc alloy is immersed in warm water at 45 to 55 ℃ and washed three times before the passivation in the step of S9.
Preferably, the silane coupling agent is a silane coupling agent kh 550.
Compared with the prior art, the invention has the beneficial effects that:
the surface treatment process of the rolled copper foil provided by the invention optimizes various basic process procedures of surface treatment of the rolled copper foil, and the whole process comprises the working procedures of cleaning, roughening twice, curing twice, plating nickel lanthanum alloy, plating tungsten zinc alloy, passivation, drying, silane coupling agent treatment and the like, and meanwhile, the components of cleaning solution, roughening solution, curing solution, electroplating solution (nickel lanthanum alloy plating solution and tungsten zinc alloy plating solution) and passivation solution and the like are optimized in formula, so that the obtained rolled copper foil has good surface smoothness and low roughness; in the invention, through two coarsening and two curing processes, the surface of the copper foil can form a coarsening tumor body with a firm structure, so that the copper foil is combined with a copper foil substrate more firmly, and meanwhile, as the silane coupling agent coated on the surface of the copper foil can generate chemical bonding action with the resin substrate and the calendering copper box, the binding force between the calendering copper foil and the printed board substrate is further improved; the passivation solution can form a layer of passivation film on the surface of the rolled copper foil in the passivation treatment process, so that the problem of color change of the rolled copper foil during high-temperature lamination can be effectively solved, and the rolled copper foil can be prevented from being directly contacted with air and moisture to generate rotten color change, thereby improving the corrosion resistance of the rolled copper foil; in addition, because the electroplating solution contains high-temperature elements such as nickel, tungsten and the like, the heat resistance of the rolled copper foil can be greatly improved after the elements are coated on the surface of the copper foil; on the whole, harmful elements such as chromium, arsenic and the like are not introduced in the whole process, so that the method is completely environment-friendly and conforms to the ROHS specification of the European Union; in conclusion, the rolled copper foil obtained by the process disclosed by the invention is low in surface roughness, excellent in heat resistance, corrosion resistance and higher in peel strength, and can meet higher requirements of industrial production.
Detailed Description
The following further describes the embodiments of the present invention. It should be noted that the description of the embodiments is provided to help understanding of the present invention, but the present invention is not limited thereto. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Example 1:
a surface treatment process of rolled copper foil comprises the following steps:
s1, cleaning: soaking the rolled copper foil in a cleaning solution for cleaning, taking out the rolled copper foil, cleaning the rolled copper foil for three times by using hot water at 50 ℃, and airing for later use; when the rolled copper foil is just rolled, the surface of the rolled copper foil is smooth, so that oil stains and an oxidation layer on the surface of the rolled copper foil need to be removed, the surface of the rolled copper foil is enabled to recover activity, in order to ensure that the surface of the rolled copper foil is cleaned, the rolled copper foil is soaked in a cleaning solution for three times for cleaning, the soaking time is 1min, and the cleaning time is three times after each soaking;
in order to effectively remove the greasy dirt and the oxidation layer on the surface of the rolled copper foil, the cleaning solution is optimized in the embodiment, and comprises the following components in percentage by weight:
15% of sodium dodecyl benzene sulfonate, 10% of fatty alcohol-polyoxyethylene ether, 8% of sulfuric acid, 1% of ethanol, 1% of potassium pyrophosphate and 65% of pure water;
the cleaning solution reasonably combines an anionic surfactant, a nonionic surfactant, sulfuric acid and the like, so that the cleaning solution can simultaneously remove oil stains and oxidation layers on the surface of the rolled copper foil, and has high cleaning efficiency;
s2, first coarsening: adding a roughening solution into the electroplating rectifier at a current density of 15A/dm2Electroplating 18S on the rolled copper foil at the temperature of 30 ℃;
coarsening is to generate copper nodules on the surface of the rolled copper foil, improve the surface area of the combination of the rolled copper foil and the substrate, further strengthen the binding force between the rolled copper foil and the substrate, and in order to improve the coarsening effect, the embodiment optimizes a coarsening solution, wherein the coarsening solution comprises 15g/L copper sulfate, 60g/L sulfuric acid, 3g/L ferrous sulfate and 1g/L nickel sulfate, and during preparation, the copper sulfate, the sulfuric acid, the ferrous sulfate and the nickel sulfate are sequentially added into pure water according to the proportion and are uniformly stirred;
s3, first curing: adding a curing liquid into the electroplating rectifier at a current density of 15A/dm2Electroplating 15S on the rolled copper foil at the temperature of 45 ℃;
the solidification has a reinforcing effect on the coarsened structure, a firm foundation is provided for subsequent treatment, and in order to improve the solidification effect, the solidification solution is optimized in the embodiment and comprises 60g/L copper sulfate, 90g/L sulfuric acid and 2g/L lecithin, and during preparation, the copper sulfate, the sulfuric acid and the lecithin are sequentially added into pure water according to the proportion and are uniformly stirred;
s4, secondary coarsening: adding the roughening solution in the first roughening step into the electroplating rectifier, and controlling the current density to be 8A/dm2Electroplating 10S on the rolled copper foil at the temperature of 20 ℃, and performing secondary roughening to improve the roughening effect of the rolled copper foil and greatly improve the binding force between the rolled copper foil and the substrate;
s5, secondary curing: adding the curing liquid in the first curing step into the electroplating rectifier, and controlling the current density to be 12A/dm2Electroplating 10S on the rolled copper foil at the temperature of 35 ℃, and performing secondary curing to reinforce the secondary coarsened structure;
s6, nickel-lanthanum alloy plating: adding a nickel-lanthanum alloy plating solution into an electroplating rectifier at a current density of 10A/dm2Electroplating 50S on the rolled copper foil at the temperature of 50 ℃, and forming a nickel-lanthanum alloy heat-resistant layer on the surface of the rolled copper foil through induced codeposition of nickel and lanthanum, so that the heat resistance and the high-temperature peeling strength of the copper foil are improved;
in order to improve the heat resistance of the copper foil, the heat-resistant plating layer is optimized in the embodiment, the nickel-lanthanum alloy plating solution comprises 35g/L nickel sulfamate, 20g/L lanthanum chloride, 3g/L urea and 2g/L sodium pyrophosphate, and during preparation, the nickel sulfamate, the lanthanum chloride, the urea and the sodium pyrophosphate are sequentially added into pure water according to the proportion, stirred and uniformly mixed, and then the pH value of the plating solution is adjusted to 3 by using citric acid;
s7, tungsten-zinc alloy plating: adding tungsten-zinc alloy plating solution into the electroplating rectifier at a current density of 5A/dm2Electroplating 25S on the rolled copper foil at the temperature of 40 ℃, forming a second heat-resistant layer, namely a tungsten-plated heat-resistant layer, on the surface of the rolled copper foil by taking sodium tungstate as a main salt and zinc nitrate as an auxiliary salt, and further improving the heat resistance and the high-temperature peeling strength of the copper foil;
in order to improve the heat resistance of the copper foil, the second heat-resistant plating layer is optimized in this embodiment, the tungsten-zinc alloy plating solution includes 20g/L sodium tungstate, 10g/L zinc nitrate, 1g/L sodium dodecyl sulfate, and 2g/L sodium citrate, and during the preparation, the sodium tungstate, the zinc nitrate, the sodium dodecyl sulfate, and the sodium citrate are sequentially added to pure water according to the above ratio, and are stirred and mixed uniformly, and then the PH is adjusted to 3 with a boric acid solution;
s8, passivation: in order to remove the redundant heat-resistant coating on the surface of the rolled copper foil and avoid the influence of the redundant heat-resistant coating on the subsequent treatment process, the rolled copper foil plated with the tungsten-zinc alloy is immersed in warm water at 45 ℃ for three times before passivation, then the passivation solution is heated to 40 ℃, and finally the rolled copper foil is immersed in the passivation solution for passivation for 35 s;
in the passivation, a layer of compact antioxidant film is formed on the surface of the rolled copper foil, so that the rolled copper foil is not in direct contact with air, the corrosion resistance of the rolled copper foil is improved, and in order to improve the oxidation resistance of the rolled copper foil, the embodiment optimizes a passivation solution, wherein the passivation solution comprises 6g/L titanium trichloride, 8g/L phytic acid, 8mL/L hydrogen peroxide and 10g/L sodium hexametaphosphate, and during preparation, the titanium trichloride, the phytic acid, the hydrogen peroxide and the sodium hexametaphosphate are sequentially added into pure water according to the proportion and uniformly stirred, and then the pH of the passivation solution is adjusted to 1 by using nitric acid;
s9, drying: placing the passivated rolled copper foil in a 50 ℃ drying oven to be dried for 10 hours;
s10, silane coupling agent treatment: firstly, preparing 3% of silane coupling agent alcohol solution by using absolute ethyl alcohol, wherein the silane coupling agent adopts silane coupling agent kh550, then soaking the dried rolled aluminum foil into the silane coupling agent alcohol solution, taking out the aluminum foil after 15s, and finally curing the aluminum foil for 3h at 70 ℃, so that the surface treatment work of the rolled copper foil can be completed, and the corrosion resistance of the rolled copper foil can be further improved by the silane coupling agent treatment process.
