Solution for preparing carrier copper foil peeling layer and method for preparing carrier copper foil peeling layer

Abstract

The present disclosure relates to the technical field of carrier copper foil, and in particular to a solution for preparing a carrier copper foil stripping layer and a method for preparing a carrier copper foil stripping layer. The solution for preparing the carrier copper foil stripping layer includes mutually isolated potions A and B, wherein the potion A includes phosphate, and the phosphate includes at least one of zinc dihydrogen phosphate, calcium dihydrogen phosphate, manganese dihydrogen phosphate, iron dihydrogen phosphate, ammonium dihydrogen phosphate, lithium dihydrogen phosphate, sodium dihydrogen phosphate and potassium dihydrogen phosphate; the potion B includes a phosphide metal, and the phosphide metal includes at least one of molybdenum phosphide, zinc phosphide, nickel phosphide, chromium phosphide and potassium phosphide. The solution for preparing the carrier copper foil stripping layer can form a stable stripping layer on the carrier layer, which is convenient for the subsequent deposition of ultra-thin copper foil. At the same time, after the ultra-thin copper foil is prepared, the stripping layer can show good stripping performance and is easy to strip from the carrier layer.

Description

Technical Field

[0001] The present disclosure relates to the technical field of carrier copper foil, and in particular to a solution for preparing a peeling layer of a carrier copper foil and a method for preparing the peeling layer of the carrier copper foil. Background Art

[0002] With the rapid development of electronic technology, electronic products are developing towards miniaturization, lightness and high performance, and the requirements for electronic materials are getting higher and higher. As one of the important basic materials in the electronics industry, the performance of copper foil directly affects the quality and performance of electronic products. In high-end electronic products, the application of ultra-thin copper foil is becoming more and more extensive. However, in the preparation process of ultra-thin copper foil, how to form a stable peeling layer on the carrier layer and how to achieve good peeling performance after the preparation of ultra-thin copper foil are completed have always been the key issues restricting the production and application of ultra-thin copper foil.

[0003] First, the traditional method of generating a stripping layer usually adopts electrophoresis or sputtering technology to form a stripping layer by depositing a layer of metal (such as nickel, nickel-phosphorus alloy, nickel-cobalt alloy or chromium, etc.) on the surface of the supporting copper foil. In this process, the metal ions move toward the cathode under the action of the electric field and approach the cathode surface from multiple directions, and finally deposit to form a stripping layer. This multi-directional deposition process makes it difficult to achieve uniform coating thickness, especially on the surface of copper foil with complex shapes or large areas, which is prone to problems of excessive or insufficient local thickness, affecting the overall performance of the copper foil.

[0004] Secondly, the traditional electroplating process has great difficulty in controlling the uniformity and thickness of the coating. Due to the complex interaction of factors such as current density, electrolysis time and electrolyte composition during the electroplating process, it is difficult to ensure that each batch of copper foil produced has completely consistent peeling layer characteristics even under the best conditions. In addition, the uneven deposition of metal ions during the electroplating process will also cause changes in the microstructure of the copper foil surface, which in turn affects the mechanical strength and conductive properties of the copper foil.

[0005] Furthermore, the traditional peeling layer preparation method often requires a separate winding step after the copper foil is generated before anti-oxidation or passivation treatment can be performed. This not only prolongs the production cycle and increases production costs, but more importantly, the copper foil surface is prone to oxidation during the time interval between winding and treatment, resulting in changes in the crystalline profile, affecting the surface quality and performance of the copper foil. Especially in high-end applications, this change in surface quality is often fatal and cannot meet the requirements of high precision and high performance.

[0006] It should be noted that the information disclosed in the above background technology section is only used to enhance the understanding of the background of the present disclosure, and therefore may include information that does not constitute the prior art known to ordinary technicians in the field. Summary of the invention

[0007] According to a first aspect of the present disclosure, a solution for preparing a carrier copper foil stripping layer is provided, comprising a solution A and a solution B isolated from each other, wherein the solution A comprises a phosphate, and the phosphate comprises at least one of zinc dihydrogen phosphate, calcium dihydrogen phosphate, manganese dihydrogen phosphate, iron dihydrogen phosphate, ammonium dihydrogen phosphate, lithium dihydrogen phosphate, sodium dihydrogen phosphate and potassium dihydrogen phosphate; and the solution B comprises a metal phosphide, and the metal phosphide comprises at least one of molybdenum phosphide, zinc phosphide, nickel phosphide, chromium phosphide and potassium phosphide.

[0008] In an exemplary embodiment of the present disclosure, based on the above scheme, the molar ratio of the phosphorus element in the potion A to the phosphorus element in the potion B is 3-5:1.

