Blackened electronic copper foil, preparation method and electronic product

Abstract

The invention relates to the technical field of electronic copper foils, in particular to a blackened electronic copper foil, a preparation method and an electronic product. The preparation method of the blackened electronic copper foil comprises the following steps: carrying out roughening treatment on the single-side surface of a raw foil to form a single-side roughened surface so as to obtain a roughened copper foil; adopting a blackening solution to perform blackening treatment on the single-side roughened surface of the roughened copper foil to obtain a blackened copper foil; the blackening solution comprises the following components: 15g / L to 30g / L of copper, 0.5 g / L to 2g / L of molybdenum, 80g / L to 150g / L of glucose, 0.5 g / L to 2g / L of citric acid and water; performing anti-oxidation treatment on the surfaces of the two sides of the blackened copper foil to obtain an anti-oxidation copper foil; and carrying out silane coating treatment on the single-side roughened surface of the anti-oxidation copper foil. According to the preparation method, the surface performance of the copper foil can be effectively improved, the contour height of the copper foil is reduced, and a good foundation is laid for subsequent treatment steps.

Description

Technical Field

[0001] The present disclosure relates to the technical field of electronic copper foil, and in particular to a blackened electronic copper foil, a preparation method thereof, and an electronic product. Background Art

[0002] With the rapid development of electronic technology, the performance requirements for electronic copper foil are getting higher and higher. In the manufacture of printed circuit boards (PCBs), copper foil is required to have an extremely low profile to meet the requirements of high-frequency and high-speed signal transmission. At the same time, it is also required to have good oxidation resistance and adhesion to substrates such as resins. Traditional copper foil preparation methods are difficult to meet these strict performance requirements at the same time. Therefore, the development of a new method for preparing extremely low-profile electronic copper foil and the corresponding solution system is of great practical significance. Summary of the invention

[0003] According to a first aspect of the present disclosure, a method for preparing a blackened electronic copper foil is provided, comprising the following steps:

[0004] Roughening the single-side surface of the original foil to form a single-side roughened surface, thereby obtaining a roughened copper foil;

[0005] The single-side roughened surface of the roughened copper foil is subjected to blackening treatment using the blackening solution to obtain a blackened copper foil; the blackening solution comprises the following components: 15 g / L to 30 g / L copper, 0.5 g / L to 2 g / L molybdenum, 80 g / L to 150 g / L glucose, 0.5 g / L to 2 g / L citric acid and water;

[0006] Performing anti-oxidation treatment on both sides of the blackened copper foil to obtain an anti-oxidation copper foil;

[0007] The single-side roughened surface of the oxidation-resistant copper foil is subjected to a silane coating treatment.

[0008] In an exemplary embodiment of the present disclosure, based on the above scheme, the pH value of the blackening solution is 2-6.

[0009] In an exemplary embodiment of the present disclosure, based on the above scheme, the temperature of the blackening solution is 20°C to 50°C.

[0010] In an exemplary embodiment of the present disclosure, based on the above scheme, the current density of the blackening treatment is 5A / dm 2 ~35A / dm 2 .

[0011] In an exemplary embodiment of the present disclosure, based on the above-mentioned solution, the blackening treatment time is 2s to 30s.

[0012] In an exemplary embodiment of the present disclosure, based on the above-mentioned solution, the transmission speed of the roughened copper foil in the blackening treatment is 0.5 m / min to 14 m / min.

[0013] In an exemplary embodiment of the present disclosure, based on the aforementioned scheme, a roughening solution is used to roughen the single-side surface of the original foil to form a single-side roughened surface; the roughening solution includes the following components: 15g / L-40g / L copper, 30g / L~60g / L sulfuric acid, 1g / L~5g / L phosphoric acid and water.

[0014] In an exemplary embodiment of the present disclosure, based on the aforementioned scheme, an anti-oxidation solution is used to perform anti-oxidation treatment on the double-side surfaces of the blackened copper foil; the anti-oxidation solution includes the following components: phytic acid 1g / L~5g / L, zinc 1g / L~10g / L, nickel 1g / L~5g / L, nitric acid 0.1g / L~5g / L and water.

[0015] In an exemplary embodiment of the present disclosure, based on the above-mentioned solution, a silane coating solution is used to perform a silane coating treatment on the single-sided roughened surface of the oxidation-resistant copper foil; the silane coating solution includes fluorinated triethoxysilane and water.

[0016] In an exemplary embodiment of the present disclosure, based on the aforementioned scheme, the preparation of the raw foil includes the following steps: the raw foil is prepared under electrolytic conditions using a copper deposition solution; the copper deposition solution includes the following components: 70 g / L to 100 g / L copper, 70 g / L to 100 g / L sulfuric acid, 1 g / L to 5 g / L brightener and water; the brightener includes polypropylene glycol, gelatin and hydroxymethyl cellulose, and the mass ratio of the polypropylene glycol, the gelatin and the hydroxymethyl cellulose is 1: (1.5 to 2.5): (0.2 to 0.8).

[0017] According to a second aspect of the present disclosure, a blackened electronic copper foil is provided, which is prepared by the preparation method of the first aspect of the present disclosure.

[0018] According to a third aspect of the present disclosure, an electronic product is provided, comprising the blackened electronic copper foil according to the third aspect of the present disclosure.

[0019] It can be seen from the above technical solution that the present disclosure has the following positive effects:

[0020] In the preparation method of the blackened electronic copper foil disclosed in the present invention, the specific formula design of the blackening solution can control the concentrations of copper ions, molybdenum ions, glucose and citric acid during the blackening process of the electronic copper foil, and the components work together to form a uniform and dense blackening layer on the surface of the copper foil, effectively improving the surface properties of the electronic copper foil, reducing its profile height, and laying a good foundation for subsequent processing steps. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] The above and other features and advantages of the present disclosure will become more apparent by describing in detail example embodiments thereof with reference to the attached drawings.

[0022] Figure 1 It is a structural schematic diagram of an integrated electronic copper foil production device in an embodiment of the present disclosure.

[0023] Figure 2 It is a structural schematic diagram of a roughening device in an integrated electronic copper foil production device in an embodiment of the present disclosure.

[0024] Figure 3 It is a schematic structural diagram of a blackened electronic copper foil in an embodiment of the present disclosure.