Example 2:
a surface treatment process of rolled copper foil comprises the following steps:
s1, cleaning: soaking the rolled copper foil in a cleaning solution for cleaning, taking out the rolled copper foil, cleaning the rolled copper foil for three times by using hot water at 65 ℃, and airing for later use; when the rolled copper foil is just rolled, the surface of the rolled copper foil is smooth, so that oil stains and an oxidation layer on the surface of the rolled copper foil need to be removed, the surface of the rolled copper foil is enabled to recover activity, in order to ensure that the surface of the rolled copper foil is cleaned, the rolled copper foil is soaked in a cleaning solution for three times for cleaning, the soaking time is 1.5min, and the rolled copper foil needs to be cleaned for three times by hot water at 65 ℃ after each soaking time;
in order to effectively remove the greasy dirt and the oxidation layer on the surface of the rolled copper foil, the cleaning solution is optimized in the embodiment, and comprises the following components in percentage by weight:
18% of sodium dodecyl benzene sulfonate, 12.5% of fatty alcohol-polyoxyethylene ether, 10% of sulfuric acid, 2% of ethanol, 2% of potassium pyrophosphate and 55.5% of pure water;
the cleaning solution reasonably combines an anionic surfactant, a nonionic surfactant, sulfuric acid and the like, so that the cleaning solution can simultaneously remove oil stains and oxidation layers on the surface of the rolled copper foil, and has high cleaning efficiency;
s2, first coarsening: adding a roughening solution into the electroplating rectifier at a current density of 18A/dm2Electroplating 15S on the rolled copper foil at the temperature of 35 ℃;
coarsening is to generate copper nodules on the surface of the rolled copper foil, improve the surface area of the combination of the rolled copper foil and the substrate, further strengthen the binding force between the rolled copper foil and the substrate, and in order to improve the coarsening effect, the embodiment optimizes a coarsening solution, wherein the coarsening solution comprises 20g/L copper sulfate, 70g/L sulfuric acid, 4g/L ferrous sulfate and 2g/L nickel sulfate, and during preparation, the copper sulfate, the sulfuric acid, the ferrous sulfate and the nickel sulfate are sequentially added into pure water according to the proportion and are uniformly stirred;
s3, firstPrimary curing: adding a curing liquid into the electroplating rectifier at a current density of 18A/dm2Electroplating 12S on the rolled copper foil at the temperature of 50 ℃;
the solidification has a reinforcing effect on the coarsened structure, a firm foundation is provided for subsequent treatment, and in order to improve the solidification effect, the solidification solution is optimized in the embodiment and comprises 65g/L copper sulfate, 95g/L sulfuric acid and 2.5g/L lecithin, and during preparation, the copper sulfate, the sulfuric acid and the lecithin are sequentially added into pure water according to the proportion and are uniformly stirred;
s4, secondary coarsening: adding the roughening solution in the first roughening step into a plating rectifier at a current density of 10A/dm2Electroplating the rolled copper foil for 8.5S at the temperature of 25 ℃, and performing secondary roughening to improve the roughening effect of the rolled copper foil and greatly improve the bonding force between the rolled copper foil and the substrate;
s5, secondary curing: adding the curing liquid in the first curing step into a plating rectifier at a current density of 13.5A/dm2Electroplating the rolled copper foil for 7.5 seconds at the temperature of 38 ℃, and performing secondary curing to reinforce the secondary coarsened structure;
s6, nickel-lanthanum alloy plating: adding a nickel-lanthanum alloy plating solution into an electroplating rectifier at a current density of 15A/dm2Electroplating 40S on the rolled copper foil at the temperature of 58 ℃, and forming a nickel-lanthanum alloy heat-resistant layer on the surface of the rolled copper foil through induced codeposition of nickel and lanthanum, so that the heat resistance and the high-temperature peeling strength of the copper foil are improved;
in order to improve the heat resistance of the copper foil, the heat-resistant plating layer is optimized in the embodiment, the nickel-lanthanum alloy plating solution comprises 40g/L nickel sulfamate, 25g/L lanthanum chloride, 4g/L urea and 2.5g/L sodium pyrophosphate, and during preparation, the nickel sulfamate, the lanthanum chloride, the urea and the sodium pyrophosphate are sequentially added into pure water according to the proportion, stirred and mixed uniformly, and then the pH value of the plating solution is adjusted to 4.5 by using citric acid;
s7, tungsten-zinc alloy plating: adding tungsten-zinc alloy plating solution into the electroplating rectifier at a current density of 8A/dm2Electroplating rolled copper foil for 20S at 45 ℃ with sodium tungstate as main saltZinc nitrate is used as auxiliary salt, and a second heat-resistant layer, namely a tungsten-plated heat-resistant layer, is formed on the surface of the rolled copper foil, so that the heat resistance and the high-temperature peeling strength of the copper foil are further improved;
in order to improve the heat resistance of the copper foil, the second heat-resistant plating layer is optimized in this embodiment, the tungsten-zinc alloy plating solution includes 25g/L sodium tungstate, 12.5g/L zinc nitrate, 1.5g/L sodium dodecyl sulfate, and 2.5g/L sodium citrate, and during the preparation, the sodium tungstate, the zinc nitrate, the sodium dodecyl sulfate, and the sodium citrate are sequentially added to pure water according to the above ratio, and are uniformly stirred, and then the PH is adjusted to 4 by using a boric acid solution;
s8, passivation: in order to remove the redundant heat-resistant coating on the surface of the rolled copper foil and avoid the influence of the redundant heat-resistant coating on the subsequent treatment process, the rolled copper foil plated with the tungsten-zinc alloy is immersed in warm water at 50 ℃ for three times before passivation, then the passivation solution is heated to 45 ℃, and finally the rolled copper foil is immersed in the passivation solution for passivation for 30 seconds;
in the passivation, a layer of compact antioxidant film is formed on the surface of the rolled copper foil, so that the rolled copper foil is not in direct contact with air, the corrosion resistance of the rolled copper foil is improved, and in order to improve the oxidation resistance of the rolled copper foil, the embodiment optimizes a passivation solution, wherein the passivation solution comprises 8g/L titanium trichloride, 10g/L phytic acid, 12mL/L hydrogen peroxide and 14g/L sodium hexametaphosphate, and during preparation, the titanium trichloride, the phytic acid, the hydrogen peroxide and the sodium hexametaphosphate are sequentially added into pure water according to the proportion and uniformly stirred, and then the pH of the passivation solution is adjusted to 2 by using nitric acid;
s9, drying: placing the passivated rolled copper foil in an oven at 55 ℃ for drying for 9 hours;
s10, silane coupling agent treatment: firstly, preparing a 4% silane coupling agent alcohol solution by using absolute ethyl alcohol, wherein the silane coupling agent adopts a silane coupling agent kh550, then soaking the dried rolled aluminum foil into the silane coupling agent alcohol solution, taking out the rolled aluminum foil after 12 seconds, and finally curing the rolled aluminum foil for 2 hours at 75 ℃ to finish the surface treatment work of the rolled copper foil, wherein the corrosion resistance of the rolled copper foil can be further improved by the silane coupling agent treatment process.