[0009] In an exemplary embodiment of the present disclosure, based on the above-mentioned solution, in the medicine A, the concentration of the phosphate is 0.1 g / L~10 g / L.

[0010] In an exemplary embodiment of the present disclosure, based on the above-mentioned solution, in the liquid medicine B, the concentration of the metal phosphide is 0.2 g / L to 20 g / L.

[0011] In an exemplary embodiment of the present disclosure, based on the above scheme, the pH of the medicine A is 1-4. The pH of the medicine B is 1-6.

[0012] According to a second aspect of the present disclosure, a method for preparing a carrier copper foil peeling layer is provided, using the above-mentioned solution for preparing a carrier copper foil peeling layer, the method for preparing a carrier copper foil peeling layer comprises the steps of: using the solution A to perform a first brush plating on the surface of the carrier layer to form a phosphating film on the surface of the carrier layer; using the solution B to perform a second brush plating on the surface of the phosphating film away from the carrier layer to form a phosphide layer on the surface of the phosphating film.

[0013] In an exemplary embodiment of the present disclosure, based on the above-mentioned solution, the thickness of the phosphating film is 0.5 nm to 20 nm.

[0014] In an exemplary embodiment of the present disclosure, based on the above-mentioned solution, the thickness of the phosphide layer is 5 nm to 50 nm.

[0015] In an exemplary embodiment of the present disclosure, based on the above scheme, the temperature of the liquid medicine A is 20°C to 50°C, and / or,

[0016] The pH value of the medicine A is 1-4; and / or,

[0017] The temperature of the medicine B is 30°C to 50°C; and / or,

[0018] The pH value of the medicine B is 1-6.

[0019] In an exemplary embodiment of the present disclosure, based on the above solution, the first brush plating is non-electrical brush plating; and / or,

[0020] The second brush plating is charged pulse brush plating, and the current density of the second brush plating is 0.2A / square decimeter to 1A / square decimeter.

[0021] In an exemplary embodiment of the present disclosure, based on the above solution,

[0022] The first brush plating uses a titanium roller to brush plate the solution A onto the surface of the carrier layer to form the phosphating film; and / or,

[0023] The second brush plating uses a titanium electrode to brush plate the solution B onto the surface of the phosphating film away from the carrier layer.

[0024] It can be seen from the above technical solution that the present disclosure has at least one of the following advantages and positive effects:

[0025] 1. In the present disclosure, the solution for preparing the carrier copper foil stripping layer can form a stable stripping layer on the carrier layer, which is convenient for the subsequent deposition of ultra-thin copper foil. At the same time, after the ultra-thin copper foil is prepared, the stripping layer can show good stripping performance and is easy to strip from the carrier layer. Specifically, the phosphate in the solution A has good chemical stability and adhesion, and can react chemically with the surface of the carrier layer to form a dense phosphating film. The metal phosphide in the solution B has good conductivity and stripping performance, and can interact with the phosphating film to form a stable stripping layer structure, so that the ultra-thin copper foil can be easily stripped from the carrier layer after preparation.

[0026] 2. The method for preparing the solution for preparing the carrier copper foil peeling layer disclosed in the present invention is simple, low-cost, and easy to realize industrial production.

[0027] 3. The solution for preparing the carrier copper foil stripping layer disclosed in the present invention can be applied to the preparation of various carrier layers and ultra-thin copper foils, and has broad application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] 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.

[0029] Figure 1 It is a schematic structural diagram of the first brush plating device in the method for preparing the peeling layer in the embodiment of the present disclosure.

[0030] Figure 2 It is a schematic structural diagram of the second brush plating equipment in the method for preparing the peeling layer in the embodiment of the present disclosure.

[0031] Figure 3It is a structural schematic diagram of an integrated carrier copper foil production device in an embodiment of the present disclosure.

[0032] Figure 4 It is a schematic structural diagram of a carrier copper foil in an embodiment of the present disclosure.

[0033] Figure 5~Figure 8 Schematic diagram of the carrier copper foil and the peeling state in the embodiment of the present disclosure.

[0034] Fig. 9 3 is a surface structure diagram of the non-cathode roller surface (S surface) of the carrier copper foil in the embodiment of the present disclosure.

[0035] Fig.10 3 is a surface structure diagram of the cathode roller surface (M surface) of the carrier copper foil in the embodiment of the present disclosure.

[0036] The main components in the figure are described as follows:

[0037] 10. First brush plating equipment; 101. First brush plating tank; 102. Chemical A; 103. First titanium roller; 104. Conveying roller; 20. Second brush plating equipment; 201. Second brush plating tank; 202. Chemical B; 203. Second titanium roller; 204. Electrode; 30. First carrier layer; 1. Electrolysis device; 2. Stripping layer generating device; 3. Copper foil layer generating device; 4. Conveying roller group; 5. Terminal processing device; 6. Carrier copper foil; 61. Second carrier layer; 62. Stripping layer; 621. First brush plating layer; 622. Second brush plating layer; 63. Copper foil layer. DETAILED DESCRIPTION

[0038] 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.

