A method for preparing copper electrodeposition solution and carrier copper foil

Abstract

The present disclosure relates to the technical field of carrier copper foil, and in particular to a copper electrodeposition solution and a method for preparing a carrier copper foil. The copper electrodeposition solution comprises the following components: phytic acid 20 g / L to 100 g / L, copper carbonate 10 g / L to 80 g / L, tartaric acid additive 0.1 g / L to 1 g / L, and a solvent. The pH value of the copper electrodeposition solution is 0.5 to 3. By combining phytic acid, copper carbonate, and tartaric acid additives at appropriate concentrations, and under the condition of a pH value of 0.5 to 3, copper grains with smaller sizes and uniform distribution can be obtained, and the number of grain boundaries can be increased. In the deformation process of the copper foil, the grain boundaries can play a role in coordinating the deformation, making the material more susceptible to plastic deformation, thereby improving the elongation of ultra-thin copper.

Description

Technical Field

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

[0002] With the continuous development of electronic products, the performance requirements for each component in the product are getting higher and higher. In electronic products, copper foil is an important basic component. However, the thickness of copper foil is difficult to reduce, which restricts the further improvement of the performance of electronic products.

[0003] Based on this, carrier copper foil came into being. Carrier copper foil is also called peelable copper foil. Its characteristic is that it has one or more carrier layers to support the ultra-thin copper foil layer. After the carrier copper foil is applied to electronic products, the carrier layer and the ultra-thin copper foil layer are separated, and the ultra-thin copper foil layer can be transferred to the electronic product.

[0004] In the related art, the elongation of the ultra-thin copper foil layer is low, which restricts the use of the ultra-thin copper foil. Therefore, it is of great significance to improve the elongation of the ultra-thin copper foil.

[0005] 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

[0006] According to a first aspect of the present disclosure, a copper electrodeposition solution is provided, comprising the following components: 20 g / L to 100 g / L of phytic acid, 10 g / L to 80 g / L of copper carbonate, 0.1 g / L to 1 g / L of tartaric acid additive, and a solvent; the pH value of the copper electrodeposition solution is 0.5 to 3.

[0007] In an exemplary embodiment of the present disclosure, based on the above scheme, the solvent is water.

[0008] According to a second aspect of the present disclosure, a method for preparing a carrier copper foil is provided, comprising the following steps:

[0009] forming a peeling layer on the surface of the carrier layer to obtain a pre-finished product;

[0010] The pre-finished product is subjected to an electroplating treatment using the copper electroplating solution of the first aspect, so as to deposit a copper foil layer on the surface of the release layer away from the carrier layer.

[0011] In an exemplary embodiment of the present disclosure, based on the above-mentioned solution, the temperature of the copper electrodeposition solution during the electrodeposition process is 35° C. to 60° C.

[0012] In an exemplary embodiment of the present disclosure, based on the above scheme, the rate of the electrodeposition process is 0.3 m / min to 1.2 m / min.

[0013] In an exemplary embodiment of the present disclosure, based on the above scheme, the current density of the electrodeposition process is 1A / dm 2 ~10A / dm 2 .

[0014] In an exemplary embodiment of the present disclosure, based on the above solution, the thickness of the copper foil layer is 0.5 μm to 5 μm.

[0015] It can be seen from the above technical solution that the present disclosure has at least one of the following advantages and positive effects:

[0016] The copper electrodeposition solution disclosed in the present invention includes the following components: phytic acid 20g / L~100g / L, copper carbonate 10g / L~80g / L, tartaric acid additive 0.1g / L~1g / L and solvent. The pH value of the copper electrodeposition solution is 0.5~3. By combining phytic acid, copper carbonate and tartaric acid additives at appropriate concentrations and under the condition of a pH value of 0.5~3, copper grains with smaller size and uniform distribution can be obtained, and the number of grain boundaries can be increased. In the deformation process of copper foil, the grain boundaries can play a role in coordinating deformation, making the material more susceptible to plastic deformation, thereby improving the elongation of ultra-thin copper. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] 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.

[0018] Figure 1 It is a structural schematic diagram of an integrated carrier copper foil production device in an embodiment of the present disclosure.

[0019] Figure 2 It is a schematic structural diagram of a carrier copper foil in an embodiment of the present disclosure.

[0020] Figure 3~Figure 6 Schematic diagram of the carrier copper foil and the peeling state in the embodiment of the present disclosure.