Example 3:
a surface treatment process of rolled copper foil comprises the following steps:
s1, cleaning: soaking the rolled copper foil in a cleaning solution for cleaning, taking out the rolled copper foil, cleaning the rolled copper foil for three times by using hot water at the temperature of 80 ℃, and airing the rolled copper foil for later use; when the rolled copper foil is just rolled, the surface of the rolled copper foil is smooth, so that oil stains and an oxidation layer on the surface of the rolled copper foil need to be removed, the surface of the rolled copper foil is enabled to recover activity, in order to ensure that the surface of the rolled copper foil is cleaned, the rolled copper foil is soaked in a cleaning solution for three times for cleaning, each soaking time is 2min, and after each soaking time, the rolled copper foil needs to be cleaned for three times by hot water at 80 ℃;
in order to effectively remove the greasy dirt and the oxidation layer on the surface of the rolled copper foil, the cleaning solution is optimized in the embodiment, and comprises the following components in percentage by weight:
20% of sodium dodecyl benzene sulfonate, 15% of fatty alcohol-polyoxyethylene ether, 12% of sulfuric acid, 3% of ethanol, 3% of potassium pyrophosphate and 47% of pure water;
the cleaning solution reasonably combines an anionic surfactant, a nonionic surfactant, sulfuric acid and the like, so that the cleaning solution can simultaneously remove oil stains and oxidation layers on the surface of the rolled copper foil, and has high cleaning efficiency;
s2, first coarsening: adding a roughening solution into the electroplating rectifier at a current density of 20A/dm2Electroplating 12S on the rolled copper foil at the temperature of 40 ℃;
coarsening is to generate copper nodules on the surface of the rolled copper foil, improve the surface area of the combination of the rolled copper foil and the substrate, further strengthen the binding force between the rolled copper foil and the substrate, and in order to improve the coarsening effect, the embodiment optimizes a coarsening solution, wherein the coarsening solution comprises 25g/L copper sulfate, 80g/L sulfuric acid, 5g/L ferrous sulfate and 3g/L nickel sulfate, and during preparation, the copper sulfate, the sulfuric acid, the ferrous sulfate and the nickel sulfate are sequentially added into pure water according to the proportion and are uniformly stirred;
s3, first curing: adding a curing liquid into the electroplating rectifier at a current density of 20A/dm2Electroplating the rolled copper foil for 8S at the temperature of 55 ℃;
the solidification has a reinforcing effect on the coarsened structure, a firm foundation is provided for subsequent treatment, and in order to improve the solidification effect, the solidification solution is optimized in the embodiment and comprises 70g/L copper sulfate, 100g/L sulfuric acid and 3g/L lecithin, and during preparation, the copper sulfate, the sulfuric acid and the lecithin are sequentially added into pure water according to the proportion and are uniformly stirred;
s4, secondary coarsening: adding the roughening solution in the first roughening step into a plating rectifier at a current density of 12A/dm2Electroplating 7S on the rolled copper foil at the temperature of 30 ℃, and performing secondary roughening to improve the roughening effect of the rolled copper foil and greatly improve the binding force between the rolled copper foil and the substrate;
s5, secondary curing: adding the curing liquid in the first curing step into the electroplating rectifier, and controlling the current density to be 15A/dm2Electroplating the rolled copper foil for 5 seconds at the temperature of 40 ℃, and performing secondary curing to reinforce the secondary coarsened structure;
s6, nickel-lanthanum alloy plating: adding a nickel-lanthanum alloy plating solution into an electroplating rectifier at a current density of 20A/dm2Electroplating 30S on the rolled copper foil at the temperature of 65 ℃, and forming a nickel-lanthanum alloy heat-resistant layer on the surface of the rolled copper foil through induced codeposition of nickel and lanthanum, so that the heat resistance and the high-temperature peeling strength of the copper foil are improved;
in order to improve the heat resistance of the copper foil, the heat-resistant plating layer is optimized in the embodiment, the nickel-lanthanum alloy plating solution comprises 45g/L nickel sulfamate, 30g/L lanthanum chloride, 5g/L urea and 3g/L sodium pyrophosphate, and during preparation, the nickel sulfamate, the lanthanum chloride, the urea and the sodium pyrophosphate are sequentially added into pure water according to the proportion, stirred and uniformly mixed, and then the pH value of the plating solution is adjusted to 6 by using citric acid;
s7, tungsten-zinc alloy plating: adding tungsten-zinc alloy plating solution into the electroplating rectifier at a current density of 10A/dm2Electroplating 25S on the rolled copper foil at the temperature of 50 ℃, forming a second heat-resistant layer, namely a tungsten-plated heat-resistant layer, on the surface of the rolled copper foil by taking sodium tungstate as a main salt and zinc nitrate as an auxiliary salt, and further improving the heat resistance and the high-temperature peeling strength of the copper foil;
in order to improve the heat resistance of the copper foil, the second heat-resistant plating layer is optimized in this embodiment, the tungsten-zinc alloy plating solution includes 30g/L sodium tungstate, 15g/L zinc nitrate, 2g/L sodium dodecyl sulfate, and 3g/L sodium citrate, and during the preparation, the sodium tungstate, the zinc nitrate, the sodium dodecyl sulfate, and the sodium citrate are sequentially added to pure water according to the above ratio, and are stirred and mixed uniformly, and then the PH is adjusted to 5 with a boric acid solution;
s8, passivation: in order to remove the redundant heat-resistant coating on the surface of the rolled copper foil and avoid the influence of the redundant heat-resistant coating on the subsequent treatment process, the rolled copper foil plated with the tungsten-zinc alloy is immersed in warm water at 55 ℃ for three times before passivation, then the passivation solution is heated to 50 ℃, and finally the rolled copper foil is immersed in the passivation solution for passivation for 25 s;
in the passivation, a layer of compact antioxidant film is formed on the surface of the rolled copper foil, so that the rolled copper foil is not in direct contact with air, the corrosion resistance of the rolled copper foil is improved, and in order to improve the oxidation resistance of the rolled copper foil, the embodiment optimizes a passivation solution, wherein the passivation solution comprises 10g/L of titanium trichloride, 12g/L of phytic acid, 15mL/L of hydrogen peroxide and 18g/L of sodium hexametaphosphate, and during preparation, the titanium trichloride, the phytic acid, the hydrogen peroxide and the sodium hexametaphosphate are sequentially added into pure water according to the proportion and uniformly stirred, and then the pH of the passivation solution is adjusted to 3 by using nitric acid;
s9, drying: placing the passivated rolled copper foil in a 60 ℃ drying oven to be dried for 8 hours;
s10, silane coupling agent treatment: firstly, preparing a 5% silane coupling agent alcohol solution by using absolute ethyl alcohol, wherein the silane coupling agent adopts a silane coupling agent kh550, then soaking the dried rolled aluminum foil into the silane coupling agent alcohol solution, taking out the aluminum foil after 10 seconds, and finally curing the aluminum foil for 1 hour at 80 ℃, so that the surface treatment work of the rolled copper foil can be completed, and the corrosion resistance of the rolled copper foil can be further improved by the silane coupling agent treatment process.