[0039] In the related carrier copper foil stripping layer technology, the stripping performance of the stripping layer is poor, which makes it difficult to effectively strip the stripping layer. In order to solve this problem, the embodiment of the present disclosure provides a solution for preparing the carrier copper foil stripping layer, including mutually isolated potion A and potion B, the potion A includes phosphate, the phosphate includes at least one of zinc dihydrogen phosphate, calcium dihydrogen phosphate, manganese dihydrogen phosphate, iron dihydrogen phosphate, ammonium dihydrogen phosphate, lithium dihydrogen phosphate, sodium dihydrogen phosphate and potassium dihydrogen phosphate; the potion B includes a phosphide metal, the phosphide metal includes at least one of molybdenum phosphide, zinc phosphide, nickel phosphide, chromium phosphide and potassium phosphide.

[0040] In the present disclosure, the solution for preparing the carrier copper foil stripping layer can form a stable stripping layer on the carrier layer, which is convenient for the subsequent deposition of ultra-thin copper foil. At the same time, after the ultra-thin copper foil is prepared, the stripping layer can show good stripping performance and is easy to strip from the carrier layer. Specifically, the phosphate in the solution A has good chemical stability and adhesion, and can react chemically with the surface of the carrier layer to form a dense phosphating film. The metal phosphide in the solution B has good conductivity and stripping performance, and can interact with the phosphating film to form a stable stripping layer structure, so that the ultra-thin copper foil can be easily stripped from the carrier layer after preparation.

[0041] Different phosphates have different properties. For example, zinc dihydrogen phosphate has good corrosion resistance and adhesion; calcium dihydrogen phosphate can improve the hardness and wear resistance of the coating; manganese dihydrogen phosphate can enhance the oxidation resistance of the coating, etc. By selecting different phosphate combinations, the performance of the stripping layer can be adjusted according to specific application requirements.

[0042] Different metal phosphides also have different properties. For example, molybdenum phosphide has good electrical conductivity and high temperature resistance; zinc phosphide has good corrosion resistance and stripping performance; nickel phosphide can improve the hardness and wear resistance of the stripping layer, etc. By selecting different metal phosphides for combination, the performance of the stripping layer can be further optimized.

[0043] In an exemplary embodiment of the present disclosure, based on the above scheme, the molar ratio of the phosphorus element in the potion A to the phosphorus element in the potion B is 3 to 5: 1. Optionally, the molar ratio of the phosphorus element in the potion A to the phosphorus element in the potion B can be 3: 1, 3.5: 1, 4: 1, 4.5: 1, 5: 1. It is understandable that the molar ratio of the phosphorus element in the potion A to the phosphorus element in the potion B can also be other suitable selections within the range of 3 to 5: 1.

[0044] In an exemplary embodiment of the present disclosure, based on the above scheme, the concentration of the phosphate in the potion A is 0.1 g / L to 10 g / L. Optionally, the concentration of the phosphate in the potion A can be 0.1 g / L, 0.5 g / L, 1 g / L, 2 g / L, 5 g / L, 8 g / L, 10 g / L. It is understandable that the concentration of the phosphate in the potion A can also be other suitable selections within the range of 0.1 g / L to 10 g / L.

[0045] In an exemplary embodiment of the present disclosure, based on the above scheme, in the potion B, the concentration of the metal phosphide is 0.2 g / L to 20 g / L. Optionally, in the potion B, the concentration of the metal phosphide can be 0.2 g / L, 0.5 g / L, 1 g / L, 2 g / L, 5 g / L, 8 g / L, 10 g / L, 12 g / L, 15 g / L, 18 g / L, 20 g / L. It is understandable that the concentration of the metal phosphide in the potion B can also be other suitable selections within the range of 0.2 g / L to 20 g / L.

[0046] In an exemplary embodiment of the present disclosure, based on the above scheme, the pH of the medicine A is 1 to 4. Optionally, the pH of the medicine A can be 1, 2, 3, or 4. It is understood that other suitable choices can be made within the pH range of 1 to 4 for the medicine A. Optionally, the pH of the medicine A can be adjusted with phosphoric acid.

[0047] In an exemplary embodiment of the present disclosure, based on the above scheme, the pH of the medicine B is 1 to 6. Optionally, the pH of the medicine B can be 1, 2, 3, 4, 5, 6. It is understandable that the pH of the medicine B is in the range of 1 to 6. Optionally, the pH of the medicine B can be adjusted with phosphoric acid.

