Manufacturing System for Composite Copper Foil Film

Abstract

The present invention discloses a manufacturing system for composite copper foil films, including a film-making device for preparing polyester films constituting the base material layer, a pre-coating treatment device for pre-treating the polyester films and forming metal copper sputtering layers on both sides thereof, and a hydro-plating device for forming a metal layer electroplating layer and a protective layer on the outer side of the metal copper sputtering layer. The manufacturing system of the present application can obtain excellent electrical properties and adhesion without damaging the surface structure of the base material layer by combining the preparation of a three-layer composite polyester film, a vacuum sputtering process, and a hydro-plating process, basically eliminating the possibility of defects such as fusing or burning through of the base material layer, and can obtain excellent electrical properties and adhesion.

Description

Technical Field

[0001] The present application relates to a manufacturing system for a composite copper foil film that can be used as a negative current collector of a lithium-ion battery. Background Art

[0002] The current collector in a lithium-ion battery is composed of a metal foil film for conducting electricity, and its main functions are to carry the electrode materials of the positive and negative electrodes, and at the same time collect current and conduct electrons. Commonly used positive current collectors are aluminum foils, and commonly used negative current collectors are copper foils.

[0003] CN 112201389 B discloses a conductive film substituting for an aluminum foil and its preparation method. The conductive film includes a metal layer, an intermediate reinforcing layer, and a polymer thin film layer. The intermediate reinforcing layer is arranged on both sides of the polymer thin film layer, and the metal layer is arranged on the outer side of the intermediate reinforcing layer. Among them, the intermediate reinforcing layer is formed on both sides of the polymer thin film layer by magnetron sputtering coating or evaporation coating; the metal layer is formed on the outer side of the intermediate reinforcing layer by evaporation coating or magnetron sputtering. For this conductive film of the prior art, it is necessary to evaporate the target material into a gas at a high temperature and then attach it to the surface of the polymer thin film layer. The higher the evaporation temperature of the target material, the more likely the polymer thin film layer is to have defects such as fusing or burning through. Therefore, generally, the composite aluminum foils are produced by magnetron sputtering or evaporation coating in the prior art, and there are few cases of preparing composite copper foils because the evaporation temperature of copper is higher. The higher the evaporation temperature of the target material, the faster the running speed of the polymer thin film layer is required, and thus the formed metal layer will be thinner, and the conductivity of the conductive film will also deteriorate accordingly, and it is not suitable for use as a negative current collector of a lithium-ion battery. Therefore, the currently prepared composite aluminum foils are usually only used as food packaging materials, and moreover, due to the very poor adhesion of the metal layer formed by evaporation coating, it is very easy to fall off.

[0004] In addition, another reason for the easy detachment of the metal layer of the composite metal foil is that the surface structure of the non-metal substrate layer for carrying the metal layer is uneven, resulting in insufficient adhesion of the metal layer to the substrate layer. In order to alleviate the influence of long-term high-temperature baking on the surface performance of the substrate layer, it is necessary to stack the metal layer gradually at intervals for multiple times. The various structural performance defects of the substrate layer will be gradually amplified by the stacked metal layer. Therefore, the existing composite metal foils and their preparation processes are difficult to be applied to the production of composite copper foil films that can be used as current collectors.

[0005] In summary, the metal layer that can be obtained on the substrate by magnetron sputtering or evaporation coating for the composite metal foil of the prior art is very thin, and it is very easy to have defects such as fusing or burning through during long-term operation at a high temperature. Its conductivity and uniformity have fatal defects. In particular, it is difficult to prepare a composite copper foil film that meets the conductive and safety requirements of lithium-ion batteries by this process. In addition, the defects of the substrate will also affect the adhesion of the metal layer. Summary of the Invention

[0006] The technical problem to be solved by this application is to provide a manufacturing system for composite copper foil films to reduce or avoid the problems mentioned above.