[0021] The main components in the figure are described as follows:

[0022] 1. Electrolysis device; 2. Stripping layer generating device; 3. Copper foil generating device; 4. Conveying roller group; 5. Terminal processing device. 6. Carrier copper foil; 61. Carrier layer; 62. Stripping layer; 621. First brush plating layer; 622. Second brush plating layer; 63. Copper foil layer. DETAILED DESCRIPTION

[0023] 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.

[0024] In the related copper electrodeposition technology, the elongation of the ultra-thin copper foil obtained by electrodeposition is low. In order to solve this technical problem, the embodiment of the present disclosure provides a copper electrodeposition solution. The copper electrodeposition solution includes the following components: phytic acid 20g / L~100g / L, copper carbonate 10g / L~80g / L, tartaric acid additive 0.1g / L~1g / L and solvent. The pH value of the copper electrodeposition solution is 0.5~3. By combining phytic acid, tartaric acid additive and copper carbonate at appropriate concentrations, and under the condition of a pH value of 0.5~3, copper grains with smaller size and uniform distribution can be obtained, and the number of grain boundaries can be increased. In the deformation process of the copper foil, the grain boundary can play a role in coordinating the deformation, making the material more susceptible to plastic deformation, thereby improving the elongation of ultra-thin copper.

[0025] Furthermore, copper carbonate can be used as a supply source of copper ions to continuously and stably provide copper ions for electrodeposition, ensuring the normal growth of copper foil. The rate of copper ion release is relatively stable, which helps to maintain the smooth progress of the electrodeposition process. Phytic acid and tartaric acid additives can form complexes with copper ions, synergistically control the deposition rate of copper ions, adjust the concentration and existence form of copper ions in the electrodeposition solution, and make the deposition of copper ions on the cathode surface more uniform and delicate, thereby obtaining a copper foil coating with denser crystals and improving its quality and performance.

[0026] In addition, tartaric acid additives can be used as grain refiners to promote the refinement of copper grains, making the microstructure of the copper foil more uniform, thereby increasing the elongation of the ultra-thin copper foil, making it more suitable for applications with high requirements on material performance, such as high-performance electronic devices.

[0027] At the same time, the tartaric acid additive can play the role of buffering the pH of the solution and maintain the relative stability of the pH value of the electrodeposition solution. During the electrodeposition process, as copper ions continue to deposit, the pH value of the solution may change, and the tartaric acid additive can slow down the fluctuation of the pH value through its own acid-base balance, providing a stable chemical environment for the electrodeposition reaction, thereby ensuring the quality and performance stability of the ultra-thin copper foil.

[0028] Furthermore, during the electrodeposition process, some impurity ions may exist, and the tartaric acid additive can react with these impurity ions to reduce the adsorption and deposition of the impurity ions on the cathode surface, thereby reducing the impact of impurities on the quality of the ultra-thin copper foil and improving the purity of the ultra-thin copper foil.

[0029] It can be understood that in the copper electrolyte of the present disclosure, the concentration of each component is expressed based on the volume of the copper electrolyte, and the mass of each component is based on the concentration of the volume of the copper electrolyte.

[0030] For example, the concentration of phytic acid represents the concentration of the mass of phytic acid based on the volume of the copper electrolyte. Optionally, the concentration of phytic acid can be, but is not limited to, 20 g / L, 25 g / L, 30 g / L, 35 g / L, 40 g / L, 45 g / L, 50 g / L, 55 g / L, 60 g / L, 65 g / L, 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 phytic acid can also be other suitable selections within the range of 20 g / L to 100 g / L.

[0031] For example, the concentration of copper carbonate represents the concentration of the mass of copper carbonate based on the volume of copper electrolyte. Optionally, the concentration of copper carbonate can be but is not limited to 10g / L, 15g / L, 20g / L, 25g / L, 30g / L, 35g / L, 40g / L, 45g / L, 50g / L, 55g / L, 60g / L, 65g / L, 70g / L, 75g / L, 80g / L. It is understandable that the concentration of copper carbonate can also be other suitable selections within the range of 10g / L to 80g / L.

[0032] In some embodiments, the pH value of the copper electrodeposition solution may be, but is not limited to, 0.5, 0.8, 1, 1.2, 1.5, 1.8, 2, 2.2, 2.5, 2.8, or 3. It is understood that the pH value of the copper electrodeposition solution may also be selected in the range of 0.5 to 3. The pH value of the copper electrodeposition solution combined with phytic acid and copper carbonate can produce fine and uniform copper particles by electrodeposition, so that the ultra-thin copper foil layer has a higher elongation.