[0048] It is understood that in the potions of the present disclosure, the concentration of each component is expressed based on the volume of the potion, and the mass of each component is based on the concentration of the corresponding volume of the potion. For example, the concentration of phosphate in potion A represents the concentration of the mass of phosphate based on the volume of potion A. The concentration of metal phosphide in potion B represents the concentration of the mass of metal phosphide based on the volume of potion B.

[0049] Optionally, the solvent in both medicine solution A and medicine solution B is water.

[0050] According to a second aspect of the present disclosure, a method for preparing a carrier copper foil peeling layer is provided, using the above-mentioned solution for preparing a carrier copper foil peeling layer, the method for preparing a carrier copper foil peeling layer comprises the steps of: using the solution A to perform a first brush plating on the surface of the carrier layer to form a phosphating film on the surface of the carrier layer; using the solution B to perform a second brush plating on the surface of the phosphating film away from the carrier layer to form a phosphide layer on the surface of the phosphating film.

[0051] In the present disclosure, the formed phosphating film helps to reduce the adhesion between the copper foil layer and the carrier layer in the subsequent stripping process, thereby achieving smooth stripping of the copper foil layer, and improving the corrosion resistance and surface properties of the stripping layer, and enhancing its bonding with subsequent coatings or plating layers. The phosphide layer further enhances the corrosion resistance and electrical conductivity of the stripping layer, while improving the mechanical strength and adhesion of the stripping layer.

[0052] In the second preparation method of the present disclosure, liquid medicine A and liquid medicine B respectively form a phosphide film and a phosphide layer on the surface of the carrier layer in turn. The preparation method is simple and easy, does not need to rely on complex processes and expensive equipment, and is easy to promote.

[0053] Optionally, the material of the carrier layer in the present disclosure may be copper, aluminum, zinc, nickel or other materials that can be generated by electrolysis.

[0054] In some embodiments, the thickness of the phosphide film is 0.5nm~20nm, and the thickness of the phosphide layer is 5nm~50nm. If the thickness of the phosphide film is too small, it is difficult to provide a good foundation for the formation of the phosphide layer. If the thickness of the phosphide film is too large, the overall thickness of the stripping layer will be too large, which will increase the difficulty of stripping the stripping layer in the later stage. At the same time, if the thickness of the phosphide film is too large, it will also cause a large waste of resources and increase the manufacturing cost of the carrier copper foil stripping layer. Optionally, the thickness of the phosphide film can be 0.5nm, 1nm, 5nm, 8nm, 10nm, 12nm, 15nm, 18nm, 20nm. If the thickness of the phosphide layer is too small, the bonding force between the copper foil and the stripping layer may be reduced, affecting the preparation of the copper foil. If the thickness of the phosphide layer is too large, the overall thickness of the stripping layer will be too large, which will increase the difficulty of stripping the stripping layer in the later stage. At the same time, if the thickness of the phosphide layer is too large, it will also cause a large waste of resources and increase the manufacturing cost of the carrier copper foil stripping layer. Optionally, the thickness of the phosphide layer may be 5 nm, 10 nm, 15 nm, 20 nm, 30 nm, 40 nm, or 50 nm.

[0055] In an exemplary embodiment of the present disclosure, based on the above scheme, the temperature of the medicine A is 20°C to 50°C. Optionally, the temperature of the medicine A can be 20°C, 30°C, 40°C, or 50°C. The temperature of the medicine B is 30°C to 50°C. Optionally, the temperature of the medicine B can be 30°C, 40°C, or 50°C.

[0056] In an exemplary embodiment of the present disclosure, based on the above scheme, the first brush plating is non-electrified brush plating. During the first brush plating process, the phosphate in the solution A reacts chemically with the surface of the carrier layer to form a phosphating film. This non-electrified brush plating method can avoid direct contact between the electrode and the carrier layer, reduce damage to the carrier layer, and also improve the uniformity and density of the phosphating film. Optionally, the first brush plating uses a titanium roller to brush the solution A onto the surface of the carrier layer to form the phosphating film.

[0057] See also Figure 1, which shows a schematic structural diagram of the first brush plating device 10 in the peeling layer preparation method. The first carrier layer 30 is transferred to the first brush plating tank 101 by the action of the transfer roller 104. The first brush plating tank 101 contains a liquid medicine A 102. When the first carrier layer 30 is transferred to the first brush plating tank 101, the first titanium roller 103 brush-plates the liquid medicine A onto the surface of the first carrier layer 30 to form a phosphate film.

