A surface treatment process for electrolytic copper foil

Abstract

The present application relates to the technical field of electrolytic copper foil, in particular to a surface treatment process of electrolytic copper foil; in the present application, a coupling agent is added to a chlorinated thiamine pyrophosphate aqueous solution, and then a glutaraldehyde aqueous solution is added thereto while stirring after temperature rising treatment; then, the reaction product is completely evaporated after heat preservation reaction; finally, the reaction occurs cross-linking reaction under the "bridge" effect of the coupling agent, and the obtained solid powder is mixed with acetone to prepare a surface layer antioxidant liquid; the copper foil is immersed in the prepared surface layer antioxidant liquid, so that a dense antioxidant protective film layer is formed on the surface of the copper foil, and the antioxidant performance of the electrolytic copper foil is effectively improved; finally, under the synergistic effect of the surface layer antioxidant liquid and the organic protective agent, not only the antioxidant performance of the electrolytic copper foil is further ensured, but also the wear resistance of the electrolytic copper foil is improved, and the service life of the electrolytic copper foil is prolonged to a certain extent, and the quality of the electrolytic copper foil is significantly improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of electrolytic copper foil, in particular to a surface treatment process of electrolytic copper foil. BACKGROUND

[0002] Electrolytic copper foil refers to the copper raw material is made into copper sulfate solution, and then the solution is deposited into copper foil under the action of direct current by using electrolytic equipment. The electrolytic copper foil is an important material for manufacturing copper-clad plate (CCL), printed circuit board (PCB) and lithium ion battery. According to the thickness of the copper foil, it can be divided into ultra-thin copper foil (≤6m), super-thin copper foil (6-12m), thin copper foil (12-18m), conventional copper foil (18-70m) and thick copper foil (>70m) according to the prevailing standard. According to the surface condition, it can be divided into double-sided bright copper foil, double-sided rough copper foil, double-sided treated copper foil, single-sided rough copper foil and low profile copper foil (RTF copper foil, VLP copper foil, HVLP copper foil) and the like.

[0003] In the patent document with the application number "CN200710126403.0", a surface treatment electrolytic copper foil and its manufacturing method and circuit substrate are disclosed. In the surface treatment electrolytic copper foil, the M surface opposite to the surface of the electrolytic copper foil in contact with the drum is subjected to surface treatment, the Rz of the M surface is below 1.0 μm, and the Ra is below 0.2 μm. The surface treatment electrolytic copper foil is manufactured by the following surface treatment electrolytic copper foil manufacturing method: using copper sulfate bath to perform copper plating electrolysis under the condition of current density of 20-50 A / dm2 to manufacture copper foil.

[0004] Although the electrolytic copper foil prepared by the above patent document has the advantages of smooth surface and easy identification, its own oxidation resistance and wear resistance are relatively poor, which to some extent affects the service life of the electrolytic copper foil, and also affects its quality and quality. Based on this, the present application provides a surface treatment process of electrolytic copper foil. SUMMARY

[0005] The purpose of the present application is to provide a surface treatment process of electrolytic copper foil. The treated electrolytic copper foil not only has excellent oxidation resistance, but also has excellent wear resistance, which prolongs the service life of the electrolytic copper foil to some extent and significantly improves its quality.

[0006] To achieve the above-mentioned purpose, the present application provides the following technical scheme:

[0007] A surface treatment process of electrolytic copper foil, comprising the following steps:

[0008] Step one, the copper foil is placed in a degreasing tank, and a sodium hydroxide solution with a temperature of 55-65℃ and a concentration of 60-75g / L is added to the tank for cleaning and degreasing; after degreasing, the copper foil is washed with water, then the copper foil is pickled, and after pickling, the copper foil is placed in a water washing tank for surface cleaning;

[0009] Step two, the copper foil treated in step one is placed in a roughening tank for roughening treatment, and after roughening, the copper foil is washed with water in a water washing tank; wherein the concentration of Cu 2+ in the roughening tank is 15-30g / L, the concentration of H2SO4 is 130-150g / L, the temperature is 30-45℃, and the electrolyte flow rate is 13-18m 3 / h;

[0010] Step three, the copper foil treated in step two is placed in a solidification tank for solidification treatment, and after solidification, the copper foil is washed with water in a water washing tank; wherein the concentration of Cu 2+ in the solidification tank is 55-75g / L, the concentration of H2SO4 is 110-130g / L, the temperature is 30-50℃, and the electrolyte flow rate is 15-20m 3 / h;