[0033] It is understood that the concentration of the tartaric acid additive represents the concentration of the mass of the additive based on the volume of the copper electrolyte. Optionally, the concentration of the tartaric acid additive can be 0.1g / L, 0.2g / L, 0.3g / L, 0.4g / L, 0.5g / L, 0.6g / L, 0.7g / L, 0.8g / L, 0.9g / L, 1g / L. It is understood that the concentration of the tartaric acid additive can also be other suitable selections within the range of 0.1g / L~1g / L.

[0034] In some embodiments, the solvent is water.

[0035] Another embodiment of the present disclosure provides a method for preparing a carrier copper foil. The method for preparing the carrier copper foil comprises the following steps: forming a peeling layer on the surface of a carrier layer to obtain a pre-finished product. The pre-finished product is subjected to an electroplating treatment using the copper electroplating liquid to deposit a copper foil layer on the surface of the peeling layer away from the carrier layer. The preparation method can obtain an ultra-thin copper foil layer with high elongation, thereby broadening the scope of use of the carrier copper foil.

[0036] In some embodiments, the temperature of the copper electrodeposition liquid during the electrodeposition treatment is 35°C to 60°C. If the temperature of the copper electrodeposition liquid is too low, it is difficult to obtain a good electrodeposition effect. If the temperature of the copper electrodeposition liquid is too high, on the one hand, it will produce higher energy consumption, and on the other hand, it will make the electrodeposition speed too fast, which increases the risk of uneven accumulation of copper particles. Optionally, the temperature of the copper electrodeposition liquid during the electrodeposition treatment is 35°C, 40°C, 45°C, 50°C, 55°C, or 60°C. It is understandable that the temperature of the copper electrodeposition liquid during the electrodeposition treatment can also be selected in the range of 35°C to 60°C.

[0037] In some embodiments, the rate of the electrodeposition treatment is 0.3m / min~1.2m / min. If the rate of the electrodeposition treatment is too high, it is difficult to obtain a copper foil layer that meets the thickness requirements. If the rate of the electrodeposition treatment is too low, the thickness of the copper foil layer may be too large, which is difficult to meet the thickness requirements of the ultra-thin copper foil, and will also cause more waste of resources. Optionally, the rate of the electrodeposition treatment can be 0.3m / min, 0.4m / min, 0.5m / min, 0.6m / min, 0.7m / min, 0.8m / min, 0.9m / min, 1m / min, 1.1m / min, 1.2m / min. It is understandable that the rate of the electrodeposition treatment can also be other suitable selections within the range of 0.3m / min~1.2m / min.

[0038] In some embodiments, the current density of the electrodeposition process is 1 A / dm 2 ~10A / dm 2 If the current density of the electroplating treatment is too small, it is difficult to obtain a high electroplating efficiency. If the current density of the electroplating treatment is too large, it is difficult to obtain a copper foil layer with good consistency. Optionally, the current density of the electroplating treatment can be 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 / dm2 It is understood that the current density of the electrodeposition process can also be 1A / dm 2 ~10A / dm 2 Make other appropriate choices within the scope.

[0039] In some embodiments, the carrier copper foil can be prepared by the following integrated carrier copper foil production equipment. Figure 1 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.

[0040] 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.

[0041] It is understood that the electrolytic device may refer to a device for depositing a carrier layer on the cathode surface through an electrochemical deposition process. The stripping layer generating device may be used to form an easily strippable intermediate layer on the preset surface of the carrier layer. The stripping layer serves as an intermediate medium between the copper foil layer and the carrier layer, so that the copper foil layer can be relatively easily stripped from the carrier layer. The copper foil layer generating device may refer to a device for forming a layer of copper foil on the stripping layer by electroplating or electrodeposition. The conveying roller group may refer to a component connecting the electrolytic device and the stripping layer generating device, which is used to transfer the carrier layer from the electrolytic device to the stripping layer generating device within a predetermined time, thereby reducing the pause and waiting time in the production process.

[0042] In addition, the conveying roller group transfers the carrier layer to the peeling layer generating device within a predetermined time, wherein the predetermined time does not exceed 20 minutes. Exemplarily, the predetermined time may be between 1 minute and 5 minutes, and the production line distance between the discharge port of the electrolysis device and the feed port of the peeling layer generating device does not exceed 3 meters. Exemplarily, the production line distance between the discharge port of the electrolysis device and the feed port of the peeling layer generating device may be between 1 meter and 2 meters.