[0058] In an exemplary embodiment of the present disclosure, based on the above scheme, the second brush plating is charged pulse brush plating. During the second brush plating process, the phosphide metal in the solution B is deposited on the surface of the phosphide film under the action of the electric field to form a phosphide layer. This charged pulse brush plating method can improve the deposition speed and deposition quality, and can also control the thickness and structure of the phosphide layer.

[0059] Optionally, the pulse of pulse brush plating is any one or combination of positive pulse or negative pulse. Among them, pulse brush plating can refer to an electroplating technology that superimposes a specific waveform pulse (such as a rectangular pulse) on a fixed direct current so that the electroplating process varies within a wide range. Positive pulse brush plating can mean that during the electroplating process, the positive direction of the current is periodically connected and disconnected. Negative pulse brush plating can mean that during the electroplating process, the negative direction of the current is periodically connected and disconnected. Pulse brush plating can improve the quality of the coating, such as the flatness and adhesion of the coating.

[0060] In an exemplary embodiment of the present disclosure, the current density of the second brush plating is 0.2A / square decimeter to 1A / square decimeter. Optionally, the current density of the second brush plating can be 0.2A / square decimeter, 0.3A / square decimeter, 0.5A / square decimeter, 0.8A / square decimeter, 1A / square decimeter. Optionally, the second brush plating uses a titanium electrode to brush plate the solution B onto the surface of the phosphating film away from the carrier layer.

[0061] See also Figure 2 , which shows a schematic diagram of the structure of the second brush plating device 20 in the stripping layer preparation method. The first carrier layer 30 after passing through the first brush plating device 10 is then transferred to the second brush plating tank 201. The second brush plating tank 201 contains a liquid medicine B 202. When the first carrier layer 30 after passing through the first brush plating device 10 is transferred to the second brush plating tank 201, the second titanium roller 203 and the electrode 204 brush-plate the liquid medicine B to the surface of the phosphide film of the first carrier layer 30 to form a phosphide layer. It can be understood that during the second brush plating, the liquid medicine B overflows from the second brush plating tank 201 and is brush-plated by the second titanium roller 203 to the surface of the phosphide film of the first carrier layer 30 to form a phosphide layer.

[0062] In some embodiments, the carrier copper foil can be prepared by the following integrated carrier copper foil production equipment. Figure 3 As shown, the integrated carrier copper foil production equipment includes an electrolytic device 1, a peeling layer generating device 2, a copper foil layer generating device 3 and a conveying roller group 4. Among them, the electrolytic device is used to generate the carrier layer; the peeling layer generating device is used to prepare the peeling layer on the preset surface of the carrier layer; the copper foil layer generating device is arranged at the rear side of the peeling layer generating device, and is used to prepare the copper foil layer on the surface of the peeling layer away from the carrier layer; the conveying roller group is connected between the electrolytic device and the peeling layer generating device, and is used to transfer the carrier layer to the peeling layer generating device within a predetermined time. It can be understood that in the copper foil generating device, the copper foil layer is prepared on the surface of the peeling layer away from the carrier layer by the above-mentioned copper electrodeposition liquid.

[0063] The carrier copper foil can be a single-sided rough copper foil or a double-sided smooth copper foil. Conventional production equipment can only form a single-sided rough copper foil, but the integrated carrier copper foil production equipment disclosed in the present invention can form copper foil on both sides of the carrier layer to obtain a carrier copper foil with double-sided smooth copper foil.

[0064] The integrated carrier copper foil production equipment disclosed in the present invention can continuously produce three key processes, namely, foil production, peeling layer preparation, and main copper foil production, and omits the winding and unwinding logistics links between work sections in the traditional process. The key to this innovative technology is the process of online preparation of the peeling layer. In the existing production process, it is necessary to configure a sputtering or electrophoresis device outside the foil production line to form the peeling layer. Due to process limitations, it is impossible to achieve online preparation of the peeling layer.

[0065] The carrier copper foil of the present disclosure is further described below.

[0066] Figure 4 The schematic diagram of the structure of a carrier copper foil 6 in the embodiment of the present disclosure is shown, which specifically includes a second carrier layer 61, a peeling layer 62 and a copper foil layer 63. It can be understood that Figure 4 In the figure, the S surface represents the non-cathode roller surface of the carrier copper foil, which is also called the non-pressing surface or S surface (Smooth surface). The M surface represents the cathode roller surface of the carrier copper foil, which is also called the pressing surface or M surface (Matte surface). In this embodiment, the peeling layer 62 is formed on the non-cathode roller surface of the second carrier layer 61. It can be seen that in this application, the method for preparing a strippable copper layer on the non-cathode roller surface is compared with the method of preparing a strippable copper layer on the cathode roller surface in the prior art, and the present method has the following significant technical advantages and effects:

[0067] Specifically, the preparation of the stripping layer on the non-cathode roller surface can make the back of the carrier copper foil finished product smooth, so as to obtain a double-sided smooth carrier copper foil product, which provides greater flexibility for the application of copper foil. When preparing the strippable copper layer on the cathode roller surface, it is difficult to generate the required roughness on the other side of the copper foil (non-cathode roller surface) due to the smooth surface of the cathode roller. This limits the performance of copper foil in certain applications. By preparing the strippable copper layer on the non-cathode roller surface, we can use specific process conditions (such as brush plating technology) to generate the required roughness on this side. This not only improves the adhesion of the copper foil, but also enhances the stability of the carrier layer in subsequent processing. For example, in the manufacturing process of printed circuit boards, the increase in roughness can significantly improve the bonding strength between the carrier layer copper foil and the substrate, and reduce the risk of peeling after lamination. As a result, the carrier layer can still be used as copper foil.

[0068] By preparing a strippable copper layer on the non-cathode roller surface and using a double-stripping technique to generate a double stripping layer, the thickness and roughness of the coating can be controlled more accurately. Specifically, the first brush plating generates a phosphating film, and the second brush plating generates a phosphating metal layer. This method not only ensures the uniformity of the coating, but also achieves fine control of the roughness by adjusting the pressure, speed and current of the brush plating roller. This is particularly important in high-end applications, because uniform coating and controllable roughness can significantly improve the performance and reliability of copper foil.

[0069] This application not only solves the shortcomings of the prior art in generating a double-sided optical carrier layer and ensuring the roughness of the back of the carrier layer by preparing a strippable copper layer on the non-cathode roller surface and combining the double-stripping layer technology, but also significantly improves the performance and application range of the copper foil by precisely controlling the uniformity and roughness of the coating. This provides a more reliable and efficient solution for the manufacture of high-end electronic products.

[0070] In this embodiment, the stripping layer 62 includes a first brush-plated layer 621 formed by the first brush plating and a second brush-plated layer 622 formed by the second brush plating. Specifically, the first brush-plated layer 621 is a phosphating film formed by using liquid medicine A, and the second brush-plated layer 622 is a phosphide layer formed by using liquid medicine B. In the process of forming the phosphide layer, an anti-oxidation treatment reaction is also included with the non-cathode roller surface of the carrier layer, and the non-cathode roller surface of the carrier layer can also be surface treated.

[0071] As shown in the figure, in the implementation of the present application, the stripping layer 62 includes a first brush-plated layer 621 formed by the first brush-plating and a second brush-plated layer 622 formed by the second brush-plating. By preparing the stripping layer 62 on the non-cathode roller surface, the first brush-plated layer 621 is formed into a phosphating film using a liquid medicine A. The formation of the phosphating film not only provides a good foundation for the subsequent second brush-plated layer 622, but also can improve the surface characteristics of the non-cathode roller surface of the carrier layer to a certain extent, and improve its uniformity and flatness.

[0072] The second brush plating layer 622 uses liquid medicine B to form a phosphide layer. During the formation of the phosphide layer, the metal ions in liquid medicine B are reduced and deposited on the surface of the phosphide film to form a uniform phosphide layer. This process not only ensures the thickness and uniformity of the stripping layer, but also achieves fine control of the roughness of the phosphide layer by adjusting the pressure, speed and current of the brush plating roller.

[0073] During the formation of the phosphide layer, an anti-oxidation treatment reaction occurs between the components in the solution B and the non-cathode roller surface of the carrier layer. This reaction effectively prevents the oxidation of the non-cathode roller surface of the carrier layer during preparation and storage, ensuring the quality and performance of the copper foil surface.

[0074] While the phosphide layer is being generated, the non-cathode roller surface of the carrier layer can also be surface treated. By adjusting the composition of solution B and brush plating conditions, the roughness and adhesion of the non-cathode roller surface of the carrier layer can be further improved, thereby improving its stability and reliability in subsequent processing.

[0075] This embodiment prepares the peeling layer 62 on the non-cathode roller surface, combines the double brush plating technology and anti-oxidation treatment, not only ensures the uniformity and roughness of the peeling layer, but also improves the surface quality and performance of the copper foil. This provides a more reliable and efficient solution for the manufacture of high-end electronic products.

[0076] In the embodiments of the present application, the present application mainly proposes a technical solution for forming a peeling layer by depositing a solvent within a range. It is obvious to those skilled in the art that the deposition formation can have various variations, including but not limited to immersion, dip coating, brush coating, spray coating, overcoating, plating, roller plating, hanging plating and other methods to apply the solvent to the preset surface of the carrier layer. In addition, the equipment using the above scheme is not limited to a one-piece machine for preparing the raw foil of the carrier foil and the post-processing equipment online or a segmented non-one-piece machine for the raw foil and the post-processing.