[0011] Step four, the solidified copper foil is placed in a barrier layer treatment tank, and a Zn-Ni-K ternary alloy treatment process is used to form a barrier layer on the surface of the copper foil; after water washing, the copper foil is immersed in a surface layer antioxidant liquid with a temperature of 50-65℃ for 5-10min;

[0012] Step five, after immersion, the copper foil is taken out and washed with absolute ethanol, then the copper foil is transferred to a vacuum drying oven, and vacuum drying treatment is carried out at a temperature of 70-90℃;

[0013] Step six, after vacuum drying, the copper foil surface is evenly sprayed with an organic protective agent, and it is dried at a temperature of 60-80℃; after drying, the copper foil is cut and packaged in sequence; finally, the surface treatment process of the electrolytic copper foil is completed.

[0014] Further, the acid solution used in step one is a sulfuric acid solution with a concentration of 110-130g / L, and the temperature is 30-50℃.

[0015] Further, in step two, the roughening current is set to 2900-3200A, and the roughening time is set to 4-7s.

[0016] Further, in step three, the solidification current is set to 2300-2700A, and the solidification time is set to 5-8s.

[0017] Further, the step four in forming the barrier layer, Zn 2+ concentration of 2-3 g / L, Ni 2+ concentration of 1.5-2 g / L, K + concentration of 90-110 g / L.

[0018] Further, the preparation method of the surface layer antioxidant solution is as follows: 0.4-0.5 times the mass of thiamine pyrophosphate chloride in 35-45 g / L thiamine pyrophosphate chloride aqueous solution is added with a coupling agent, the mixture is uniformly stirred and heated to 75-85℃, then 1.5-2.5 times the mass of the coupling agent with 20-25% glutaraldehyde aqueous solution is slowly added dropwise to the mixture while stirring; after the addition is completed, the reaction is kept for 4-6 h, and after the reaction is completed, the liquid in the reaction product is completely evaporated, the obtained solid powder is put into 7-10 times the mass of acetone, the mixture is uniformly stirred, and the surface layer antioxidant solution is obtained.

[0019] Further, the coupling agent is selected from any one of γ-aminopropyl trimethoxysilane, N-(β-aminoethyl)-γ-aminopropyl methyldimethoxysilane and γ-aminopropyl methyldiethoxysilane.

[0020] Further, the preparation method of the organic protective agent comprises the following steps:

[0021] First step, 0.6-0.8 times the mass of ethylene glycol is put into 4-6 wt% butanol aldehyde ethyl ether solution, concentrated hydrochloric acid is added to the mixture, the obtained mixture is reacted at 120-130℃ for 8-12 h, after the reaction is completed, the obtained product is rotary evaporated, and the reaction product is stored and used;

[0022] Second step, 1.05-1.1 times the mass of the reaction product is added to 0.05-0.08 g / mL 5-methyl-1H-benzotriazole trichloromethane solution, the temperature is increased to 60-70℃, and the mixture is stirred to dissolve, then 1.4-1.5 times the mass of toluene-2, 4-diisocyanate is slowly added dropwise to the mixture while stirring, after the addition is completed, the reaction is kept for 50-70 min;

[0023] Third step, after the reaction is completed, 30-40% of the volume of the product with 2-4 mol / L hydrochloric acid aqueous solution is added, and the mixture is kept at 45-55℃ for 5-7 h; after the reaction is completed, the product is rotary evaporated, then the obtained liquid composition is mixed with anhydrous ethanol at a volume ratio of 1:4-6, and the mixture is uniformly stirred to obtain the organic protective agent.

[0024] Further, the concentration of the concentrated hydrochloric acid in the first step is 36-38 wt%, and the amount of concentrated hydrochloric acid is 0.4-0.5 times the volume of the ether.

[0025] Compared with the prior art, the present application has the following advantages:

[0026] 1. In the present application, a coupling agent is added to a chlorinated thiamine pyrophosphate aqueous solution, and then a glutaraldehyde aqueous solution is added thereto under stirring after temperature rising. The reaction product is completely evaporated, and finally the cross-linking reaction of the reactants is carried out under the bridging action of the coupling agent. The obtained solid powder is mixed with acetone to prepare a surface layer antioxidant. The copper foil is immersed in the prepared surface layer antioxidant, and a dense antioxidant protective film layer is formed on the surface of the copper foil, which can effectively improve the antioxidant performance of the electrolytic copper foil.