[0043] The material of the carrier layer in the embodiment of the present disclosure can be copper, aluminum, zinc, nickel or other materials that can be generated by electrolysis. Exemplarily, the integrated carrier copper foil production equipment also includes an end processing device 5. The end processing device is located at the end of the foil production line. Exemplarily, the end processing can be a winding mechanism for neatly winding the continuously produced carrier copper foil into a roll for storage, transportation and subsequent use. Exemplarily, the end processing can be a transition roller for transferring the foil delivered by the copper foil layer generating device to a subsequent processing device for processing.

[0044] In some embodiments, forming a peeling layer on the surface of the carrier layer comprises the following steps: performing a first brush plating on the surface of the carrier layer using a phosphating solution to form a phosphating film on the surface of the carrier layer. Performing a second brush plating on the surface of the phosphating film away from the carrier layer using a phosphating metal to form a phosphide layer on the surface of the phosphating film. Optionally, the phosphating solution 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 phosphating metal comprises at least one of molybdenum phosphide, zinc phosphide, nickel phosphide, chromium phosphide and potassium phosphide. In some embodiments, the first brush plating is uncharged; the second brush plating is charged.

[0045] Correspondingly, the stripping layer generating device includes a first brush plating component and a second brush plating component, wherein the first brush plating component is used to perform a first brush plating on a preset surface of a carrier layer using a phosphating liquid to generate a phosphating film; the second brush plating component is used to perform a second brush plating on the phosphating film using a phosphating metal to obtain a stripping layer, and the second brush plating component is after the first brush plating component. Among them, the first brush plating component can be used to brush plate one or more layers of a specific material, such as a phosphating film, on the surface of the carrier layer, and the brush plating process of the first brush plating component is not charged, and 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 second brush plating component can be used to perform brush plating on the phosphating film formed by the first brush plating component to form a phosphide layer, and the brush plating process of the second brush plating component is charged. The phosphide layer further enhances the corrosion resistance and electrical conductivity of the stripping layer, and at the same time improves the mechanical strength and adhesion of the stripping layer.

[0046] In some embodiments, the brush plating method of the brush plating component is pulse brush plating, and the pulse of the pulse brush plating is any one or a combination of positive pulses or negative pulses. Among them, pulse brush plating can refer to an electroplating technology that superimposes a specific waveform 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.

[0047] In some embodiments, the electrolysis device includes an electrodeposition tank, a titanium cathode roller, and a stripping roller. The electrodeposition tank can be used to place an electrolyte; the titanium cathode roller can be used to deposit metal ions in the electrolysis process of the electrolyte to generate a carrier layer; and the stripping roller can be used to strip the carrier layer from the titanium cathode roller. Exemplarily, when the carrier layer is copper, the electrolyte can be a copper sulfate solution. Exemplarily, when the carrier layer is aluminum, the electrolyte can be an aluminum sulfate solution.

[0048] The embodiment of the present disclosure also provides a method for preparing an integrated carrier copper foil, and the method for preparing an integrated copper foil specifically comprises the following steps:

[0049] Step S210, performing surface treatment on the raw foil surface of the electrolysis device to obtain the raw foil surface with preset copper foil metallographic structure parameters.

[0050] Step S220 , preparing a carrier layer based on the raw foil surface of the electrolysis device.

[0051] Step S230, brush plating the carrier layer to prepare a peeling layer on a preset surface of the carrier layer. Specifically, forming the peeling layer on the surface of the carrier layer includes the following steps: first brush plating the surface of the carrier layer with a phosphating solution to form a phosphating film on the surface of the carrier layer; and second brush plating the surface of the phosphating film away from the carrier layer with a phosphating metal to form a phosphide layer on the surface of the phosphating film. It is understood that the product is subjected to surface anti-oxidation treatment after the brush plating treatment.

[0052] Step S240, electroplating the foil after brush plating to prepare a copper foil layer on the side of the stripping layer away from the carrier layer to obtain a carrier copper foil. When preparing the copper foil layer, the copper electroplating solution includes the following components: phytic acid 20g / L~100g / L, copper carbonate 10g / L~80g / L, tartaric acid additive 0.1g / L~1g / L and solvent. The pH value of the copper electroplating solution is 0.5~3.

[0053] Among them, the raw foil surface can represent the surface of the titanium cathode roller in the electrolysis device, which can be made of titanium material and is used to provide an adhesion surface for metal ions on the cathode by electrolysis or other chemical deposition methods. The preset parameters can be preset roughness, cleanliness, crystallinity, etc. The copper foil metallographic structure parameters can represent a series of parameters describing the internal microstructure and organizational characteristics of the copper foil, such as grain shape and size, dislocation density, porosity, etc. By obtaining the raw foil surface with preset copper foil metallographic structure parameters, the copper foil layer generated subsequently can meet the performance requirements thereof. In addition, after the carrier copper foil is generated, the carrier copper foil can also be rolled up.