Example 4:
a surface treatment process of rolled copper foil comprises the following steps:
s1, cleaning: soaking the rolled copper foil in a cleaning solution for cleaning, taking out the rolled copper foil, cleaning the rolled copper foil for three times by using hot water at 65 ℃, and airing for later use; when the rolled copper foil is just rolled, the surface of the rolled copper foil is smooth, so that oil stains and an oxidation layer on the surface of the rolled copper foil need to be removed, the surface of the rolled copper foil is enabled to recover activity, in order to ensure that the surface of the rolled copper foil is cleaned, the rolled copper foil is soaked in a cleaning solution for three times for cleaning, the soaking time is 1.5min, and the rolled copper foil needs to be cleaned for three times by hot water at 65 ℃ after each soaking time;
in order to effectively remove the greasy dirt and the oxidation layer on the surface of the rolled copper foil, the cleaning solution is optimized in the embodiment, and comprises the following components in percentage by weight:
18% sodium stearate, 12.5% coconut diethanolamide, 10% sulfuric acid, 2% isopropanol, 2% sodium nitrite and 55.5% pure water;
the cleaning solution reasonably combines an anionic surfactant, a nonionic surfactant, sulfuric acid and the like, so that the cleaning solution can simultaneously remove oil stains and oxidation layers on the surface of the rolled copper foil, and has high cleaning efficiency;
s2, first coarsening: adding a roughening solution into the electroplating rectifier at a current density of 18A/dm2Electroplating 15S on the rolled copper foil at the temperature of 35 ℃;
coarsening is to generate copper nodules on the surface of the rolled copper foil, improve the surface area of the combination of the rolled copper foil and the substrate, further strengthen the binding force between the rolled copper foil and the substrate, and in order to improve the coarsening effect, the embodiment optimizes a coarsening solution, wherein the coarsening solution comprises 20g/L copper sulfate, 70g/L sulfuric acid, 4g/L ferrous sulfate and 2g/L nickel sulfate, and during preparation, the copper sulfate, the sulfuric acid, the ferrous sulfate and the nickel sulfate are sequentially added into pure water according to the proportion and are uniformly stirred;
s3, first curing: adding a curing liquid into the electroplating rectifier at a current density of 18A/dm2Electroplating 12S on the rolled copper foil at the temperature of 50 ℃;
the solidification has a reinforcing effect on the coarsened structure, a firm foundation is provided for subsequent treatment, and in order to improve the solidification effect, the solidification solution is optimized in the embodiment and comprises 65g/L copper sulfate, 95g/L sulfuric acid and 2.5g/L lecithin, and during preparation, the copper sulfate, the sulfuric acid and the lecithin are sequentially added into pure water according to the proportion and are uniformly stirred;
s4, twiceCoarsening: adding the roughening solution in the first roughening step into a plating rectifier at a current density of 10A/dm2Electroplating the rolled copper foil for 8.5S at the temperature of 25 ℃, and performing secondary roughening to improve the roughening effect of the rolled copper foil and greatly improve the bonding force between the rolled copper foil and the substrate;
s5, secondary curing: adding the curing liquid in the first curing step into a plating rectifier at a current density of 13.5A/dm2Electroplating the rolled copper foil for 7.5 seconds at the temperature of 38 ℃, and performing secondary curing to reinforce the secondary coarsened structure;
s6, nickel-lanthanum alloy plating: adding a nickel-lanthanum alloy plating solution into an electroplating rectifier at a current density of 15A/dm2Electroplating 40S on the rolled copper foil at the temperature of 58 ℃, and forming a nickel-lanthanum alloy heat-resistant layer on the surface of the rolled copper foil through induced codeposition of nickel and lanthanum, so that the heat resistance and the high-temperature peeling strength of the copper foil are improved;
in order to improve the heat resistance of the copper foil, the heat-resistant plating layer is optimized in the embodiment, the nickel-lanthanum alloy plating solution comprises 40g/L nickel sulfamate, 25g/L lanthanum chloride, 4g/L urea and 2.5g/L sodium pyrophosphate, and during preparation, the nickel sulfamate, the lanthanum chloride, the urea and the sodium pyrophosphate are sequentially added into pure water according to the proportion, stirred and mixed uniformly, and then the pH value of the plating solution is adjusted to 4.5 by using citric acid;
s7, tungsten-zinc alloy plating: adding tungsten-zinc alloy plating solution into the electroplating rectifier at a current density of 8A/dm2Electroplating 20S on the rolled copper foil at the temperature of 45 ℃, forming a second heat-resistant layer, namely a tungsten-plated heat-resistant layer, on the surface of the rolled copper foil by taking sodium tungstate as a main salt and zinc nitrate as an auxiliary salt, and further improving the heat resistance and the high-temperature peeling strength of the copper foil;
in order to improve the heat resistance of the copper foil, the second heat-resistant plating layer is optimized in this embodiment, the tungsten-zinc alloy plating solution includes 25g/L sodium tungstate, 12.5g/L zinc nitrate, 1.5g/L sodium dodecyl sulfate, and 2.5g/L sodium citrate, and during the preparation, the sodium tungstate, the zinc nitrate, the sodium dodecyl sulfate, and the sodium citrate are sequentially added to pure water according to the above ratio, and are uniformly stirred, and then the PH is adjusted to 4 by using a boric acid solution;
s8, passivation: in order to remove the redundant heat-resistant coating on the surface of the rolled copper foil and avoid the influence of the redundant heat-resistant coating on the subsequent treatment process, the rolled copper foil plated with the tungsten-zinc alloy is immersed in warm water at 50 ℃ for three times before passivation, then the passivation solution is heated to 45 ℃, and finally the rolled copper foil is immersed in the passivation solution for passivation for 30 seconds;
in the passivation, a layer of compact antioxidant film is formed on the surface of the rolled copper foil, so that the rolled copper foil is not in direct contact with air, the corrosion resistance of the rolled copper foil is improved, and in order to improve the oxidation resistance of the rolled copper foil, the embodiment optimizes a passivation solution, wherein the passivation solution comprises 8g/L titanium trichloride, 10g/L phytic acid, 12mL/L hydrogen peroxide and 14g/L sodium hexametaphosphate, and during preparation, the titanium trichloride, the phytic acid, the hydrogen peroxide and the sodium hexametaphosphate are sequentially added into pure water according to the proportion and uniformly stirred, and then the pH of the passivation solution is adjusted to 2 by using nitric acid;
s9, drying: placing the passivated rolled copper foil in an oven at 55 ℃ for drying for 9 hours;
s10, silane coupling agent treatment: firstly, preparing a 4% silane coupling agent alcohol solution by using absolute ethyl alcohol, wherein the silane coupling agent adopts a silane coupling agent kh550, then soaking the dried rolled aluminum foil into the silane coupling agent alcohol solution, taking out the rolled aluminum foil after 12 seconds, and finally curing the rolled aluminum foil for 2 hours at 75 ℃ to finish the surface treatment work of the rolled copper foil, wherein the corrosion resistance of the rolled copper foil can be further improved by the silane coupling agent treatment process.