[0027] 2. In the present application, ethylene glycol is added to the butanol aldehyde ether solution, and then concentrated hydrochloric acid is added after uniform mixing and stirring. The obtained reaction product is added to the 5-methyl-1H-benzotriazole chloroform solution, and toluene-2,4-diisocyanate is slowly added thereto under stirring. Hydrochloric acid aqueous solution is added to the obtained product composition after temperature rising reaction, and then the obtained liquid composition is uniformly mixed with anhydrous ethanol to finally prepare an organic protective agent. The prepared organic protective agent is uniformly sprayed on the surface of the copper foil, which can react with the exposed copper metal and form a protective film on the surface of the copper foil. Finally, under the synergistic effect of the surface layer antioxidant and the organic protective agent, not only the antioxidant performance of the electrolytic copper foil is further ensured, but also the wear resistance of the electrolytic copper foil is improved, which prolongs the service life of the electrolytic copper foil and significantly improves its quality. DETAILED DESCRIPTION

[0028] The technical solutions in the embodiments of the present application will be clearly and completely described below in combination with the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0029] Embodiment 1

[0030] A surface treatment process of an electrolytic copper foil, comprising the following steps:

[0031] Step one, the copper foil is placed in the degreasing tank, and a sodium hydroxide solution with a temperature of 55℃ and a concentration of 60g / L is added to the tank for cleaning and degreasing; after degreasing, the copper foil is washed with water, then the copper foil is pickled, after pickling, the copper foil is placed in the water washing tank for surface cleaning; the acid solution used is a sulfuric acid solution with a concentration of 110g / L, and the temperature is 30℃;

[0032] Step two, the copper foil treated in step one is placed in the roughening tank for roughening treatment, and after roughening, the copper foil is washed with water in the water washing tank; the concentration of Cu 2+ in the roughening tank is 15g / L, the concentration of H2SO4 is 130g / L, the temperature is 30℃, and the electrolyte flow rate is 13m 3 / h; wherein, during the roughening treatment of the copper foil, the roughening current is set to 2900A, and the roughening time is set to 4s;

[0033] Step three, the copper foil treated in step two is placed in the solidification tank for solidification treatment, and after solidification, the copper foil is washed with water in the water washing tank; the concentration of Cu 2+ in the solidification tank is 55g / L, the concentration of H2SO4 is 110g / L, the temperature is 30℃, and the electrolyte flow rate is 15m 3 / h; wherein, during the solidification treatment of the copper foil, the solidification current is set to 2300A, and the solidification time is set to 5s;

[0034] Step four, the solidified copper foil is placed in the barrier layer treatment tank, and a Zn-Ni-K ternary alloy treatment process is used to form a barrier layer on the surface of the copper foil; after water washing, the copper foil is immersed in a surface layer antioxidant liquid with a temperature of 50℃ for 10min; wherein, during the formation of the barrier layer, the concentration of Zn 2+ is 2g / L, the concentration of Ni 2+ is 1.5g / L, and the concentration of K + is 90g / L;

[0035] Step five, after the immersion is completed, the copper foil is taken out and washed with absolute ethanol, then the copper foil is transferred to a vacuum drying oven, and vacuum drying treatment is carried out at a temperature of 70℃;

[0036] Step six, after vacuum drying is completed, the copper foil surface is evenly sprayed with an organic protective agent, and it is dried at a temperature of 60℃; after drying is completed, the copper foil is sequentially cut and packaged; finally, the surface treatment process of the electrolytic copper foil is completed.

[0037] The preparation method of the surface antioxidant solution is as follows: 0.4 times the mass of the thiocyanate pyrophosphate chloride in 35 g / L thiocyanate pyrophosphate chloride aqueous solution is added with γ-aminopropyltrimethoxysilane, and the mixture is stirred uniformly and heated to 75°C, then 1.5 times the mass of the γ-aminopropyltrimethoxysilane, 20% glutaraldehyde aqueous solution is slowly added dropwise to the obtained mixture while stirring; after the addition is completed, the reaction is kept for 4 h, and after the reaction is completed, the liquid in the reaction product is completely evaporated, and the obtained solid powder is put into 7 times the mass of acetone, and the mixture is stirred uniformly to obtain the surface antioxidant solution.