[0025] The main components in the figure are described as follows:

[0026] 1. Integrated electronic copper foil production equipment; 2. Sedimentation tank; 3. Roughening tank; 31. First positive electrode plate; 32. Second positive electrode plate; 33. Third positive electrode plate; 34. Fourth positive electrode plate; 4. Blackening tank; 5. Anti-oxidation tank; 6. Washing tank; 7. Titanium cathode roller; 8. Transfer roller; 10. Original foil (copper foil); 20. Blackened electronic copper foil; 201. Roughened surface; 202. Non-roughened surface; 203. Blackened layer. DETAILED DESCRIPTION

[0027] Example embodiments will now be described more fully with reference to the accompanying drawings. However, example embodiments can be implemented in a variety of forms and should not be construed as limited to the embodiments set forth herein; rather, these embodiments are provided so that this disclosure will be comprehensive and complete and will fully convey the concepts of the example embodiments to those skilled in the art. The same reference numerals in the figures represent the same or similar structures, and thus their detailed description will be omitted.

[0028] An embodiment of the present disclosure provides a method for preparing a blackened electronic copper foil, comprising the following steps: roughening the single-side surface of the original foil to form a single-side roughened surface to obtain a roughened copper foil. The single-side roughened surface of the roughened copper foil is blackened using a blackening solution to obtain a blackened copper foil. The blackening solution includes the following components: 15g / L to 30g / L copper, 0.5g / L to 2g / L molybdenum, 80g / L to 150g / L glucose, 0.5g / L to 2g / L citric acid, and water. Anti-oxidation treatment is performed on both sides of the blackened copper foil to obtain an anti-oxidation copper foil. The single-side roughened surface of the anti-oxidation copper foil is subjected to a silane coating treatment.

[0029] In the preparation method of the blackened electronic copper foil disclosed in the present invention, the specific formula design of the blackening solution can control the concentrations of copper ions, molybdenum ions, glucose and citric acid during the blackening process of the electronic copper foil. The components work together to form a uniform and dense blackening layer on the surface of the copper foil, effectively improve the surface properties of the copper foil, reduce its profile height, and lay a good foundation for subsequent processing steps.

[0030] The redox reaction of copper ions and glucose has an important influence on the formation of the black layer. Glucose, as a reducing agent, can reduce some copper ions to metallic copper. These newly formed metallic copper atoms will gradually accumulate on the surface of the copper foil and together with other components build the skeleton of the black layer. The copper content is within the range of 15g / L-30g / L, which can ensure that the black layer has enough copper elements to maintain the stability and density of its structure.

[0031] The content of molybdenum ions in the blackening solution is 0.5g / L to 2g / L, which can play a catalytic and modifying role. On the one hand, molybdenum can promote the redox reaction in the solution and accelerate the blackening process. For example, molybdenum can catalyze the reaction between glucose and copper ions, speed up the reaction rate, and thus improve the blackening efficiency. On the other hand, the presence of molybdenum can improve the microstructure of the blackening layer. It can form alloys or compounds with elements such as copper, refine the grains of the blackening layer, and make the blackening layer more dense and uniform. In synergy with other ingredients, molybdenum and citric acid may also interact with each other to adjust the potential and ion activity of the solution, and further optimize the conditions of the blackening reaction.

[0032] In the blackening solution, glucose mainly participates in the redox reaction, reducing copper ions to metallic copper while being oxidized itself. This reaction not only provides a source of metallic copper for the blackening layer, but the intermediates produced during the reaction also affect the performance of the blackening layer. For example, the organic groups produced by the oxidation of glucose may be adsorbed on the surface of the copper foil and form a protective film structure together with other components. When acting in synergy with citric acid, glucose can adjust the pH of the solution. Because citric acid is a weak acid, the presence of glucose can affect the degree of dissociation of citric acid, thereby stabilizing the pH value of the solution and creating a suitable environment for the blackening reaction.

[0033] Citric acid, as an organic acid, has a content of 0.5g / L to 2g / L in the solution, and can act as a complexing agent and pH regulator. As a complexing agent, citric acid can form complexes with metal ions (such as copper ions) in the solution. This complexing action can control the deposition rate of metal ions and prevent metal ions from depositing too quickly on the surface of the copper foil, resulting in an uneven blackening layer. At the same time, citric acid can adjust the pH value of the solution to keep the solution within a pH range suitable for the blackening reaction. In addition, the interaction between citric acid and molybdenum can change the existence form of molybdenum, allowing it to better play a catalytic role. Citric acid and glucose can jointly adjust the chemical environment of the solution to ensure that the redox reaction can proceed smoothly, which is conducive to the formation of a high-quality blackening layer.

[0034] It can be understood that in the blackening solution of the present disclosure, the concentration of each component is expressed based on the volume of the blackening solution, and the mass of each component is based on the concentration of the volume of the blackening solution.

[0035] For example, the concentration of copper indicates the concentration of copper mass based on the volume of the blackening solution. Optionally, the concentration of copper can be, but is not limited to, 15 g / L, 18 g / L, 20 g / L, 22 g / L, 25 g / L, 28 g / L, 30 g / L. It is understood that the concentration of copper can also be other suitable selections within the range of 15 g / L-30 g / L.

[0036] For example, the concentration of molybdenum indicates the mass of molybdenum based on the volume of the blackening solution. Optionally, the concentration of molybdenum can be, but is not limited to, 0.5 g / L, 0.6 g / L, 0.7 g / L, 0.8 g / L, 0.9 g / L, 1 g / L, 1.1 g / L, 1.2 g / L, 1.3 g / L, 1.4 g / L, 1.5 g / L, 1.6 g / L, 1.7 g / L, 1.8 g / L, 1.9 g / L, 2 g / L. It is understood that the concentration of molybdenum can also be other suitable selections within the range of 0.5 g / L to 2 g / L.

[0037] For example, the concentration of glucose indicates the concentration of the mass of glucose based on the volume of the blackening solution. Optionally, the concentration of glucose can be, but is not limited to, 80 g / L, 85 g / L, 90 g / L, 95 g / L, 100 g / L, 105 g / L, 110 g / L, 115 g / L, 120 g / L, 125 g / L, 130 g / L, 135 g / L, 140 g / L, 145 g / L, 150 g / L. It is understood that the concentration of glucose can also be other suitable selections within the range of 80 g / L to 150 g / L.

[0038] For example, the concentration of citric acid indicates the mass of citric acid based on the volume of the blackening solution. Optionally, the concentration of citric acid can be, but is not limited to, 0.5 g / L, 0.6 g / L, 0.7 g / L, 0.8 g / L, 0.9 g / L, 1 g / L, 1.1 g / L, 1.2 g / L, 1.3 g / L, 1.4 g / L, 1.5 g / L, 1.6 g / L, 1.7 g / L, 1.8 g / L, 1.9 g / L, 2 g / L. It is understood that the concentration of citric acid can also be other suitable selections within the range of 0.5 g / L to 2 g / L.