[0077] Through these different deposition methods and equipment configurations, the technical solution of the present application can flexibly adapt to different production and process requirements, ensuring that a high-quality peeling layer is prepared on the preset surface of the carrier layer. Regardless of which specific deposition method or equipment type is used, as long as the peeling layer is prepared on the preset surface of the carrier layer by the above method, it falls within the protection scope of the present application.

[0078] The thickness of the copper foil layer is 0.5μm~5μm. The copper foil layer with a thickness in this range can meet the thickness requirements of electronic products for ultra-thin copper foil layers. At the same time, the copper foil layer has a high elongation, so it has a good application prospect. Optionally, the thickness of the copper foil layer can be 0.5μm, 1μm, 1.5μm, 2μm, 2.5μm, 3μm, 3.5μm, 4μm, 4.5μm, 5μm, etc. It is understandable that the thickness of the copper foil layer can also be other suitable choices within the range of 0.5μm~5μm.

[0079] When the thickness of the copper foil layer is 1.5 μm, the unit area weight of the carrier copper foil can be 18 g / m 2 Up to 22g / m 2 When the thickness of the copper foil layer is 3 μm, the unit area weight of the carrier copper foil can be 31 g / m 2 Up to 35g / m 2 When the thickness of the copper foil layer is 5 μm, the unit area weight of the carrier copper foil can be 48 g / m 2 Up to 54g / m 2 range; of course, in other embodiments of the present disclosure, the unit area weight of the carrier copper foil can also be other suitable values. Exemplarily, the roughness of the copper foil layer on the side close to the carrier layer is less than 2μm, and the roughness of the copper foil layer on the side away from the carrier layer is also less than 2μm, the thickness of the carrier layer is 18μm, and the peel strength of the peeling layer at room temperature is not less than 3g / cm, and not more than 30g / cm. The carrier copper foil has the characteristics of ultra-thinness, low roughness, high peel strength and good etching properties, and is suitable for other suitable application scenarios such as high-frequency and high-speed copper clad laminates, flexible printed circuit boards, and high-density interconnect technology boards.

[0080] Figure 5~Figure 8 Schematic diagram showing the carrier copper foil and peeling state in the embodiment of the present disclosure. Figure 5~Figure 8 It can be seen that the carrier copper foil in the present disclosure has good peeling performance and no residue is left after peeling. Through testing, the width of the carrier copper foil in the present disclosure can reach 1295mm, and the width, thickness, etc. have good customizability, which can effectively meet the different needs of consumers.

[0081] The performance indicators of the carrier copper foil of the present invention are tested, and the results are shown in the following table. It can be seen that the carrier copper foil of the present invention has excellent thickness, roughness, peel strength, etc. and has good customizability.

[0082]

[0083] Example 1

[0084] In this embodiment, the component of medicine A is: 0.1 g / L zinc dihydrogen phosphate.

[0085] The components of potion B are: 0.2g / L chromium phosphide.

[0086] The preparation method of the carrier copper foil in this embodiment is:

[0087] S101: Surface treatment is performed on the carrier copper layer to remove oil stains, impurities, etc. on the surface.

[0088] S102: Adoption Figure 1 The first brush plating device and the chemical solution A shown perform the first brush plating without charge on the surface of the carrier layer to form a phosphate film on the surface of the carrier layer. The temperature of the chemical solution A is 20° C., and the pH value of the chemical solution A is 1. The speed of the first brush plating is 1 m / min, and the time of the first brush plating is 5S.

[0089] S103: Adoption Figure 2 The second brush plating device and the chemical solution B shown perform a charged second brush plating on the surface of the phosphating film away from the carrier layer to form a phosphide layer on the surface of the phosphating film. The temperature of the chemical solution B is 30°C, and the pH value of the chemical solution B is 1. The second pulse period is 1:6, the current density is 0.2A / square decimeter, the speed of the second brush plating is 1m / min, and the time of the second brush plating is 10min.

[0090] S104: depositing an ultra-thin copper layer with a thickness of 5 microns on the surface of the phosphide layer.

[0091] Further, Figure 9~Figure 10 The surface structures of the non-cathode roller surface (S surface) and the cathode roller surface (M surface) of the carrier copper foil in this embodiment are shown respectively. It can be seen that both the S surface and the M surface of the carrier copper foil disclosed in the present invention have a relatively uniform surface structure, that is, have a relatively uniform roughness.

[0092] Example 2

[0093] Compared with Example 1, Example 2 is different in that: the component of potion A is: 5 g / L zinc dihydrogen phosphate. The component of potion B is: 10 g / L chromium phosphide.