Example 5:
a surface treatment process of rolled copper foil comprises the following steps:
s1, cleaning: soaking the rolled copper foil in a cleaning solution for cleaning, taking out the rolled copper foil, cleaning the rolled copper foil for three times by using hot water at 65 ℃, and airing for later use; when the rolled copper foil is just rolled, the surface of the rolled copper foil is smooth, so that oil stains and an oxidation layer on the surface of the rolled copper foil need to be removed, the surface of the rolled copper foil is enabled to recover activity, in order to ensure that the surface of the rolled copper foil is cleaned, the rolled copper foil is soaked in a cleaning solution for three times for cleaning, the soaking time is 1.5min, and the rolled copper foil needs to be cleaned for three times by hot water at 65 ℃ after each soaking time;
in order to effectively remove the greasy dirt and the oxidation layer on the surface of the rolled copper foil, the cleaning solution is optimized in the embodiment, and comprises the following components in percentage by weight:
18% of lauryl alcohol, 12.5% of alkylphenol polyoxyethylene, 10% of sulfuric acid, 2% of butanol, 2% of sodium benzoate and 55.5% of pure water;
the cleaning solution reasonably combines an anionic surfactant, a nonionic surfactant, sulfuric acid and the like, so that the cleaning solution can simultaneously remove oil stains and oxidation layers on the surface of the rolled copper foil, and has high cleaning efficiency;
s2, first coarsening: adding a roughening solution into the electroplating rectifier at a current density of 18A/dm2Electroplating 15S on the rolled copper foil at the temperature of 35 ℃;
coarsening is to generate copper nodules on the surface of the rolled copper foil, improve the surface area of the combination of the rolled copper foil and the substrate, further strengthen the binding force between the rolled copper foil and the substrate, and in order to improve the coarsening effect, the embodiment optimizes a coarsening solution, wherein the coarsening solution comprises 20g/L copper sulfate, 70g/L sulfuric acid, 4g/L ferrous sulfate and 2g/L nickel sulfate, and during preparation, the copper sulfate, the sulfuric acid, the ferrous sulfate and the nickel sulfate are sequentially added into pure water according to the proportion and are uniformly stirred;
s3, first curing: adding a curing liquid into the electroplating rectifier at a current density of 18A/dm2Electroplating 12S on the rolled copper foil at the temperature of 50 ℃;
the solidification has a reinforcing effect on the coarsened structure, a firm foundation is provided for subsequent treatment, and in order to improve the solidification effect, the solidification solution is optimized in the embodiment and comprises 65g/L copper sulfate, 95g/L sulfuric acid and 2.5g/L lecithin, and during preparation, the copper sulfate, the sulfuric acid and the lecithin are sequentially added into pure water according to the proportion and are uniformly stirred;
s4, secondary coarsening: adding the roughening solution in the first roughening step into a plating rectifier at a current density of 10A/dm2Electroplating the rolled copper foil for 8.5S at the temperature of 25 ℃, and performing secondary roughening to improve the roughening effect of the rolled copper foil and greatly improve the bonding force between the rolled copper foil and the substrate;
s5, secondary curing: adding the curing liquid in the first curing step into a plating rectifier at a current density of 13.5A/dm2Electroplating the rolled copper foil for 7.5 seconds at the temperature of 38 ℃, and performing secondary curing to reinforce the secondary coarsened structure;
s6, nickel-lanthanum alloy plating: adding a nickel-lanthanum alloy plating solution into an electroplating rectifier at a current density of 15A/dm2Electroplating 40S on the rolled copper foil at the temperature of 58 ℃, and forming a nickel-lanthanum alloy heat-resistant layer on the surface of the rolled copper foil through induced codeposition of nickel and lanthanum, so that the heat resistance and the high-temperature peeling strength of the copper foil are improved;
in order to improve the heat resistance of the copper foil, the heat-resistant plating layer is optimized in the embodiment, the nickel-lanthanum alloy plating solution comprises 40g/L nickel sulfamate, 25g/L lanthanum chloride, 4g/L urea and 2.5g/L sodium pyrophosphate, and during preparation, the nickel sulfamate, the lanthanum chloride, the urea and the sodium pyrophosphate are sequentially added into pure water according to the proportion, stirred and mixed uniformly, and then the pH value of the plating solution is adjusted to 4.5 by using citric acid;
s7, tungsten-zinc alloy plating: adding tungsten-zinc alloy plating solution into the electroplating rectifier at a current density of 8A/dm2Electroplating 20S on the rolled copper foil at the temperature of 45 ℃, forming a second heat-resistant layer, namely a tungsten-plated heat-resistant layer, on the surface of the rolled copper foil by taking sodium tungstate as a main salt and zinc nitrate as an auxiliary salt, and further improving the heat resistance and the high-temperature peeling strength of the copper foil;
in order to improve the heat resistance of the copper foil, the second heat-resistant plating layer is optimized in this embodiment, the tungsten-zinc alloy plating solution includes 25g/L sodium tungstate, 12.5g/L zinc nitrate, 1.5g/L sodium dodecyl sulfate, and 2.5g/L sodium citrate, and during the preparation, the sodium tungstate, the zinc nitrate, the sodium dodecyl sulfate, and the sodium citrate are sequentially added to pure water according to the above ratio, and are uniformly stirred, and then the PH is adjusted to 4 by using a boric acid solution;
s8, passivation: in order to remove the redundant heat-resistant coating on the surface of the rolled copper foil and avoid the influence of the redundant heat-resistant coating on the subsequent treatment process, the rolled copper foil plated with the tungsten-zinc alloy is immersed in warm water at 50 ℃ for three times before passivation, then the passivation solution is heated to 45 ℃, and finally the rolled copper foil is immersed in the passivation solution for passivation for 30 seconds;
in the passivation, a layer of compact antioxidant film is formed on the surface of the rolled copper foil, so that the rolled copper foil is not in direct contact with air, the corrosion resistance of the rolled copper foil is improved, and in order to improve the oxidation resistance of the rolled copper foil, the embodiment optimizes a passivation solution, wherein the passivation solution comprises 8g/L titanium trichloride, 10g/L phytic acid, 12mL/L hydrogen peroxide and 14g/L sodium hexametaphosphate, and during preparation, the titanium trichloride, the phytic acid, the hydrogen peroxide and the sodium hexametaphosphate are sequentially added into pure water according to the proportion and uniformly stirred, and then the pH of the passivation solution is adjusted to 2 by using nitric acid;
s9, drying: placing the passivated rolled copper foil in an oven at 55 ℃ for drying for 9 hours;
s10, silane coupling agent treatment: firstly, preparing a 4% silane coupling agent alcohol solution by using absolute ethyl alcohol, wherein the silane coupling agent adopts a silane coupling agent kh550, then soaking the dried rolled aluminum foil into the silane coupling agent alcohol solution, taking out the rolled aluminum foil after 12 seconds, and finally curing the rolled aluminum foil for 2 hours at 75 ℃ to finish the surface treatment work of the rolled copper foil, wherein the corrosion resistance of the rolled copper foil can be further improved by the silane coupling agent treatment process.
Example 6:
a surface treatment process of rolled copper foil comprises the following steps:
s1, cleaning: soaking the rolled copper foil in a cleaning solution for cleaning, taking out the rolled copper foil, cleaning the rolled copper foil for three times by using hot water at 65 ℃, and airing for later use; when the rolled copper foil is just rolled, the surface of the rolled copper foil is smooth, so that oil stains and an oxidation layer on the surface of the rolled copper foil need to be removed, the surface of the rolled copper foil is enabled to recover activity, in order to ensure that the surface of the rolled copper foil is cleaned, the rolled copper foil is soaked in a cleaning solution for three times for cleaning, the soaking time is 1.5min, and the rolled copper foil needs to be cleaned for three times by hot water at 65 ℃ after each soaking time;
in order to effectively remove the greasy dirt and the oxidation layer on the surface of the rolled copper foil, the cleaning solution is optimized in the embodiment, and comprises the following components in percentage by weight:
18% vinyl ether, 12.5% polyoxyethylene fatty acid ester, 10% sulfuric acid, 2% ethanol, 2% sodium sulfate and 55.5% pure water;
the cleaning solution reasonably combines an anionic surfactant, a nonionic surfactant, sulfuric acid and the like, so that the cleaning solution can simultaneously remove oil stains and oxidation layers on the surface of the rolled copper foil, and has high cleaning efficiency;