[0039] In some embodiments, the blackening solution is composed of the following components: 15 g / L to 30 g / L copper, 0.5 g / L to 2 g / L molybdenum, 80 g / L to 150 g / L glucose, 0.5 g / L to 2 g / L citric acid, and water. It is understood that in the electronic copper foil blackening solution of this embodiment, the concentration of copper, the concentration of molybdenum, the concentration of glucose, and the concentration of citric acid can be selected from the concentrations listed above, and will not be repeated here.

[0040] In some embodiments, the pH value of the blackening solution is 2 to 6. A pH value in this range can further improve the blackening effect and obtain a more uniform blackening layer. Optionally, the pH value of the blackening solution can be, but is not limited to, 2, 3, 4, 5, 6. It is understood that the pH value of the blackening solution can also be other suitable choices within the range of 2 to 6.

[0041] In some embodiments, when preparing blackened electronic copper foil, the thickness of the original foil is 4 μm to 12 μm, and based on the original foil within this thickness range, a blackened electronic copper foil with better performance can be obtained. Further preferably, the thickness of the original foil is 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, or 12 μm.

[0042] It is understandable that the original foil may be a copper foil obtained by electrolytic deposition, or may be a copper foil obtained by electrolytic deposition after some surface treatment.

[0043] It is also understood that when naming copper foil, the "raw foil" and "copper foil" in the present disclosure do not strictly distinguish between copper foils, but only formally distinguish between copper foils at different processing stages. For example, in the drawings of the present disclosure, the raw foil and the copper foil can be represented by the same reference numeral.

[0044] In some embodiments, the temperature of the blackening solution is 20°C to 50°C. During the blackening treatment, if the temperature of the blackening solution is too low, the blackening efficiency is low, and the activity of the blackening solution is low, it is difficult to obtain a good blackening effect; and when the temperature of the blackening solution is too high, on the one hand, too much energy is consumed, and on the other hand, the blackening speed may be too fast, making it difficult to obtain a uniform blackening layer. Optionally, during the blackening treatment, the temperature of the blackening solution can be but is not limited to 20°C, 25°C, 30°C, 35°C, 40°C, 45°C, and 50°C. It is understandable that the temperature of the blackening solution can also be other suitable choices within the range of 20°C to 50°C.

[0045] In some embodiments, the current density of the blackening process is 5A / dm 2 ~35A / dm 2 During the blackening treatment, if the current density of the blackening treatment is too small, it is difficult to obtain a high blackening efficiency, and if the current density of the blackening treatment is too large, it may be difficult to obtain a blackened surface with good consistency. Optionally, during the blackening treatment, the current density of the blackening treatment can be but is not limited to 5A / dm 2 , 8A / dm 2 、10A / dm 2 、12A / dm 2 、15A / dm 2 、18A / dm 2 、20A / dm 2 、25A / dm 2 、30A / dm 2 、35A / dm 2 It is understandable that the current density of the blackening treatment can also be 5A / dm 2 ~35A / dm 2 Make other appropriate choices within the scope.

[0046] In some embodiments, the blackening treatment time is 2s to 30s. During the blackening treatment, if the blackening treatment time is too short, it is difficult to obtain a good blackening effect. If the blackening treatment time is too long, on the one hand, it will produce higher energy consumption, and on the other hand, it may cause excessive corrosion to the copper foil, affecting the performance of the electronic copper foil. Optionally, during the blackening treatment, the blackening treatment time can be but is not limited to 2s, 5s, 10s, 15s, 20s, 25s, 30s. It is understandable that during the blackening treatment, the blackening treatment time can also be other suitable selections within the range of 2s to 30s.

[0047] In some embodiments, the transmission speed of the roughened copper foil during the blackening treatment is 0.5 m / min to 14 m / min. During the blackening treatment, if the transmission speed of the roughened copper foil is too low, it may result in excessive blackening, which may cause excessive corrosion to the electronic copper foil and affect the performance of the electronic copper foil. If the transmission speed of the roughened copper foil is too high, it is difficult to obtain a sufficient blackening effect, which affects the performance of the blackening layer of the electronic copper foil. Optionally, during the blackening treatment, the transmission speed of the roughened copper foil can be but is not limited to 0.5 m / min, 1 m / min, 5 m / min, 10 m / min, and 14 m / min. It is understandable that during the blackening treatment, the transmission speed of the roughened copper foil can also be other suitable selections within the range of 0.5 m / min to 14 m / min.

[0048] In some embodiments, a roughening solution is used to roughen the single-side surface of the original foil to form a single-side roughened surface; the roughening solution includes the following components: 15g / L to 40g / L copper, 30g / L to 60g / L sulfuric acid, 1g / L to 5g / L phosphoric acid, and water. When the roughening solution of the present disclosure is used to roughen the electronic copper foil, the copper ions, sulfuric acid, and phosphoric acid cooperate with each other at the corresponding concentration to achieve fine control of the surface microstructure of the copper foil. Among them, sulfuric acid with a concentration of 30g / L to 60g / L can effectively etch the surface of the copper foil and control the surface roughness of the copper foil. Phosphoric acid with a concentration of 1g / L to 5g / L can play a good role in buffering and assisting the etching of sulfuric acid, making the surface roughness of the roughened surface of the copper foil more uniform, reducing the risk of over-etching or uneven etching. In the roughening process, copper with a concentration of 15g / L to 40g / L helps to maintain the electrochemical balance of the solution and ensure the stability and continuity of the roughening process. The roughened surface of the electronic copper foil treated with the roughening solution can obtain an ideal surface roughness, thereby significantly increasing the surface area of ​​the roughened surface and laying a solid foundation for subsequently improving the bonding strength with the substrate.

[0049] In some embodiments, when the surface of the electronic copper foil is roughened by the roughening solution of the present disclosure, the roughness Rz of the roughened surface of the electronic copper foil can be made less than 2 μm, thereby obtaining a blackened electronic copper foil.

[0050] At the same time, compared with the existing roughening solution, the roughening solution disclosed in the present invention can increase the surface area of ​​the electronic copper foil by 200% to 500%, greatly improving the bonding force between the roughened surface of the electronic copper foil and the substrate.

[0051] It can be understood that in the roughening solution of the present disclosure, the concentration of each component is expressed based on the volume of the roughening solution, and the mass of each component is based on the concentration of the volume of the roughening solution.

[0052] For example, the concentration of copper indicates the concentration of the mass of copper based on the volume of the roughening solution. Optionally, the concentration of copper can be, but is not limited to, 15 g / L, 18 g / L, 20 g / L, 22 g / L, 25 g / L, 28 g / L, 30 g / L, 32 g / L, 35 g / L, 38 g / L, 40 g / L. It is understood that the concentration of copper can also be other suitable selections within the range of 15 g / L to 40 g / L.