[0094] Example 3

[0095] Compared with Example 1, Example 3 is different in that: the component of potion A is: 10 g / L zinc dihydrogen phosphate. The component of potion B is: 20 g / L chromium phosphide.

[0096] Comparative Example 1

[0097] Compared with Example 1, Comparative Example 1 is different in that the first brush plating is not included.

[0098] Comparative Example 2

[0099] Compared with Example 1, Comparative Example 2 is different in that the second brush plating is not included.

[0100] Comparative Example 3

[0101] The preparation method of the carrier copper foil in Comparative Example 3 is:

[0102] S101: Surface treatment is performed on the carrier copper layer to remove oil stains, impurities, etc. on the surface.

[0103] S102: preparing a peeling layer on the surface of the carrier layer by electrophoresis.

[0104] S103: depositing an ultra-thin copper layer with a thickness of 5 microns on the surface of the peeling layer.

[0105] Comparative Example 4

[0106] The preparation method of the carrier copper foil in Comparative Example 4 is:

[0107] S101: Surface treatment is performed on the carrier copper layer to remove oil stains, impurities, etc. on the surface.

[0108] S102: preparing a peeling layer on the surface of the carrier layer by sputtering.

[0109] S103: depositing an ultra-thin copper layer with a thickness of 5 microns on the surface of the peeling layer.

[0110] Test Case

[0111] The copper layer of the carrier copper foil prepared in the examples and comparative examples was attached to the surface of the substrate. Then the peeling force of the peeling layer and the copper foil was tested, as well as the residual state of the peeling layer. Peeling force test conditions: 200°C, 20kg / cm 2 The pressing was carried out for 3 hours. The results are shown in the following table.

[0112]

[0113] As can be seen from the above table, in Examples 1-3, the peeling force when peeling the peeling layer from the copper foil is less than that in Comparative Examples 1-4, indicating that the peeling layer obtained by the peeling layer solution disclosed in the present invention is easier to peel from the copper foil. In addition, when peeling the layer, there is no residue in the peeling layer in Examples 1-3, and there is a small amount of residue in the peeling layer in Comparative Examples 1-4, indicating that the peeling layer obtained by the peeling layer solution disclosed in the present invention is not only easier to peel, but also has no residue after peeling, which will not affect the subsequent use of the ultra-thin copper layer.

[0114] 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 carrier copper foil peeling layer, characterized in that: A solution for preparing a carrier copper foil stripping layer is used, the solution for preparing a carrier copper foil stripping layer comprises a mutually isolated solution A and a solution B, the solution A comprises a phosphate, the phosphate comprises at least one of zinc dihydrogen phosphate, calcium dihydrogen phosphate, manganese dihydrogen phosphate, iron dihydrogen phosphate, ammonium dihydrogen phosphate, lithium dihydrogen phosphate, sodium dihydrogen phosphate and potassium dihydrogen phosphate; the solution B comprises a metal phosphide, the metal phosphide comprises at least one of molybdenum phosphide, zinc phosphide, nickel phosphide and chromium phosphide; in the solution A, the concentration of the phosphate is 1 g / L to 10 g / L; in the solution B, the concentration of the metal phosphide is 0.2 g / L to 20 g / L; the pH of the solution A is 1 to 4; and / or the pH of the solution B is 1 to 6; The method for preparing the carrier copper foil peeling layer comprises the following steps: Using the liquid medicine A to perform a first brush plating on the surface of the carrier layer to form a phosphating film on the surface of the carrier layer; Using the chemical solution B to perform a second brush plating on the surface of the phosphating film away from the carrier layer to form a phosphide layer on the surface of the phosphating film; The thickness of the phosphide film is 0.5 nm to 20 nm and the thickness of the phosphide layer is 5 nm to 50 nm.

2. The method for preparing a carrier copper foil peeling layer according to claim 1, characterized in that: The molar ratio of the phosphorus element in the potion A to the phosphorus element in the potion B is 3-5:

1.

3. The method for preparing a carrier copper foil peeling layer according to claim 1, characterized in that: The temperature of the medicine A is 20°C to 50°C; and / or, The temperature of the medicine B is 30°C to 50°C.

4. The method for preparing a carrier copper foil peeling layer according to claim 1, characterized in that: The first brush plating is non-electrical brush plating; and / or, The second brush plating is charged pulse brush plating, and the current density of the second brush plating is 0.2A / square decimeter to 1A / square decimeter.

5. The method for preparing a carrier copper foil peeling layer according to any one of claims 1 to 4, characterized in that: The first brush plating uses a titanium roller to brush the solution A onto the surface of the carrier layer to form the phosphate film; and / or, The second brush plating uses a titanium electrode to brush plate the solution B onto the surface of the phosphating film away from the carrier layer.

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