s2, first coarsening: adding a roughening solution into the electroplating rectifier at a current density of 18A/dm2Electroplating 15S on the rolled copper foil at the temperature of 35 ℃;
coarsening is to generate copper nodules on the surface of the rolled copper foil, improve the surface area of the combination of the rolled copper foil and the substrate, further strengthen the binding force between the rolled copper foil and the substrate, and in order to improve the coarsening effect, the embodiment optimizes a coarsening solution, wherein the coarsening solution comprises 20g/L copper sulfate, 70g/L sulfuric acid, 4g/L ferrous sulfate and 2g/L nickel sulfate, and during preparation, the copper sulfate, the sulfuric acid, the ferrous sulfate and the nickel sulfate are sequentially added into pure water according to the proportion and are uniformly stirred;
s3, first curing: adding a curing liquid into the electroplating rectifier at a current density of 18A/dm2Electroplating 12S on the rolled copper foil at the temperature of 50 ℃;
the solidification has a reinforcing effect on the coarsened structure, a firm foundation is provided for subsequent treatment, and in order to improve the solidification effect, the solidification solution is optimized in the embodiment and comprises 65g/L copper sulfate, 95g/L sulfuric acid and 2.5g/L lecithin, and during preparation, the copper sulfate, the sulfuric acid and the lecithin are sequentially added into pure water according to the proportion and are uniformly stirred;
s4, secondary coarsening: adding the roughening solution in the first roughening step into a plating rectifier at a current density of 10A/dm2Electroplating the rolled copper foil for 8.5S at the temperature of 25 ℃, and performing secondary roughening to improve the roughening effect of the rolled copper foil and greatly improve the bonding force between the rolled copper foil and the substrate;
s5, secondary curing: adding the curing liquid in the first curing step into a plating rectifier at a current density of 13.5A/dm2Electroplating the rolled copper foil for 7.5 seconds at the temperature of 38 ℃, and performing secondary curing to reinforce the secondary coarsened structure;
s6, nickel-lanthanum alloy plating: adding a nickel-lanthanum alloy plating solution into an electroplating rectifier at a current density of 15A/dm2Electroplating 40S on the rolled copper foil at the temperature of 58 ℃, and forming a nickel-lanthanum alloy heat-resistant layer on the surface of the rolled copper foil through induced codeposition of nickel and lanthanum, so that the heat resistance and the high-temperature peeling strength of the copper foil are improved;
in order to improve the heat resistance of the copper foil, the heat-resistant plating layer is optimized in the embodiment, the nickel-lanthanum alloy plating solution comprises 40g/L nickel sulfamate, 25g/L lanthanum chloride, 4g/L urea and 2.5g/L sodium pyrophosphate, and during preparation, the nickel sulfamate, the lanthanum chloride, the urea and the sodium pyrophosphate are sequentially added into pure water according to the proportion, stirred and mixed uniformly, and then the pH value of the plating solution is adjusted to 4.5 by using citric acid;
s7, tungsten-zinc alloy plating: adding tungsten-zinc alloy plating solution into the electroplating rectifier at a current density of 8A/dm2Electroplating 20S on the rolled copper foil at the temperature of 45 ℃, forming a second heat-resistant layer, namely a tungsten-plated heat-resistant layer, on the surface of the rolled copper foil by taking sodium tungstate as a main salt and zinc nitrate as an auxiliary salt, and further improving the heat resistance and the high-temperature peeling strength of the copper foil;
in order to improve the heat resistance of the copper foil, the second heat-resistant plating layer is optimized in this embodiment, the tungsten-zinc alloy plating solution includes 25g/L sodium tungstate, 12.5g/L zinc nitrate, 1.5g/L sodium dodecyl sulfate, and 2.5g/L sodium citrate, and during the preparation, the sodium tungstate, the zinc nitrate, the sodium dodecyl sulfate, and the sodium citrate are sequentially added to pure water according to the above ratio, and are uniformly stirred, and then the PH is adjusted to 4 by using a boric acid solution;
s8, passivation: in order to remove the redundant heat-resistant coating on the surface of the rolled copper foil and avoid the influence of the redundant heat-resistant coating on the subsequent treatment process, the rolled copper foil plated with the tungsten-zinc alloy is immersed in warm water at 50 ℃ for three times before passivation, then the passivation solution is heated to 45 ℃, and finally the rolled copper foil is immersed in the passivation solution for passivation for 30 seconds;
in the passivation, a layer of compact antioxidant film is formed on the surface of the rolled copper foil, so that the rolled copper foil is not in direct contact with air, the corrosion resistance of the rolled copper foil is improved, and in order to improve the oxidation resistance of the rolled copper foil, the embodiment optimizes a passivation solution, wherein the passivation solution comprises 8g/L titanium trichloride, 10g/L phytic acid, 12mL/L hydrogen peroxide and 14g/L sodium hexametaphosphate, and during preparation, the titanium trichloride, the phytic acid, the hydrogen peroxide and the sodium hexametaphosphate are sequentially added into pure water according to the proportion and uniformly stirred, and then the pH of the passivation solution is adjusted to 2 by using nitric acid;
s9, drying: placing the passivated rolled copper foil in an oven at 55 ℃ for drying for 9 hours;
s10, silane coupling agent treatment: firstly, preparing a 4% silane coupling agent alcohol solution by using absolute ethyl alcohol, wherein the silane coupling agent adopts a silane coupling agent kh550, then soaking the dried rolled aluminum foil into the silane coupling agent alcohol solution, taking out the rolled aluminum foil after 12 seconds, and finally curing the rolled aluminum foil for 2 hours at 75 ℃ to finish the surface treatment work of the rolled copper foil, wherein the corrosion resistance of the rolled copper foil can be further improved by the silane coupling agent treatment process.
Example 7:
a surface treatment process of rolled copper foil comprises the following steps:
s1, cleaning: soaking the rolled copper foil in a cleaning solution for cleaning, taking out the rolled copper foil, cleaning the rolled copper foil for three times by using hot water at 65 ℃, and airing for later use; when the rolled copper foil is just rolled, the surface of the rolled copper foil is smooth, so that oil stains and an oxidation layer on the surface of the rolled copper foil need to be removed, the surface of the rolled copper foil is enabled to recover activity, in order to ensure that the surface of the rolled copper foil is cleaned, the rolled copper foil is soaked in a cleaning solution for three times for cleaning, the soaking time is 1.5min, and the rolled copper foil needs to be cleaned for three times by hot water at 65 ℃ after each soaking time;
in order to effectively remove the greasy dirt and the oxidation layer on the surface of the rolled copper foil, the cleaning solution is optimized in the embodiment, and comprises the following components in percentage by weight:
18% of glyceride, 12.5% of fatty alcohol-polyoxyethylene ether, 10% of sulfuric acid, 2% of ethanol, 2% of potassium pyrophosphate and 55.5% of pure water;
the cleaning solution reasonably combines an anionic surfactant, a nonionic surfactant, sulfuric acid and the like, so that the cleaning solution can simultaneously remove oil stains and oxidation layers on the surface of the rolled copper foil, and has high cleaning efficiency;
s2, first coarsening: adding a roughening solution into the electroplating rectifier at a current density of 18A/dm2Electroplating 15S on the rolled copper foil at the temperature of 35 ℃;
coarsening is to generate copper nodules on the surface of the rolled copper foil, improve the surface area of the combination of the rolled copper foil and the substrate, further strengthen the binding force between the rolled copper foil and the substrate, and in order to improve the coarsening effect, the embodiment optimizes a coarsening solution, wherein the coarsening solution comprises 20g/L copper sulfate, 70g/L sulfuric acid, 4g/L ferrous sulfate and 2g/L nickel sulfate, and during preparation, the copper sulfate, the sulfuric acid, the ferrous sulfate and the nickel sulfate are sequentially added into pure water according to the proportion and are uniformly stirred;
s3, first curing: adding a curing liquid into the electroplating rectifier at a current density of 18A/dm2Electroplating 12S on the rolled copper foil at the temperature of 50 ℃;
the solidification has a reinforcing effect on the coarsened structure, a firm foundation is provided for subsequent treatment, and in order to improve the solidification effect, the solidification solution is optimized in the embodiment and comprises 65g/L copper sulfate, 95g/L sulfuric acid and 2.5g/L lecithin, and during preparation, the copper sulfate, the sulfuric acid and the lecithin are sequentially added into pure water according to the proportion and are uniformly stirred;