[0053] For example, the concentration of sulfuric acid indicates the mass of sulfuric acid based on the volume of the roughening solution. Optionally, the concentration of sulfuric acid can be, but is not limited to, 30 g / L, 32 g / L, 35 g / L, 38 g / L, 40 g / L, 42 g / L, 45 g / L, 48 g / L, 50 g / L, 52 g / L, 55 g / L, 58 g / L, 60 g / L. It is understood that the concentration of sulfuric acid can also be other suitable selections within the range of 30 g / L to 60 g / L.

[0054] For example, the concentration of phosphoric acid indicates the concentration of the mass of phosphoric acid based on the volume of the roughening solution. Optionally, the concentration of phosphoric acid can be, but is not limited to, 1 g / L, 1.2 g / L, 1.5 g / L, 1.8 g / L, 2 g / L, 2.2 g / L, 2.5 g / L, 2.8 g / L, 3 g / L, 3.2 g / L, 3.5 g / L, 3.8 g / L, 4 g / L, 4.2 g / L, 4.5 g / L, 4.8 g / L, 5 g / L. It is understood that the concentration of phosphoric acid can also be other suitable selections within the range of 1 g / L to 5 g / L.

[0055] In some embodiments, the roughening solution is composed of the following components: 15 g / L to 40 g / L copper, 30 g / L to 60 g / L sulfuric acid, 1 g / L to 5 g / L phosphoric acid, and water. It is understood that in the roughening solution of this embodiment, the concentration of copper, the concentration of sulfuric acid, and the concentration of phosphoric acid can be selected from the concentrations listed above, which will not be repeated here.

[0056] In some embodiments, the pH value of the roughening solution is 0.5 to 3. The pH value in this range can further improve the roughening effect, so that the roughened surface of the electronic copper foil can better balance the extremely low profile and the larger surface area. Optionally, the pH value of the roughening solution can be 0.5, 0.8, 1, 1.2, 1.5, 1.8, 2, 2.2, 2.5, 2.8, 3. It is understood that the pH value of the roughening solution can also be other suitable choices within the range of 0.5 to 3.

[0057] In some embodiments, the temperature of the roughening solution is 15°C to 25°C. During the roughening treatment, if the temperature of the roughening solution is too low, the roughening efficiency is low, and the activity of the roughening solution is low, it is difficult to obtain a good roughening effect; when the temperature of the roughening solution is too high, on the one hand, too much energy is consumed, and on the other hand, the roughening speed may be too fast, making it difficult to control the stable growth of the surface area of ​​the roughened surface of the electronic copper foil. Optionally, during the roughening treatment, the temperature of the roughening solution can be but is not limited to 15°C, 16°C, 17°C, 18°C, 19°C, 20°C, 21°C, 22°C, 23°C, 24°C, 25°C. It is understandable that the temperature of the roughening solution can also be other suitable choices within the range of 15°C to 25°C.

[0058] In some embodiments, the current density of the roughening process is 10A / dm 2 ~50A / dm 2 During the roughening treatment, if the current density of the roughening treatment is too small, it is difficult to obtain a high roughening efficiency, and if the current density of the roughening treatment is too large, it may be difficult to obtain a roughened surface with good consistency. Optionally, during the roughening treatment, the current density of the roughening treatment can be but is not limited to 10A / dm 2 、15A / dm 2 、20A / dm 2 、25A / dm 2 、30A / dm 2 、35A / dm 2 , 40A / dm 2 、45A / dm 2 、50A / dm 2 It is understood that the current density of the roughening treatment can also be 10A / dm 2 ~50A / dm 2 Make other appropriate choices within the scope.

[0059] In some embodiments, the time of the roughening treatment is 3s to 10s. During the roughening treatment, if the time of the roughening treatment is too short, it is difficult to obtain a good roughening effect. If the time of the roughening treatment is too long, on the one hand, it will produce higher energy consumption, and on the other hand, it may cause excessive damage to the electronic copper foil, affecting the performance of the electronic copper foil. Optionally, during the roughening treatment, the time of the roughening treatment can be but is not limited to 3s, 4s, 5s, 6s, 7s, 8s, 9s, 10s. It is understandable that the time of the roughening treatment can also be other suitable selections within the range of 3s to 10s.

[0060] In some embodiments, the transmission speed of the original foil during the roughening process is 0.5m / min to 14m / min. During the roughening process, if the transmission speed of the original foil is too small, it may result in excessive roughening, which may cause excessive damage to the electronic copper foil and affect the performance of the electronic copper foil. If the transmission speed of the original foil is too large, it is difficult to obtain a sufficient roughening effect, which affects the performance of the roughened surface of the electronic copper foil. Optionally, during the roughening process, the transmission speed of the original foil can be but is not limited to 0.5m / min, 0.8m / min, 1m / min, 2m / min, 3m / min, 4m / min, 5m / min, 6m / min, 7m / min, 8m / min, 9m / min, 10m / min, 11m / min, 12m / min, 13m / min, 14m / min. It is understandable that during the roughening process, the transmission speed of the original foil can also be other suitable choices within the range of 0.5m / min to 14m / min.

[0061] In some embodiments, an anti-oxidation solution is used to perform an anti-oxidation treatment on the double-sided surfaces of the blackened copper foil. The anti-oxidation solution includes the following components: phytic acid 1g / L~5g / L, zinc 1g / L~10g / L, nickel 1g / L~5g / L, nitric acid 0.1g / L~5g / L and water. By combining phytic acid, zinc, nickel and nitric acid, a solution with good anti-oxidation effect on electronic copper foil can be obtained. In particular, after the electronic copper foil is treated with the solution for anti-oxidation, the anti-oxidation performance of the electronic copper foil at high temperature can be effectively improved, so that the electronic copper foil maintains stable performance when hot-pressed with the substrate, and effectively promotes the improvement of the bonding force between the electronic copper foil and the substrate. At the same time, after the electronic copper foil is treated with the solution for anti-oxidation, the electronic copper foil can maintain good electrical and thermal conductivity. After the electronic copper foil is applied to electronic products, the electronic products can maintain good performance.

[0062] Furthermore, the protective film formed on the surface of the electronic copper foil using the anti-oxidation solution disclosed in the present invention can improve the corrosion resistance of the copper foil. The complex formed by phytic acid and metal ions can fill the tiny pores on the surface of the copper foil, making the surface of the electronic copper foil smoother and flatter, reducing the adhesion and penetration of the corrosive medium on the surface of the copper foil, thereby enhancing the resistance of the electronic copper foil to corrosive media such as acids, alkalis, and salts.