[0054] For example, the surface of the raw foil of the electrolysis device is treated by cleaning the surface of the cathode roller with deionized water, diluted acid or alkaline solution to remove grease, dust and other pollutants. The surface of the cathode roller can also be ground and polished with abrasives (such as sandpaper, polishing paste), polishing machines, etc. to obtain a preset roughness.

[0055] The carrier copper foil of the present disclosure is further described below.

[0056] Figure 2 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 carrier layer 61, a peeling layer 62 and a copper foil layer 63. It can be understood that Figure 2 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 carrier layer 61. It can be seen that in the present 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:

[0057] 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.

[0058] 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.

[0059] 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.

[0060] 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 the first brush plating, and the second brush-plated layer 622 is a phosphide layer formed by the second brush plating. In the process of forming the phosphide layer, an anti-oxidation treatment reaction with the non-cathode roller surface of the carrier layer is also included, and the non-cathode roller surface of the carrier layer can also be surface treated.

[0061] 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.

[0062] 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.

[0063] 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.

[0064] 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.

[0065] 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.

[0066] Figure 3~Figure 6 Schematic diagram showing the carrier copper foil and peeling state in the embodiment of the present disclosure. Figure 3~Figure 6 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.

[0067] 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.

[0068]

[0069] Example 1

[0070] In this embodiment, the components of the copper electrodeposition solution are: phytic acid 20g / L, copper carbonate 10g / L, tartaric acid additive 0.3g / L, and the solvent is water. The pH value of the copper electrodeposition solution is 2. When preparing the copper foil layer, the electrodeposition temperature is 40°C, the rate is 0.6 m / min, and the current density is 3A / dm 2 .

[0071] Example 2

[0072] Compared with Example 1, the difference of this example is that the concentration of phytic acid is 50 g / L and the concentration of copper carbonate is 10 g / L.

[0073] Example 3

[0074] Compared with Example 1, the difference of this example is that the concentration of phytic acid is 100 g / L and the concentration of copper carbonate is 10 g / L.

[0075] Example 4

[0076] Compared with Example 1, the difference of this example is that the concentration of phytic acid is 50 g / L and the concentration of copper carbonate is 50 g / L.

[0077] Example 5

[0078] Compared with Example 1, the difference of this example is that the concentration of phytic acid is 50 g / L and the concentration of copper carbonate is 80 g / L.

[0079] Comparative Example 1

[0080] Compared with Example 1, the difference of this comparative example is that the copper electrodeposition solution is: 130 g / L potassium pyrophosphate, 25 g / L copper, 2 g / L citric acid additive, the solvent is water, and the pH value is 8.5.

[0081] The elongation of the copper foil layer obtained in the embodiment and the comparative example was tested, and the results are shown in Table 1:

[0082] Table 1

[0083]

[0084] It can be seen from the above table that the combination of phytic acid and copper carbonate used in the present disclosure can effectively improve the elongation of the copper foil layer.

[0085] 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 copper electrodeposition solution, characterized in that: The invention comprises the following components: 20 g / L to 100 g / L of phytic acid, 10 g / L to 80 g / L of copper carbonate, 0.1 g / L to 1 g / L of tartaric acid additive and a solvent; the pH value of the copper electrodeposition solution is 0.5 to 3.

2. The copper electrodeposition solution according to claim 1, characterized in that The solvent is water.

3. A method for preparing a carrier copper foil, characterized in that: The steps include: forming a peeling layer on the surface of the carrier layer to obtain a pre-finished product; The pre-finished product is subjected to an electroplating treatment using the copper electroplating solution described in any one of claims 1 to 2, so as to deposit a copper foil layer on the surface of the stripping layer away from the carrier layer.

4. The method for preparing a carrier copper foil according to claim 3, characterized in that: During the electrodeposition treatment, the temperature of the copper electrodeposition solution is 35° C. to 60° C.

5. The method for preparing a carrier copper foil according to claim 3, characterized in that: The rate of the electrodeposition treatment is 0.3 m / min to 1.2 m / min.

6. The method for preparing a carrier copper foil according to claim 3, characterized in that: The current density of the electrodeposition treatment is 1A / dm 2 ~10A / dm 2 .

7. The method for preparing a carrier copper foil according to any one of claims 3 to 6, characterized in that: The thickness of the copper foil layer is 0.5 μm to 5 μm.

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