[0038] The preparation method of the organic protective agent comprises the following steps:

[0039] Step 1: 0.6 times the mass of ethylene glycol is added to 4 wt% butanol aldehyde ethyl ether solution, and concentrated hydrochloric acid is added to the mixture, and the obtained mixture is reacted at 120°C for 8 h, and after the reaction is completed, the obtained product is rotary evaporated, and the obtained reaction product is stored for use; wherein the concentration of the concentrated hydrochloric acid is 36 wt%, and the amount of the concentrated hydrochloric acid is 0.4 times the volume of the ethyl ether;

[0040] Step 2: 1.05 times the mass of the reaction product is added to 0.05 g / mL 5-methyl-1H-benzotriazole trichloromethane solution, and the temperature is raised to 60°C to fully dissolve the mixture, then 1.4 times the mass of the 5-methyl-1H-benzotriazole, toluene-2,4-diisocyanate is slowly added dropwise to the mixture while stirring, and after the addition is completed, the reaction is kept for 50 min;

[0041] Step 3: after the reaction is completed, 30% by volume of the product, 2 mol / L hydrochloric acid aqueous solution is added to the obtained product, and the reaction is kept at 45°C for 5 h; after the reaction is completed, the product is rotary evaporated; then the obtained liquid composition is mixed with anhydrous ethanol at a volume ratio of 1:4, and the mixture is uniformly stirred by mechanical stirring to obtain the organic protective agent.

[0042] Example 2

[0043] A surface treatment process for electrolytic copper foil comprises the following steps:

[0044] Step 1: the copper foil is placed in a degreasing tank, and a 70 g / L sodium hydroxide aqueous solution with a temperature of 60°C is added to the tank to clean and degrease the copper foil; after degreasing, the copper foil is washed with water, then the copper foil is pickled, and after pickling, the copper foil is placed in a water washing tank to clean the surface of the copper foil; wherein the acid solution used is a 120 g / L sulfuric acid aqueous solution, and the temperature thereof is 40°C;

[0045] Step 2: the copper foil treated in step 1 is placed in a roughening tank for roughening treatment, and after roughening, the copper foil is washed with water in a water washing tank; wherein the concentration of Cu2+ CuSO4 concentration is 25g / L, H2SO4 concentration is 140g / L, temperature is 40℃, electrolyte flow is 15m 3 / h; wherein, when roughening the copper foil, roughening current is set to 3000A, roughening time is set to 5s;

[0046] Step three, the copper foil after roughening treatment in step two is placed in a solidification tank for solidification treatment, and after solidification is completed, the copper foil is placed in a water washing tank for water washing; wherein, Cu 2+ concentration in the solidification tank is 65g / L, H2SO4 concentration is 120g / L, temperature is 40℃, electrolyte flow is 15m 3 / h; wherein, when solidifying the copper foil, solidification current is set to 2500A, solidification time is set to 6s;

[0047] Step four, the solidified copper foil is placed in a barrier layer processing tank, and a Zn-Ni-K ternary alloy processing process is used to form a barrier layer on the surface of the copper foil; after water washing, the copper foil is immersed in a surface layer antioxidant liquid at a temperature of 60℃ for 8min; wherein, when forming the barrier layer, Zn 2+ concentration is 2.5g / L, Ni 2+ concentration is 1.5g / L, K + concentration is 100g / L;

[0048] Step five, after the immersion is completed, the copper foil is fished out and washed clean with anhydrous ethanol, and then the copper foil is transferred into a vacuum drying oven and vacuum dried at a temperature of 80℃;

[0049] Step six, after the vacuum drying is completed, the copper foil surface is evenly sprayed with an organic protective agent and dried at a temperature of 70℃; after drying is completed, the copper foil is sequentially subjected to slitting and packaging treatment; finally, the surface treatment process of the electrolytic copper foil is completed.

[0050] The preparation method of the surface layer antioxidant liquid is as follows: 0.45 times the mass of the thiocyanate pyrophosphoric acid chloride aqueous solution is added to 40g / L of thiocyanate pyrophosphoric acid chloride aqueous solution, uniformly mixed and stirred, heated to 80℃, and then 2 times the mass of N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane and 20% glutaraldehyde aqueous solution with a concentration of 20% are slowly added to the obtained mixed solution while stirring; after the addition is completed, the reaction is maintained for 5h, and after the reaction is completed, the liquid in the reaction product is completely evaporated, the obtained solid powder is put into 8 times the mass of acetone, uniformly mixed and stirred, and the surface layer antioxidant liquid is obtained.