s4, secondary coarsening: adding the roughening solution in the first roughening step into a plating rectifier at a current density of 10A/dm2Electroplating the rolled copper foil for 8.5S at the temperature of 25 ℃, and performing secondary roughening to improve the roughening effect of the rolled copper foil and greatly improve the bonding force between the rolled copper foil and the substrate;
s5, secondary curing: adding the curing liquid in the first curing step into a plating rectifier at a current density of 13.5A/dm2Electroplating the rolled copper foil for 7.5 seconds at the temperature of 38 ℃, and performing secondary curing to reinforce the secondary coarsened structure;
s6, nickel-lanthanum alloy plating: adding a nickel-lanthanum alloy plating solution into an electroplating rectifier at a current density of 15A/dm2Electroplating 40S on the rolled copper foil at the temperature of 58 ℃, and performing induced codeposition on nickel and lanthanum on the surface of the rolled copper foil to form a nickel-lanthanum alloy heat-resistant layerThe heat resistance and the high-temperature peeling strength of the copper foil are improved;
in order to improve the heat resistance of the copper foil, the heat-resistant plating layer is optimized in the embodiment, the nickel-lanthanum alloy plating solution comprises 40g/L nickel sulfamate, 25g/L lanthanum chloride, 4g/L urea and 2.5g/L sodium pyrophosphate, and during preparation, the nickel sulfamate, the lanthanum chloride, the urea and the sodium pyrophosphate are sequentially added into pure water according to the proportion, stirred and mixed uniformly, and then the pH value of the plating solution is adjusted to 4.5 by using citric acid;
s7, tungsten-zinc alloy plating: adding tungsten-zinc alloy plating solution into the electroplating rectifier at a current density of 8A/dm2Electroplating 20S on the rolled copper foil at the temperature of 45 ℃, forming a second heat-resistant layer, namely a tungsten-plated heat-resistant layer, on the surface of the rolled copper foil by taking sodium tungstate as a main salt and zinc nitrate as an auxiliary salt, and further improving the heat resistance and the high-temperature peeling strength of the copper foil;
in order to improve the heat resistance of the copper foil, the second heat-resistant plating layer is optimized in this embodiment, the tungsten-zinc alloy plating solution includes 25g/L sodium tungstate, 12.5g/L zinc nitrate, 1.5g/L sodium dodecyl sulfate, and 2.5g/L sodium citrate, and during the preparation, the sodium tungstate, the zinc nitrate, the sodium dodecyl sulfate, and the sodium citrate are sequentially added to pure water according to the above ratio, and are uniformly stirred, and then the PH is adjusted to 4 by using a boric acid solution;
s8, passivation: in order to remove the redundant heat-resistant coating on the surface of the rolled copper foil and avoid the influence of the redundant heat-resistant coating on the subsequent treatment process, the rolled copper foil plated with the tungsten-zinc alloy is immersed in warm water at 50 ℃ for three times before passivation, then the passivation solution is heated to 45 ℃, and finally the rolled copper foil is immersed in the passivation solution for passivation for 30 seconds;
in the passivation, a layer of compact antioxidant film is formed on the surface of the rolled copper foil, so that the rolled copper foil is not in direct contact with air, the corrosion resistance of the rolled copper foil is improved, and in order to improve the oxidation resistance of the rolled copper foil, the embodiment optimizes a passivation solution, wherein the passivation solution comprises 8g/L titanium trichloride, 10g/L phytic acid, 12mL/L hydrogen peroxide and 14g/L sodium hexametaphosphate, and during preparation, the titanium trichloride, the phytic acid, the hydrogen peroxide and the sodium hexametaphosphate are sequentially added into pure water according to the proportion and uniformly stirred, and then the pH of the passivation solution is adjusted to 2 by using nitric acid;
s9, drying: placing the passivated rolled copper foil in an oven at 55 ℃ for drying for 9 hours;
s10, silane coupling agent treatment: firstly, preparing a 4% silane coupling agent alcohol solution by using absolute ethyl alcohol, wherein the silane coupling agent adopts a silane coupling agent kh550, then soaking the dried rolled aluminum foil into the silane coupling agent alcohol solution, taking out the rolled aluminum foil after 12 seconds, and finally curing the rolled aluminum foil for 2 hours at 75 ℃ to finish the surface treatment work of the rolled copper foil, wherein the corrosion resistance of the rolled copper foil can be further improved by the silane coupling agent treatment process.
Comparative example:
the comparative example is a common surface treatment process of rolled copper foil, and specifically comprises the following steps:
(1) and oil removal: soaking the rolled copper foil in 15% sodium hydroxide solution for 3min, and then cleaning with clear water for three times;
(2) acid washing: soaking the rolled copper foil in 10% sulfuric acid solution for 3min, and then cleaning with clear water for three times;
(3) and coarsening: adding a roughening solution into the electroplating bath at a current density of 40A/dm2Electroplating the rolled copper foil for 5S at the temperature of 30 ℃;
the coarsening liquid comprises 30g/L copper sulfate, 90g/L sulfuric acid, 4g/L gelatin and 1g/L gallium arsenide;
(4) and curing: adding a roughening solution into the electroplating bath at a current density of 30A/dm2Electroplating the rolled copper foil for 8S at the temperature of 50 ℃;
the curing liquid comprises 60g/L copper sulfate and 105g/L sulfuric acid;
(5) and zinc-nickel alloy plating: adding a zinc-nickel alloy plating solution into the plating bath at a current density of 20A/dm2Electroplating 45S on the rolled copper foil at the temperature of 50 ℃;
the zinc-nickel alloy plating solution comprises 60g/L of zinc sulfate, 40g/L of nickel sulfate, 40g/L of sodium acetate and 40g/L of sodium sulfate, and the PH of the plating solution is adjusted to 4 by using dilute sulfuric acid;
(6) and passivating: firstly, heating the passivation solution to 65 ℃, and then soaking the rolled copper foil plated with the zinc-nickel alloy in the passivation solution for passivation for 3 min;
the passivation solution comprises 50g/L of chromium chloride, 125g/L of sodium nitrate and 50g/L of sodium fluoride, and the pH of the plating solution is adjusted to 2 by nitric acid;
(7) and (3) treating by using a silane coupling agent: and (3) soaking the passivated rolled aluminum foil into 10% silane coupling agent alcohol solution, wherein the silane coupling agent is mainly silane coupling agent KH560, taking out after 1min, and finally drying by using hot air at 150 ℃.
And (3) performance testing:
firstly, measuring the peel strength:
experiment design:
the rolled copper foils prepared in examples 1 to 7 and comparative examples were press-fitted with a resin substrate by a laminator to prepare copper clad laminates using examples 1 to 7 and comparative examples as experimental groups, then the peel strength (N/mm) between the rolled copper foils and the resin substrate in examples and comparative examples was tested by a tensile tester, the minimum load (Lm, N) value and the tested sample width (Ws, mm) were recorded, 3 repetitions of measurement were conducted for each experimental group, and the average minimum load (Lm, N) value and the average tested sample width (Ws, mm) were taken as final results.
The peel strength (N/mm) was calculated as follows:
peel strength (N/mm) minimum load (Lm)/width of specimen to be tested (Ws)
The experimental results are as follows:
as can be seen from the results of the peel strength test of the rolled copper foils of examples 1 to 7 and comparative example, the peel strength (N/mm) of the rolled copper foils of examples 1 to 7 was 2.09 to 2.23, while the peel strength (N/mm) of the rolled copper foils of comparative example was 1.57, indicating that the rolled copper foils obtained using the present invention had better peel strength and better adhesion to the substrate.
Table for measuring peel strength of rolled copper foils in examples 1 to 7 and comparative example
Group of Peel strength (N/mm)
Example 1 2.15
Example 2 2.23
Example 3 2.09
Example 4 2.17
Example 5 2.22
Example 6 2.19
Example 7 2.17
Comparative example 1.57
(II) corrosion resistance test (salt spray test):
experiment design:
the rolled copper foils prepared in examples 1-7 and comparative examples are used as experimental groups respectively, corrosion resistance tests are carried out on the rolled copper foils of the experimental groups by using a circulating corrosion test box, each experimental group is tested for three times, a 5% sodium chloride solution is adopted for carrying out a spraying experiment under the conditions that the temperature is 33-37 ℃ and the pH value is 6.5-7.2, the experiment is carried out for 1 time every 3 hours, whether the corrosion phenomenon occurs in a sample is checked, if the corrosion phenomenon is observed, the experiment is stopped immediately, and the corrosion time is recorded.