[0063] Specifically, phytic acid is an organic acid with strong chelating ability, and its molecular structure contains multiple phosphate groups. In the anti-oxidation solution, phytic acid can quickly react with copper ions on the surface of copper foil to form a tightly packed protective film with certain barrier properties. At the same time, the hydroxyl and phosphate groups of phytic acid can also complex with zinc ions and nickel ions, further strengthening the structural integrity and stability of the protective film, making it less likely to be destroyed in high temperature environments.

[0064] Zinc ions have a dual role in the solution. On the one hand, zinc is relatively chemically active and can undergo a certain degree of replacement reaction on the surface of the copper foil to form a zinc protective film. This zinc layer can act as a sacrificial anode and preferentially undergo oxidation reaction with oxygen in the surrounding environment, thereby delaying the oxidation process of the copper foil. On the other hand, after zinc ions are complexed with phytic acid, they can be evenly dispersed in the protective film, enhancing the overall protective performance of the protective film.

[0065] Nickel ions can form alloy phases or intermetallic compounds with phytic acid and copper atoms on the surface of copper foil. This special structure can significantly improve the hardness, wear resistance and high-temperature oxidation resistance of the protective film. Under high temperature conditions, the presence of nickel helps maintain the structural stability of the protective film and prevents it from softening, cracking or decomposing, thereby providing long-lasting and reliable protection for the copper foil.

[0066] Nitric acid plays a major role in adjusting the pH of the solution and promoting the dissolution and reaction of metal ions. By controlling the content of nitric acid, the reaction activity of the solution can be optimized to ensure that phytic acid, zinc ions and nickel ions can be fully dissolved and evenly distributed in the solvent, so that they can react efficiently when in contact with copper foil, forming a uniform, dense and high-performance anti-oxidation protective film.

[0067] The concentration of phytic acid in the anti-oxidation solution refers to the concentration of the mass of phytic acid based on the volume of the anti-oxidation solution. Optionally, the concentration of phytic acid can be 1g / L, 1.5g / L, 2g / L, 2.5g / L, 3g / L, 3.5g / L, 4g / L, 4.5g / L, 5g / L, etc. It is understood that the concentration of phytic acid can also be other suitable selections within the range of 1g / L to 5g / L.

[0068] The concentration of zinc in the anti-oxidation solution means the concentration of the mass of zinc based on the volume of the anti-oxidation solution. Optionally, the concentration of zinc can be 1g / L, 1.5g / L, 2g / L, 2.5g / L, 3g / L, 3.5g / L, 4g / L, 4.5g / L, 5g / L, 5.5g / L, 6g / L, 6.5g / L, 7g / L, 7.5g / L, 8g / L, 8.5g / L, 9g / L, 9.5g / L, 10g / L, etc. It is understood that the concentration of zinc can also be other suitable selections within the range of 1g / L to 10g / L.

[0069] The concentration of nickel in the anti-oxidation solution refers to the concentration of the mass of nickel based on the volume of the anti-oxidation solution. Optionally, the concentration of nickel can be 1g / L, 1.5g / L, 2g / L, 2.5g / L, 3g / L, 3.5g / L, 4g / L, 4.5g / L, 5g / L, etc. It is understood that the concentration of nickel can also be other suitable selections within the range of 1g / L to 5g / L.

[0070] The concentration of nitric acid in the anti-oxidation solution means the concentration of the mass of nitric acid based on the volume of the anti-oxidation solution. Optionally, the concentration of nitric acid can be 0.1 g / L, 0.2 g / L, 0.3 g / L, 0.4 g / L, 0.5 g / L, 0.6 g / L, 0.7 g / L, 0.8 g / L, 0.9 g / L, 1 g / L, 1.5 g / L, 2 g / L, 2.5 g / L, 3 g / L, 3.5 g / L, 4 g / L, 4.5 g / L, 5 g / L, etc. It is understood that the concentration of nitric acid can also be other suitable selections within the range of 0.1 g / L to 5 g / L.

[0071] In some embodiments, in the anti-oxidation solution, the mass ratio of phytic acid, zinc, and nickel is 1:3:1.

[0072] In some embodiments, the concentration of chromium in the anti-oxidation solution is 0. In this embodiment, by designing the anti-oxidation solution, the anti-oxidation solution can still maintain a good anti-oxidation effect without using toxic metal chromium, which is conducive to promoting the green development of electronic copper foil production.

[0073] In some embodiments, the pH value of the anti-oxidation solution is 1 to 5. Within this pH range, phytic acid, zinc, nickel and nitric acid can cooperate better to further improve the anti-oxidation effect of the solution on electronic copper foil. It is understood that the pH value of the anti-oxidation solution can be adjusted by nitric acid. Optionally, the pH value of the anti-oxidation solution can be 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, etc. It is understood that the pH value of the anti-oxidation solution can also be other suitable choices within the range of 1 to 5.

[0074] In some embodiments, the current density of the anti-oxidation treatment is 0.1 A / dm 2 ~10A / dm 2 If the current density is too small or too large, it is difficult to form a dense anti-oxidation film, which is not conducive to improving the anti-oxidation effect. Optionally, the current density of the anti-oxidation treatment can be 0.1A / dm 2 , 0.2A / dm 2 , 0.5A / dm 2 , 0.8A / dm 2 , 1A / dm 2 , 2A / dm 2 、3A / dm 2 , 4A / dm 2 , 5A / dm 2 、6A / dm 2 , 7A / dm 2 , 8A / dm 2 、9A / dm 2 、10A / dm 2It is understood that the current density of the anti-oxidation treatment can also be 0.1A / dm 2 ~10A / dm 2 Make other appropriate choices within the scope.

[0075] In some embodiments, during the anti-oxidation treatment, the temperature of the anti-oxidation solution is 20°C to 25°C. If the temperature of the anti-oxidation solution is too low or too high, it is difficult to form a dense anti-oxidation film, which is not conducive to improving the anti-oxidation effect. In this embodiment, anti-oxidation treatment at room temperature can provide a good anti-oxidation effect for the electronic copper foil. Optionally, the temperature of the anti-oxidation treatment can be 20°C, 21°C, 22°C, 23°C, 24°C, 25°C, etc. It is understandable that the temperature of the anti-oxidation solution can also be selected in the range of 20°C to 25°C.