[0051] The preparation method of the organic protective agent includes the following steps:

[0052] The first step, to 5wt% butyl alcohol aldehyde in diethyl ether solution into the mass of butyl alcohol aldehyde 0.7 times of ethylene glycol, after mixing and stirring uniform to which add concentrated hydrochloric acid, the resulting mixture is reacted at 125℃ temperature for 10h, after the reaction is completed, the resulting product components are rotary evaporated, the resulting reaction product is preserved, ready for use; wherein, the concentration of concentrated hydrochloric acid is 36wt%, and the amount of concentrated hydrochloric acid is 0.45 times the volume of diethyl ether;

[0053] The second step, to 0.06g / mL 5-methyl-1H-benzotriazole in chloroform solution is added to the mass of 1.05 times of the reaction product, the temperature is raised to 65℃ stirring to make it fully dissolved, then slowly drop into the mass of 1.45 times of toluene-2, 4-diisocyanate in 5-methyl-1H-benzotriazole while stirring, after the drop is completed, incubation reaction for 60min;

[0054] The third step, after the reaction is completed, the resulting product components are added to the volume of 35% of its, the concentration of 3mol / L hydrochloric acid aqueous solution, and incubated at 50℃ temperature for 6h; after the reaction is completed, the product components are rotary evaporated; then the resulting liquid composition is mixed with anhydrous ethanol at a volume ratio of 1:5, after mechanical stirring uniform, the organic protective agent is obtained.

[0055] Example 3

[0056] An electrolytic copper foil surface treatment process, comprising the following steps:

[0057] Step one, the copper foil is placed in the degreasing tank, and a sodium hydroxide aqueous solution with a temperature of 65℃ and a concentration of 75g / L is added to the tank for cleaning and degreasing; after degreasing, the copper foil is washed with water, and then the copper foil is pickled; after pickling, the copper foil is placed in a water washing tank for surface cleaning; wherein the acid solution used in step one is a sulfuric acid aqueous solution with a concentration of 130g / L, and the temperature is 50℃;

[0058] Step two, the copper foil treated in step one is placed in a roughening tank for roughening treatment, and after roughening, the copper foil is washed with water in a water washing tank; wherein the concentration of Cu 2+ in the roughening tank is 30g / L, the concentration of H2SO4 is 150g / L, the temperature is 45℃, and the electrolyte flow rate is 18m 3 / h; wherein, during the roughening treatment of the copper foil, the roughening current is set to 3200A, and the roughening time is set to 7s;

[0059] Step three, the copper foil treated in step two is placed in a solidification tank for solidification treatment, and after solidification, the copper foil is washed with water in a water washing tank; wherein the concentration of Cu 2+ in the solidification tank is 75g / L, the concentration of H2SO4 is 130g / L, the temperature is 50℃, and the electrolyte flow rate is 20m 3 / h; wherein, when the copper foil is subjected to the solidification treatment, the solidification current is set to 2700A, and the solidification time is set to 8s;

[0060] Step four, the solidified copper foil is placed in a barrier layer processing tank, and a Zn-Ni-K ternary alloy processing process is used to form a barrier layer on the surface of the copper foil; after water washing treatment, the copper foil is immersed in a surface layer antioxidant liquid at a temperature of 65°C for 10 min; wherein, in step four, when the barrier layer is formed, the Zn 2+ concentration is 3g / L, the Ni 2+ concentration is 2g / L, and the K + concentration is 110g / L.

[0061] Step five, after the immersion is completed, the copper foil is fished out and washed clean with anhydrous ethanol, and then the copper foil is transferred into a vacuum drying oven and subjected to vacuum drying treatment at a temperature of 90°C.

[0062] Step six, after the vacuum drying is completed, an organic protective agent is uniformly sprayed on the surface of the copper foil, and the copper foil is dried at a temperature of 80°C; after the drying is completed, the copper foil is subjected to slitting and packaging treatment in sequence; finally, the surface treatment process of the electrolytic copper foil is completed.