[0007] To solve the above technical problem, this application proposes a manufacturing system for composite copper foil films, including a film manufacturing device for preparing polyester films that make up the base material layer, a pre-coating treatment device for pre-treating the polyester film and forming a metal copper sputtering layer on both sides thereof, and a hydro-plating device for forming a metal layer electroplating layer and a protective layer on the outside of the metal copper sputtering layer; wherein, the film manufacturing device includes a mixer and a first extruder for preparing polyester functional masterbatch, and the polyester functional masterbatch output from the first extruder and the ordinary PET resin input through the ordinary PET resin feed pipe are uniformly mixed through a pipeline and further input into the second extruder; the molten polyester functional masterbatch is respectively input into the film preparation mechanism through the surface layer pipeline and the bottom layer pipeline to obtain the surface layer A of the polyester film and the bottom layer C, and the ordinary PET resin is input into the film preparation mechanism through the third extruder and the core layer pipeline to obtain the core layer B of the polyester film.

[0008] Preferably, the pre-coating treatment device includes a corona chamber for corona-treating the surface of the polyester film obtained by the film manufacturing device to obtain a corona layer, an annular vacuum sputtering chamber, and a material receiving chamber; the corona-treated polyester film is input from the corona chamber into the annular vacuum sputtering chamber, and through the annular vacuum sputtering chamber, a barrier layer is sputtered and formed on the outside of the corona layer, and a metal copper sputtering layer is sputtered and formed on the outside of the barrier layer; the polyester film formed with the metal copper sputtering layer is input from the annular vacuum sputtering chamber into the material receiving chamber to wind up and collect the polyester film into a roll.

[0009] Preferably, the hydro-plating device includes a copper electroplating tank and a protective electroplating tank. The polyester film formed with the metal copper sputtering layer is input from the pre-coating treatment device into the copper electroplating tank, and a metal copper electroplating layer is formed on the outside of the metal copper sputtering layer by electroplating; the polyester film formed with the metal copper electroplating layer is input from the copper electroplating tank into the protective electroplating tank, and a protective layer is formed on the outside of the metal copper electroplating layer by electroplating.

[0010] Preferably, the annular vacuum sputtering chamber includes at least one barrier material sputtering chamber arranged upstream, and at least one copper material sputtering chamber is arranged downstream of the barrier material sputtering chamber.

[0011] Preferably, at least one first infrared heating unit for baking out moisture from the input polyester film is arranged on one side of the feed port of the annular vacuum sputtering chamber.

[0012] Preferably, at least one second infrared heating unit for heating the material conveying roller is arranged on one side of the discharge port of the annular vacuum sputtering chamber, and the material conveying roller further heats the output polyester film.

[0013] Preferably, both the feed inlet and the discharge outlet of the annular vacuum sputtering chamber are provided with material change gates for isolating the annular vacuum sputtering chamber from the corona chamber and the material collection chamber during material change.

[0014] Preferably, the following raw materials in parts by weight are added to the mixer: 30-50 parts by weight of poly(m-phenylene isophthalamide), 1-3 parts by weight of cobalt neodecanoate, 3-5 parts by weight of dibutylhydroxytoluene, 5-10 parts by weight of 1,4-diiodobenzene, 20-30 parts by weight of silicon dioxide, and 50-100 parts by weight of PET.

[0015] The manufacturing system of the present application, through the combination of preparing a three-layer composite polyester film, a vacuum sputtering process, and a hydroelectroplating process, can obtain excellent electrical properties and adhesion without damaging the surface structure of the substrate layer, basically eliminating the possibility of defects such as melting or burning through of the substrate layer, and can obtain excellent electrical properties and adhesion. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] The following drawings are only intended to illustrate and explain the present application schematically and do not limit the scope of the present application.

[0017] Figure 1 Shows a schematic structural diagram of a composite copper foil film according to a specific embodiment of the present application.

[0018] Figure 2 Shows a schematic structural diagram of a composite copper foil film according to another specific embodiment of the present application.

[0019] Figure 3 Shows a schematic structural diagram of a manufacturing system for a composite copper foil film according to a specific embodiment of the present application.

[0020] Figure 4 Shows a schematic structural diagram of a pre-coating treatment device of a manufacturing system for a composite copper foil film according to another specific embodiment of the present application. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0021] In order to have a clearer understanding of the technical features, objectives, and effects of the present application, the specific embodiments of the present application are now described with reference to the accompanying drawings. Among them, the same components are denoted by the same reference numerals.