[0076] In some embodiments, the transmission speed of the blackened copper foil in the anti-oxidation treatment is 0.2m / min to 15m / min. If the transmission speed of the blackened copper foil is too low, the production efficiency is low, and if the transmission speed of the blackened copper foil is too high, it is difficult to form a good anti-oxidation film. Optionally, the transmission speed of the blackened copper foil in the anti-oxidation treatment can be 0.2m / min, 0.5m / min, 0.8m / min, 1m / min, 2m / min, 5m / min, 8m / min, 10m / min, 12m / min, 15m / min, etc. It is understandable that the transmission speed of the blackened copper foil in the anti-oxidation treatment can also be other suitable selections within the range of 0.2m / min to 15m / min.

[0077] In some embodiments, a silane coating solution is used to perform silane coating on the single-sided roughened surface of the anti-oxidation copper foil. The silane coating solution includes fluorinated triethoxysilane and water. The silane coating solution is mainly composed of fluorinated triethoxysilane and water. The silane alkoxy group (-Si-OEt) in the fluorinated triethoxysilane molecule can undergo a hydrolysis reaction to generate silanol (-Si-OH). These silanol groups can react chemically with the oxide (such as copper oxide) on the surface of the copper foil and the active hydroxyl groups in the microstructure formed by the roughening to form a strong chemical bond, thereby tightly fixing the silane molecules on the surface of the copper foil. The fluorine group at the other end of the silane molecule has low surface energy and good chemical stability, and it can produce strong intermolecular forces with the substrate used subsequently, such as van der Waals forces and hydrogen bonds. The synergistic effect of this chemical bonding and intermolecular forces effectively improves the bonding force between the electronic copper foil and the substrate. At the same time, the presence of the fluorine group also gives the electronic copper foil a certain hydrophobicity and corrosion resistance, further improving the comprehensive performance of the electronic copper foil.

[0078] Optionally, the silane coating solution may be sprayed onto the single-side roughened surface of the oxidation-resistant copper foil.

[0079] Optionally, the mass percentage of fluorinated triethoxysilane in the silane coating solution is 0.1% to 2%. Optionally, the mass percentage of fluorinated triethoxysilane in the silane coating solution is 0.1%, 0.5%, 0.8%, 1%, 1.2%, 1.5%, 1.8%, 2%, etc. It is understandable that the mass percentage of fluorinated triethoxysilane in the silane coating solution can also be other suitable selections within the range of 0.1% to 2%.

[0080] In some embodiments, the preparation of the raw foil includes the following steps: preparing the raw foil under electrolytic conditions using a copper deposition solution. The copper deposition solution includes the following components: 70 g / L to 100 g / L copper, 70 g / L to 100 g / L sulfuric acid, 1 g / L to 5 g / L brightener, and water. The brightener includes polypropylene glycol, gelatin, and hydroxymethyl cellulose, and the mass ratio of polypropylene glycol, gelatin, and hydroxymethyl cellulose is 1: (1.5 to 2.5): (0.2 to 0.8). The raw foil with excellent surface quality can be obtained by the copper deposition solution. For example, the brightener including polypropylene glycol, gelatin, and hydroxymethyl cellulose can effectively improve the surface flatness and glossiness of the copper foil. During the electrolytic deposition process, these components can be adsorbed on the crystal plane of copper growth, inhibit the uneven growth of crystals, and reduce the formation of surface defects such as pitting and scratches, thereby making the surface of the copper foil smoother and flatter, which is beneficial for subsequent processing (such as roughening, anti-oxidation, etching, plating, etc.), and can improve processing accuracy and product yield.

[0081] The concentration of copper in the copper deposition solution indicates the concentration of the mass of copper based on the volume of the copper deposition solution. Optionally, the concentration of copper may be 70 g / L, 75 g / L, 80 g / L, 85 g / L, 90 g / L, 95 g / L, 100 g / L. It is understood that the concentration of copper may also be other suitable selections within the range of 70 g / L to 100 g / L.

[0082] The concentration of sulfuric acid in the copper deposition solution refers to the concentration of the mass of sulfuric acid based on the volume of the copper deposition solution. Optionally, the concentration of sulfuric acid can be 70 g / L, 75 g / L, 80 g / L, 85 g / L, 90 g / L, 95 g / L, 100 g / L. It is understood that the concentration of sulfuric acid can also be other suitable selections within the range of 70 g / L to 100 g / L.

[0083] The concentration of the brightener in the copper deposition solution indicates the concentration of the mass of the brightener based on the volume of the copper deposition solution. Optionally, the concentration of the brightener may be 1 g / L, 1.5 g / L, 2 g / L, 2.5 g / L, 3 g / L, 3.5 g / L, 4 g / L, 4.5 g / L, 5 g / L, etc. It is understood that the concentration of the brightener may also be other suitable selections within the range of 1 g / L to 5 g / L.

[0084] Optionally, in the brightener, the mass ratio of polypropylene glycol, gelatin and hydroxymethyl cellulose can be 1:1.5:0.2, 1:1.5:0.5, 1:1.5:0.8, 1:2:0.2, 1:2:0.5, 1:2:0.8, 1:2.5:0.2, 1:2.5:0.5, 1:2.5:0.8. It is understandable that the mass ratio of polypropylene glycol, gelatin and hydroxymethyl cellulose can also be selected in the range of 1:(1.5-2.5):(0.2-0.8).

[0085] In some embodiments, when preparing the original foil, the temperature of the copper deposition liquid is 48°C to 52°C. If the temperature of the copper deposition liquid is too low, the deposition efficiency is low, and the activity of the copper deposition liquid is low, and it is difficult to obtain a good deposition effect; when the temperature of the copper deposition liquid is too high, on the one hand, too much energy is consumed, and on the other hand, the deposition speed may be too fast, making it difficult to control the stable deposition of the original foil. Optionally, when preparing the original foil, the temperature of the copper deposition liquid can be but is not limited to 48°C, 49°C, 50°C, 51°C, and 52°C. It is understandable that the temperature of the copper deposition liquid can also be other suitable selections within the range of 48°C to 52°C.

[0086] In some embodiments, the method for preparing the blackened electronic copper foil further includes: before blackening the single-side roughened surface of the roughened copper foil, washing the roughened copper foil with water. The washing with water can remove the residual solution on the surface of the roughened copper foil, thereby improving the effect of the subsequent blackening treatment.

[0087] In some embodiments, the present disclosure also provides an integrated electronic copper foil production device. Figure 1 As shown, the integrated electronic copper foil production equipment 1 includes a deposition tank 2, a roughening tank 3, a blackening tank 4 and an anti-oxidation tank 5. The deposition tank is used to prepare the original foil 10 by using a copper deposition liquid under electrolysis of a titanium cathode roller 7. The roughening tank 3 is used to roughen the single-side surface of the original foil 10 to form a single-side roughened surface. The blackening tank 4 is used to blacken the single-side roughened surface of the roughened copper foil to form a single-side blackened surface. The anti-oxidation tank 5 is used to perform anti-oxidation treatment on the double-side surfaces of the blackened copper foil.