[0063] The preparation method of the surface layer antioxidant liquid is as follows: 0.5 times the mass of thiamine chloride pyrophosphate in 45g / L thiamine chloride pyrophosphate aqueous solution is added with γ-aminopropylmethyldiethoxysilane, and after uniform mixing and stirring, the temperature is raised to 85°C, and then 2.5 times the mass of γ-aminopropylmethyldiethoxysilane, 25% glutaraldehyde aqueous solution is slowly added dropwise to the obtained mixture while stirring; after the addition is completed, the reaction is kept for 6h, and after the reaction is completed, the liquid in the reaction product is completely evaporated, and the obtained solid powder is put into 10 times the mass of acetone, and after uniform mixing and stirring, the surface layer antioxidant liquid is obtained.

[0064] The preparation method of the organic protective agent includes the following steps:

[0065] First step, 0.8 times the mass of ethylene glycol is put into 6wt% butanol aldehyde ethyl ether solution, and after uniform mixing and stirring, concentrated hydrochloric acid is added, and the obtained mixture is reacted at a temperature of 130°C for 12h, and after the reaction is completed, the obtained product is rotary evaporated, and the obtained reaction product is preserved for use; wherein, the concentration of the concentrated hydrochloric acid is 38wt%, and the amount of the concentrated hydrochloric acid is 0.5 times the volume of the ethyl ether.

[0066] Second step, 1.1 times the mass of the reaction product is added to 0.08g / mL 5-methyl-1H-benzotriazole trichloromethane solution, the temperature is raised to 70°C for stirring to fully dissolve, and then 1.5 times the mass of toluene-2,4-diisocyanate is slowly added dropwise to the obtained mixture while stirring, and after the addition is completed, the reaction is kept for 70min.

[0067] The third step, after the reaction is completed, add the hydrochloric acid solution with the volume of 40% of the product and the concentration of 4mol / L, and keep the temperature at 55℃ for 7h. After the reaction is completed, spin the product. Then mix the liquid composition with the volume ratio of 1:6 with the anhydrous ethanol, and get the organic protective agent after the mechanical stirring.

[0068] The difference between the example 1 and the comparative example 1 is that the copper foil is not immersed in the surface layer antioxidant liquid in the example 1.

[0069] The difference between the example 1 and the comparative example 2 is that the copper foil is not sprayed with the organic protective agent in the example 2.

[0070] Performance test: the electrolytic copper foil samples treated by the examples 1-3 and the comparative examples 1-2 are placed on the same rough surface, and the same pressure and tension are applied for 50 times, 80 times and 100 times. Then the copper foils are placed in the humid oxygen (temperature is 25℃ and humidity is 40%) for 7 days. Then the changes of the copper foil surface are observed. The test data are recorded in the following table:

[0071]

[0072] According to the comparison and analysis of the data in the table, the electrolytic copper foil treated by the application has excellent oxidation resistance and excellent wear resistance, which prolongs the service life of the electrolytic copper foil and improves the quality of the electrolytic copper foil. Therefore, the electrolytic copper foil surface treatment process provided by the application has a broader market prospect and is more suitable for promotion.

[0073] In the description of the present specification, the description of the terms "one embodiment", "example", "specific example" and the like means that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present application. In the present specification, the illustrative description of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0074] The preferred embodiments of the application disclosed above are only to facilitate the elucidation of the application. The preferred embodiments do not describe all the details of the application and limit the application to the specific embodiments described. Obviously, many modifications and variations can be made in light of the teachings above. The description is chosen and described in order to best explain the principles of the application and its practical application to thereby enable others skilled in the art to best utilize the application and get the best results from the application. The application is only limited by the claims and their full scope and equivalents.