[0022] Such as Figure 1-2As shown in the figure, the present invention provides a composite copper foil film that can be used as the negative electrode current collector of a lithium-ion battery. The composite copper foil film is composed of a substrate layer 1 and conductive layers 2 attached to both sides of the substrate layer 1. The conductive layer 2 is mainly composed of metallic copper. As mentioned above, due to the high evaporation temperature of metallic copper, if it is attached to the surface of the substrate layer 1 made of a polymer material by evaporation coating, the uniformity of the surface structure of the substrate layer 1 will be damaged, and it is difficult to obtain a thickness sufficient for the required electrical performance. Moreover, the greater the stacked thickness, the easier it is to peel off and powder, making it unsuitable for use as a negative electrode current collector.

[0023] In view of this, the present application provides a composite copper foil film, in which the conductive layer 2 adopts a multi-layer conductive structure. In the specific embodiment shown in the figure, the conductive layer 2 sequentially includes a metallic copper sputtering layer 21, a metallic copper electroplating layer 22, and a protective layer 23 from the inside out. Among them, the metallic copper sputtering layer 21 is a layer of metallic copper with a thickness of 5 - 15 nm formed on both sides of the substrate layer 1 by a vacuum sputtering process. The metallic copper electroplating layer 22 is a layer of metallic copper with a thickness of 100 - 500 nm grown on the outer surface of the metallic copper sputtering layer 21 by a hydroelectroplating process. The protective layer 23 is a dense protective layer formed by passivating the outer surface of the metallic copper electroplating layer 22 through an electroplating or chemical etching process. Preferably, the protective layer 23 is a layer of metallic chromium protective layer with a thickness of 5 - 15 nm formed by an electroplating process.

[0024] In the composite copper foil film of the present application, the compactness and adhesion of the metallic copper sputtering layer formed by vacuum sputtering are far superior to those of the evaporation coating process. Moreover, since the required thickness is very thin, the running speed of the substrate layer can be very fast, basically eliminating the possibility of defects such as the substrate layer being melted or burned through. Although the thickness of the metallic copper sputtering layer is very thin, it can provide basic electrical conductivity. Therefore, a thicker metallic copper layer can be further grown on its surface by hydroelectroplating. Through the combination of the vacuum sputtering process and the hydroelectroplating process, the present application can obtain excellent electrical performance and adhesion without damaging the surface structure of the substrate layer, which will be further described later.

[0025] In addition, in order to avoid the problem of insufficient adhesion of the metallic copper layer caused by the uneven surface structure of the substrate layer, the present application also provides an improved substrate layer 1. In a specific embodiment of the present application, the substrate layer 1 of the present application is made of a polyester film added with a polyester functional masterbatch. The substrate layer 1 can be a three-layer polyester film including a surface layer A, a core layer B, and a bottom layer C with the polyester functional masterbatch added to the surface layer and the bottom layer ( Figure 1 ), or a single-layer polyester film added with a polyester functional masterbatch ( Figure 2 ).

[0026] The polyester referred to in the present invention means a polyester formed by one or more than two selected from polycarboxylic acids containing dibasic acids and their ester-forming derivatives, and one or more than two selected from polyols containing diols; or a polyester formed by hydroxycarboxylic acids and their ester-forming derivatives; or a polyester formed by cyclic esters. The manufacture of the polyester can be carried out according to the existing well-known methods. For example, taking the preparation of PET as an example, it can be obtained by the following methods: the method of polycondensation after the esterification of terephthalic acid and ethylene glycol; or the method of polycondensation after the transesterification reaction of an alkyl ester of terephthalic acid such as dimethyl terephthalate and ethylene glycol. The polyester of the present invention is preferably PET.

[0027] In a specific embodiment, the polyester film constituting the substrate layer 1 is a single-layer polyester film containing 5-20 wt% of a polyester functional masterbatch, or a three-layer polyester film including a surface layer A, a core layer B, and a bottom layer C, where the surface layer A and the bottom layer C contain 5-20 wt% of the polyester functional masterbatch. The polyester functional masterbatch is prepared from raw materials including the following parts by weight: 30-50 parts by weight of poly(m-phenylene isophthalamide), 1-3 parts by weight of cobalt neodecanoate, 3-5 parts by weight of dibutylhydroxytoluene, 5-10 parts by weight of 1,4-diiodobenzene, 20-30 parts by weight of silica, and 50-100 parts by weight of PET.