[0088] It is understandable that the integrated electronic copper foil production equipment 1 further includes a transmission roller 8 , which is used to transmit the original foil 10 .

[0089] The integrated electronic copper foil production equipment disclosed in the present invention can realize continuous production of four key processes including foil production, roughening, blackening and anti-oxidation, thereby improving the production efficiency of electronic copper foil.

[0090] Optionally, the integrated electronic copper foil production equipment 1 further includes a water washing tank 6. The water washing tank 6 is located between the roughening tank 3 and the blackening tank 4.

[0091] It can be understood that the deposition tank is filled with copper deposition solution, the roughening tank is filled with roughening solution, the blackening tank is filled with blackening solution, the anti-oxidation tank is filled with anti-oxidation solution, and the washing tank is filled with washing solution.

[0092] See also Figure 2 , a first positive electrode plate 31, a second positive electrode plate 32, a third positive electrode plate 33 and a fourth positive electrode plate 34 are arranged in the roughening tank 3. On the transmission path of the original foil 10, the first positive electrode plate 31 and the second positive electrode plate 32 are located on the same side of the original foil 10, the third positive electrode plate 33 and the fourth positive electrode plate 34 are located on the same side of the original foil 10, and the first positive electrode plate 31 and the third positive electrode plate are located on opposite sides of the original foil 10. When the single-side surface of the original foil 10 is roughened, the first positive electrode plate 31 and the second positive electrode plate 32 may be opened, and the third positive electrode plate 33 and the fourth positive electrode plate 34 may be closed; or the first positive electrode plate 31 and the second positive electrode plate 32 may be closed, and the third positive electrode plate 33 and the fourth positive electrode plate 34 may be opened.

[0093] It is understandable that the integrated electronic copper foil production device 1 can be used to prepare the blackened electronic copper foil.

[0094] See also Figure 3 , which shows a blackened electronic copper foil 20 in an embodiment of the present disclosure. The blackened electronic copper foil 20 has a roughened surface 201 and a non-roughened surface 202 opposite to the roughened surface 201 , and a blackened layer 203 is formed on the roughened surface 201 .

[0095] In some embodiments, the method for preparing blackened electronic copper foil comprises the following steps:

[0096] S101: Prepare the original foil by using copper deposition solution under electrolytic conditions; the copper deposition solution includes the following components: 70 g / L to 100 g / L copper, 70 g / L to 100 g / L sulfuric acid, 1 g / L to 5 g / L brightener and water; the brightener includes polypropylene glycol, gelatin and hydroxymethyl cellulose, and the mass ratio of polypropylene glycol, gelatin and hydroxymethyl cellulose is 1: (1.5 to 2.5): (0.2 to 0.8). When preparing the original foil, the temperature of the copper deposition solution is 48°C to 52°C.

[0097] S102: Roughening the single-side surface of the original foil with a roughening solution to form a single-side roughened surface to obtain a roughened copper foil. The roughening solution includes the following components: 15 g / L to 40 g / L copper, 30 g / L to 60 g / L sulfuric acid, 1 g / L to 5 g / L phosphoric acid, and water. The pH value of the roughening solution is 0.5 to 3. The temperature of the roughening solution is 15°C to 25°C. The current density of the roughening treatment is 10 A / dm 2 ~50A / dm 2The roughening treatment time is 3s to 10s. The conveying speed of the original foil during the roughening treatment is 0.5m / min to 14m / min.

[0098] S103: The roughened copper foil is washed with water.

[0099] S104: Use a blackening solution to blacken the single-side surface of the roughened copper foil after water washing to obtain a blackened copper foil. The blackening solution includes the following components: 15g / L to 30g / L copper, 0.5g / L to 2g / L molybdenum, 80g / L to 150g / L glucose, 0.5g / L to 2g / L citric acid, and water. The pH value of the blackening solution is 2 to 6. The temperature of the blackening solution is 20℃ to 50℃. The current density of the blackening treatment is 5A / dm 2 ~35A / dm 2 The blackening treatment time is 2s to 30s. The transmission speed of the roughened copper foil during the blackening treatment is 0.5m / min to 14m / min.

[0100] S105: Anti-oxidation treatment is performed on both sides of the blackened copper foil using an anti-oxidation solution to obtain an anti-oxidation copper foil. The anti-oxidation solution includes the following components: phytic acid 1g / L to 5g / L, zinc 1g / L to 10g / L, nickel 1g / L to 5g / L, nitric acid 0.1g / L to 5g / L and water. The pH value of the anti-oxidation solution is 1 to 5. The current density of the anti-oxidation treatment is 0.1A / dm 2 ~10A / dm 2 The temperature of the anti-oxidation solution is 20° C. to 25° C. The transmission speed of the roughened copper foil during the anti-oxidation treatment is 0.2 m / min to 15 m / min.

[0101] S106: using a silane coating solution to perform a silane coating treatment on the roughened surface of the anti-oxidation copper foil on one side. The silane coating solution includes fluorotriethoxysilane and water. The mass percentage of fluorotriethoxysilane in the silane coating solution is 0.1% to 2%.

[0102] Example 1

[0103] The method for preparing the blackened electronic copper foil in this embodiment includes the following steps:

[0104] S101: Prepare the original foil by using copper deposition solution under electrolytic conditions. The copper deposition solution includes the following components: 80 g / L copper, 80 g / L sulfuric acid, 2 g / L brightener and water. The brightener includes polypropylene glycol, gelatin and hydroxymethyl cellulose, and the mass ratio of polypropylene glycol, gelatin and hydroxymethyl cellulose is 1:2:0.5. The temperature of the copper deposition solution is 50°C. The thickness of the original foil is 5 μm.

[0105] S102: Roughening the single-side surface of the original foil with a roughening solution to form a single-side roughened surface, thereby obtaining a roughened copper foil. The roughening solution includes the following components: 25 g / L copper, 45 g / L sulfuric acid, 3 g / L phosphoric acid, and water. The temperature of the roughening solution is 20°C. The current density of the roughening treatment is 20 A / dm 2 The roughening treatment time was 5 s. The conveying speed of the original foil during the roughening treatment was 5 m / min.

[0106] S103: The roughened copper foil is washed with water.

[0107] S104: blackening the single-side roughened surface of the roughened copper foil after the water washing treatment with a blackening solution to obtain a blackened copper foil. The blackening solution includes the following components: 20 g / L copper, 1 g / L molybdenum, 100 g / L glucose, 1 g / L citric acid and water. The temperature of the blackening solution is 40°C. The current density of the blackening treatment is 35 A / dm 2 The blackening treatment time is 15s.