The experimental results are as follows:
it was found by the corrosion resistance test experiments that the rolled copper foil of the comparative example showed slight corrosion and small and irregular white rust on the copper foil at 119h, whereas the rolled copper foils of examples 1 to 7 showed no corrosion, and thus the rolled copper foil obtained by the present invention had better corrosion resistance.
(III) testing heat resistance:
experiment design:
the rolled copper foils prepared in examples 1 to 7 and comparative example were used as test groups, and the copper foils of each test group were immersed in solder solutions at 288 ℃, 300 ℃ and 350 ℃ for 1min, and after being taken out, the test samples were observed to see if blistering was observed, and the test was repeated three times for each test group.
The experimental results are as follows:
through a heat resistance test experiment, the rolled copper foils prepared in examples 1-7 and comparative example have no bubble phenomenon after being soaked in the soldering tin liquid at 288 ℃ and 300 ℃ for 1 min; however, after soaking in the solder solution at 350 ℃ for 1min, the rolled copper foil in the comparative example generates obvious bubbling, while the rolled copper foils in examples 1-7 do not generate bubbling, so that the rolled copper foil obtained by the invention has better heat resistance which is far higher than the market standard (288 ℃).
(IV) surface roughness measurement:
experiment design:
the surface roughness (Ra) of the rolled copper foil is an arithmetic mean value of absolute distances between the top peak and the bottom valley of the surface of a sample to be measured, and is an important parameter for reflecting the surface profile characteristics of the sample, and the lower the surface roughness is, the more favorable the circuit with low dielectric loss is manufactured. In this experiment, rolled copper foils prepared in examples 1 to 7 and comparative example were used as test groups, and surface roughness measurements were performed on rolled copper foil samples of each test group using a surface roughness measuring instrument, 5 points were randomly selected on the surface of the copper foil sample for measurement, and the height values of the top and bottom of the peak at each point were recorded, and the surface roughness (R) of the copper foil was obtained by calculating the average of the 5 measurements.
The experimental results are as follows:
as can be seen from the results of measuring the surface roughness (Ra) of the rolled copper foils of examples 1 to 7 and comparative example, the surface roughness (Ra) of the rolled copper foils of examples 1 to 7 was 0.96 to 1.11, while the surface roughness (Ra) of the rolled copper foils of comparative example was 1.57, which indicates that the rolled copper foils obtained by the present invention had lower surface roughness and could satisfy the signal transmission requirements of high-end high-frequency printed circuits.
Measurement Table of surface roughness (Ra) of rolled copper foils in examples 1 to 7 and comparative example
Group of Surface roughness (Ra)
Example 1 1.11
Example 2 0.96
Example 3 1.07
Example 4 1.04
Example 5 1.03
Example 6 1.09
Example 7 1.07
Comparative example 1.57
The embodiments of the present invention have been described in detail, but the present invention is not limited to the described embodiments. It will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, and the scope of protection is still within the scope of the invention.

Claims (9)

1. A surface treatment process of rolled copper foil is characterized in that: the method comprises the following steps:
s1, cleaning: soaking the rolled copper foil in a cleaning solution for cleaning, taking out the rolled copper foil, cleaning the rolled copper foil for three times by using hot water at the temperature of 50-80 ℃, and airing for later use;
the cleaning solution comprises the following components in percentage by weight:
15-20% of anionic surfactant, 10-15% of nonionic surfactant, 8-12% of sulfuric acid, 1-3% of solubilizer, 1-3% of builder and 47-65% of pure water;
s2, first coarsening: adding a roughening solution into the electroplating rectifier at a current density of 15-20A/dm2Electroplating 12-18S on the rolled copper foil at the temperature of 30-40 ℃;
the coarsening liquid comprises 15-25g/L copper sulfate, 60-80 g/L sulfuric acid, 3-5g/L ferric sulfite and 1-3g/L nickel sulfate;
s3, first curing: adding a curing liquid into the electroplating rectifier at a current density of 15-20A/dm2Electroplating the rolled copper foil for 8-15S at the temperature of 45-55 ℃;
the curing liquid comprises 60-70g/L copper sulfate, 90-100 g/L sulfuric acid and 2-3g/L lecithin;
s4, secondary coarsening: adding the roughening solution in the first roughening step into an electroplating rectifier, wherein the current density is 8-12A/dm2Electroplating the rolled copper foil for 7-10S at the temperature of 20-30 ℃;
s5, secondary curing: adding the curing liquid in the first curing step into an electroplating rectifier, wherein the current density is 12-15A/dm2Electroplating the rolled copper foil for 5-10S at the temperature of 35-40 ℃;
s6, nickel-lanthanum alloy plating: adding a nickel-lanthanum alloy plating solution into an electroplating rectifier at a current density of 10-20A/dm2Electroplating 30-50S on the rolled copper foil at the temperature of 50-65 ℃;
the nickel-lanthanum alloy plating solution comprises 35-45g/L nickel sulfamate, 20-30g/L lanthanum chloride, 3-5g/L urea and 2-3g/L sodium pyrophosphate, and the PH of the plating solution is adjusted to 3-6 by using citric acid;
s7, tungsten-zinc alloy plating: adding a tungsten-zinc alloy plating solution into an electroplating rectifier at a current density of 5-10A/dm2Electroplating 15-25S on the rolled copper foil at the temperature of 40-50 ℃;
the tungsten-zinc alloy plating solution comprises 20-30g/L of sodium tungstate, 10-15g/L of zinc nitrate, 1-2g/L of sodium dodecyl sulfate and 2-3g/L of stabilizer, and the pH value is adjusted to 3-5 by using boric acid solution;
s8, passivation: firstly heating the passivation solution to 40-50 ℃, and then soaking the rolled copper foil in the passivation solution for passivation for 25-35 s;
the passivation solution comprises 6-10g/L of titanium trichloride, 8-12g/L of phytic acid, 8-15mL/L of hydrogen peroxide and 10-18g/L of sodium hexametaphosphate, and the pH of the passivation solution is adjusted to 1-3 by nitric acid;
s9, drying: placing the passivated rolled copper foil in an oven at 50-60 ℃ to dry for 8-10 h;
s10, silane coupling agent treatment: preparing 3-5% of silane coupling agent alcohol solution by using absolute ethyl alcohol, then soaking the dried rolled aluminum foil into the silane coupling agent alcohol solution, taking out the rolled aluminum foil after 10-15s, and finally curing the rolled aluminum foil for 1-3h at the temperature of 70-80 ℃ to finish the surface treatment work of the rolled copper foil.
2. The surface treatment process of a rolled copper foil according to claim 1, characterized in that: and in the step S1, soaking the rolled copper foil in the cleaning solution for three times for cleaning, wherein the soaking time is 1-2min, and the cleaning time is three times after the soaking time is finished by using hot water at 50-80 ℃.
3. The surface treatment process of a rolled copper foil according to claim 1, characterized in that: the anionic surfactant is any one of sodium dodecyl benzene sulfonate, sodium stearate, lauryl alcohol, vinyl ether and glyceride.
4. The surface treatment process of a rolled copper foil according to claim 1, characterized in that: the nonionic surfactant is any one of fatty alcohol-polyoxyethylene ether, coconut oil fatty acid diethanolamide, alkylphenol ethoxylates and fatty acid-polyoxyethylene ester.
5. The surface treatment process of a rolled copper foil according to claim 1, characterized in that: the solubilizer is any one of ethanol, isopropanol and butanol.
6. The surface treatment process of a rolled copper foil according to claim 1, characterized in that: the builder is any one of sodium pyrophosphate, potassium pyrophosphate, sodium nitrite, sodium benzoate and sodium sulfate.
7. The surface treatment process of a rolled copper foil according to claim 1, characterized in that: the stabilizing agent in the step S7 is sodium citrate.
8. The surface treatment process of a rolled copper foil according to claim 1, characterized in that: before the passivation of the step S9, the rolled copper foil plated with the tungsten-zinc alloy is immersed in warm water at 45-55 ℃ and washed three times.
9. The surface treatment process of a rolled copper foil according to claim 1, characterized in that: the silane coupling agent is a silane coupling agent kh 550.
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