Claims

1. An electrolytic copper foil surface treatment process characterized by, It comprises the following steps: Step one, the copper foil is placed in the degreasing tank, and a sodium hydroxide solution with a temperature of 55-65℃ and a concentration of 60-75g / L is added to the tank for cleaning and degreasing; after degreasing, the copper foil is washed with water, then pickled, and after pickling, the copper foil is placed in the water washing tank for surface cleaning; Step two, the copper foil treated in step one is placed in a roughening tank for roughening treatment, and after the roughening is completed, the copper foil is placed in a water washing tank for water washing; wherein the concentration of Cu in the roughening tank is 18-23 g / L, the concentration of H2SO4 is 140-145 g / L, the temperature is 30-40 ℃, and the electrolyte flow is 13-18 m3 / h; 2+ ​ Step three, the copper foil after the roughening treatment in step two is placed in a solidification tank for solidification treatment, and after the solidification is completed, the copper foil is placed in a water washing tank for water washing; wherein the concentration of Cu 2+ in the solidification tank is 60-65 g / L, the concentration of H2SO4 is 120-125 g / L, the temperature is 30-50°C, and the electrolyte flow is 15-20 m3 / h; Step four, the solidified copper foil is placed in the barrier layer processing tank, and a Zn-Ni-K ternary alloy processing process is used to form a barrier layer on the surface of the copper foil; after water washing, the copper foil is immersed in a surface layer antioxidant liquid with a temperature of 50-60℃ for 5-10min; Step five, after immersion, the copper foil is taken out and washed with anhydrous ethanol, then the aluminum foil is transferred to a vacuum drying oven and vacuum dried at a temperature of 70-85℃; Step six, after vacuum drying, the aluminum foil surface is evenly sprayed with an organic protective agent and dried at a temperature of 60-70℃; after drying, the copper foil is cut and packaged in sequence; finally, the surface treatment process of the electrolytic copper foil is completed; The preparation method of the surface layer antioxidant liquid is as follows: 35-45g / L of a chlorothionamide pyrophosphate aqueous solution is added with a coupling agent with a mass of 0.4-0.5 times that of the chlorothionamide pyrophosphate, and after uniform mixing and stirring, the temperature is raised to 75-85℃, then 1.5-2.5 times the mass of the coupling agent, i.e. 20-25% glutaraldehyde aqueous solution, is slowly added dropwise to the mixture while stirring; after the addition is completed, the reaction is kept for 4-6h, and after the reaction is completed, the liquid in the reaction product is completely evaporated, and the obtained solid powder is put into 7-10 times the mass of acetone, and after uniform mixing and stirring, the surface layer antioxidant liquid is obtained; The preparation method of the organic protective agent comprises the following steps: First step, 4-6wt% butanol aldehyde ethyl ether solution is added with 0.6-0.8 times the mass of ethylene glycol, concentrated hydrochloric acid is added to the mixture, and the obtained mixture is reacted at a temperature of 120-130℃ for 8-12h; after the reaction is completed, the obtained product is rotary evaporated, and the reaction product is stored for use; Second step, 0.05-0.08g / mL 5-methyl-1H-benzotriazole trichloromethane solution is added with 1.05-1.1 times the mass of the reaction product, the temperature is raised to 60-70℃ for stirring to fully dissolve, then 1.4-1.5 times the mass of toluene-2, 4-diisocyanate is slowly added dropwise to the mixture while stirring; after the addition is completed, the reaction is kept for 50-70min; Third step, after the reaction is completed, 30-40% of the volume of the obtained product, i.e. 2-4mol / L hydrochloric acid aqueous solution, is added, and the reaction is kept at a temperature of 45-55℃ for 5-7h; after the reaction is completed, the product is rotary evaporated; then the obtained liquid composition is mixed with anhydrous ethanol at a volume ratio of 1:4-6, and after uniform mechanical stirring, the organic protective agent is obtained.

2. The surface treatment process of an electrolytic copper foil according to claim 1, characterized by: The acid solution used in step one is 120-130g / L sulfuric acid aqueous solution, and the temperature is 30-40℃.

3. The surface treatment process of an electrolytic copper foil according to claim 1, characterized by: In the second step, the roughening current is set to 2900-3200 A, and the roughening time is set to 4-7 s.

4. The surface treatment process of an electrolytic copper foil according to claim 1, characterized by: In the third step, the solidification current is set to 2300-2700 A, and the solidification time is set to 5-8 s.

5. The surface treatment process of an electrolytic copper foil according to claim 1, characterized by: In the step four, when forming the barrier layer, Zn 2+ concentration of 2-3 g / L, Ni 2+ concentration of 1.5-2 g / L, K + concentration of 90-110 g / L.

6. The process for surface treatment of electrolytic copper foil according to claim 1, wherein: The coupling agent is selected from any one of gamma-aminopropyltrimethoxysilane, N-(beta-aminoethyl)-gamma-aminopropylmethyldimethoxysilane and gamma-aminopropylmethyldiethoxysilane.

7. The process of claim 1, wherein: In the first step, the concentration of the concentrated hydrochloric acid is 36-38 wt%, and the amount of the concentrated hydrochloric acid is 0.4-0.5 times the volume of the ether.

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