[0108] S105: Anti-oxidation treatment is performed on both sides of the blackened copper foil after water washing to obtain an anti-oxidation copper foil. The anti-oxidation solution includes the following components: phytic acid 2g / L, zinc 6g / L, nickel 2g / L, nitric acid 2g / L and water. The current density of the anti-oxidation treatment is 5A / dm 2 The temperature of the anti-oxidation solution was 20° C. The transmission speed of the blackened copper foil during the anti-oxidation treatment was 5 m / min.

[0109] S106: using a silane coating solution to perform a silane coating treatment on the roughened surface of one side of the oxidation-resistant copper foil; the silane coating solution includes fluorinated triethoxysilane and water, and the mass percentage of fluorinated triethoxysilane in the silane coating solution is 1%.

[0110] Examples 2 to 5, Comparative Examples 1 to 8

[0111] Compared with Example 1, the difference between Examples 2 to 5 and Comparative Examples 1 to 8 is that the composition of the blackening solution is different, as shown in Table 1.

[0112] Comparative Example 9

[0113] The preparation method of the electronic copper foil in this comparative example comprises the following steps:

[0114] The roughening solution was used to roughen the single-side surface of the original foil with a thickness of 5 μm to form a single-side roughened surface. The roughening solution includes the following components: 10 g / L copper, 80 g / L sulfuric acid, 1 g / L iron, 2 g / L molybdenum and water, and the temperature of the roughening solution is 20°C. The curing solution was used to cure the double-side surfaces of the roughened copper foil, and the curing solution includes the following components: 60 g / L copper, 60 g / L sulfuric acid, and the temperature of the curing solution is 40°C. The single-side roughened surface of the copper foil after curing was blackened using a blackening solution. The blackening solution includes the following components: 40 g / L copper, 100 g / L amino acid, 1 g / L iron, 2 g / L cobalt, 2 g / L vanadium, and the temperature of the blackening solution is 20°C.

[0115] The roughness of the roughened surface of the electronic copper foil obtained in the embodiment and the comparative example (Rz, in micrometers), the bonding strength between the roughened surface and the epoxy resin substrate after hot pressing at 200°C for 3 hours (in kg / cm), and the tensile strength of the electronic copper foil (in kg / mm 2 ), the elongation of the electronic copper foil and the oxidation condition of the electronic copper foil after baking at 200°C for 3h were tested, and the results are shown in Table 1.

[0116] Table 1

[0117]

[0118]

[0119] It can be seen from Table 1 that the roughened surface of the electronic copper foil in the embodiment has a smaller Rz and has good bonding strength with the substrate. At the same time, the blackened electronic copper foil has a higher tensile strength and a larger elongation, and has better anti-oxidation performance.

[0120] It should be understood that the present disclosure does not limit its application to the detailed structure and arrangement of the components proposed in the present disclosure. The present disclosure can have other embodiments and can be implemented and executed in a variety of ways. The aforementioned variations and modifications fall within the scope of the present disclosure. It should be understood that the present disclosure and the limited present disclosure extend to all alternative combinations of two or more individual features mentioned or evident in the text and / or the drawings. All of these different combinations constitute multiple alternative aspects of the present disclosure. The embodiments described in the present disclosure illustrate the best modes known for implementing the present disclosure and will enable those skilled in the art to utilize the present disclosure.

Claims

1. A method for preparing a blackened electronic copper foil, characterized in that: The steps include: Roughening the single-side surface of the original foil to form a single-side roughened surface, thereby obtaining a roughened copper foil; The single-side roughened surface of the roughened copper foil is subjected to blackening treatment using a blackening solution to obtain a blackened copper foil; the blackening solution comprises the following components: 15 g / L to 30 g / L copper, 0.5 g / L to 2 g / L molybdenum, 80 g / L to 150 g / L glucose, 0.5 g / L to 2 g / L citric acid, and water; Performing anti-oxidation treatment on both sides of the blackened copper foil to obtain an anti-oxidation copper foil; The single-side roughened surface of the oxidation-resistant copper foil is subjected to a silane coating treatment.

2. The method for preparing the blackened electronic copper foil according to claim 1, characterized in that: The pH value of the blackening solution is 2-6.

3. The method for preparing the blackened electronic copper foil according to claim 1, characterized in that: The temperature of the blackening solution is 20°C to 50°C.

4. The method for preparing the blackened electronic copper foil according to claim 1, characterized in that: The current density of the blackening treatment is 5A / dm 2 ~35A / dm 2 and / or, The blackening treatment time is 2s to 30s; The transmission speed of the roughened copper foil in the blackening treatment is 0.5 m / min to 14 m / min.

5. The method for preparing the blackened electronic copper foil according to claim 1, characterized in that: Using a roughening solution to roughen the single-side surface of the original foil to form a single-side roughened surface; The roughening solution includes the following components: 15 g / L to 40 g / L copper, 30 g / L to 60 g / L sulfuric acid, 1 g / L to 5 g / L phosphoric acid and water.

6. The method for preparing the blackened electronic copper foil according to claim 1, characterized in that: Using an anti-oxidation solution to perform anti-oxidation treatment on both sides of the blackened copper foil; The anti-oxidation solution comprises the following components: 1 g / L to 5 g / L of phytic acid, 1 g / L to 10 g / L of zinc, 1 g / L to 5 g / L of nickel, 0.1 g / L to 5 g / L of nitric acid and water.

7. The method for preparing the blackened electronic copper foil according to claim 1, characterized in that: Using a silane coating solution to perform a silane coating treatment on the single-side roughened surface of the anti-oxidation copper foil; The silane coating solution includes fluorotriethoxysilane and water.

8. The method for preparing a blackened electronic copper foil according to any one of claims 1 to 7, characterized in that: The preparation of the raw foil comprises the following steps: The raw foil is prepared by using a copper deposition solution under electrolytic conditions; The copper deposition solution includes the following components: 70 g / L to 100 g / L copper, 70 g / L to 100 g / L sulfuric acid, 1 g / L to 5 g / L brightener and water; the brightener includes polypropylene glycol, gelatin and hydroxymethyl cellulose, and the mass ratio of the polypropylene glycol, the gelatin and the hydroxymethyl cellulose is 1: (1.5 to 2.5): (0.2 to 0.8).

9. A blackened electronic copper foil, characterized in that: The method is prepared according to any one of claims 1 to 8.

10. An electronic product, characterized in that: It includes the blackened electronic copper foil as described in claim 9.

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