[0028] The polyester functional masterbatch of the present invention can be prepared in the form of granules or slices and added to ordinary polyester during the production of polyester film to obtain the substrate layer 1 of the present invention. For example, 80-95 wt% of polyester without other components can be melt-blended with 5-20 wt% of the polyester functional masterbatch of the present invention, and then the single-layer structure of the substrate layer 1 can be produced through processes such as stretching, or the surface structure of the substrate layer 1 of the present invention can be obtained through a multi-layer co-extrusion process.

[0029] Each raw material component of the polyester functional masterbatch of the present invention can be uniformly mixed in the form of pellets and then extruded and granulated using equipment such as an extruder to obtain the polyester functional masterbatch of the present invention.

[0030] In a specific embodiment, at room temperature, 50-100 parts by weight of powdered PET, 20-30 parts by weight of nano-silica, 30-50 parts by weight of powdered poly(m-phenylene isophthalamide), 1-3 parts by weight of powdered cobalt neodecanoate, 3-5 parts by weight of powdered dibutylhydroxytoluene, and 5-10 parts by weight of powdered 1,4-diiodobenzene can be added to a mixer for pre-dispersion and mixing at a rotation speed of 1500-2000 rpm for 30-60 minutes to form a mixed material. Then, it is melt-extruded through a twin-screw extruder and then water-cooled and granulated or sliced to obtain the polyester functional masterbatch.

[0031] In another specific embodiment, for example, after obtaining the polyester functional masterbatch chips, 5-20 wt% of the polyester functional masterbatch is taken and added to 80-95 wt% of PET particles for uniform mixing. The two are melt-blended, and finally a single-layer substrate layer 1 is produced through processes such as stretching, or the surface layer A and the bottom layer B of the three-layer substrate layer 1 are obtained through a multi-layer co-extrusion process.

[0032] Taking a single-layer polyester film as an example, the preparation method of the polyester film for composite copper foil film of the present invention will be further described. The preparation method of the polyester film for composite copper foil film of the present invention includes the following steps:

[0033] Components with the following weight ratios: 80-95 wt% of PET resin and 5-20 wt% of polyester functional masterbatch are respectively weighed by an electronic scale and enter a mixing bin for mixing to form a mixture.

[0034] After that, the mixture enters an exhaust-type twin-screw extruder, and the temperature of the twin-screw extruder is adjusted to 270°C - 280°C.

[0035] After the materials are melted in the extruder, they are filtered and extruded into thick sheets. The thickness and profile of the thick sheets can be adjusted by the extrusion amount of the extruder, the rotation speed of the casting roll, and the die opening.

[0036] The above thick sheets are preheated at a temperature of 50°C - 90°C, enter an infrared heating zone of 300°C - 500°C, and are longitudinally stretched at a linear speed of 40 - 150 m / min. The longitudinal stretching ratio is 4.0 to obtain stretched sheets.

[0037] The stretched sheets are preheated at a temperature of 90°C - 120°C and are transversely stretched at a temperature of 100°C - 160°C. The transverse stretching ratio is 3.8. Then they are shaped at a temperature of 160°C - 240°C and cooled from 160°C to 50°C to obtain the polyester film for composite copper foil film.

[0038] The thickness of the obtained polyester film is 6 - 10 μm.

[0039] Taking a three-layer polyester film as an example, the preparation method of the polyester film for composite copper foil film of the present invention will be further described. The preparation method of the polyester film for composite copper foil film of the present invention includes the following steps:

[0040] Components with the following weight ratios: 80-95 wt% of PET resin and 5-20 wt% of polyester functional masterbatch are respectively weighed by an electronic scale and enter a mixing bin for mixing to form a mixture.

[0041] After that, the mixture enters an exhaust-type twin-screw extruder E.

[0042] Put 100% PET resin into the pre-crystallizer and pre-crystallize it at 160°C for 15 minutes. Then the PET material enters the drying tower and is dried at 160°C for 6 hours. After that, it enters the single-screw extruder F.

[0043] Adjust the temperatures of the twin-screw extruder E and the single-screw extruder F to 270°C - 280°C.

[0044] After the material is melted in the two extruders and filtered, the material extruded from the twin-screw extruder E is used as the surface layer A and the bottom layer C, and the material extruded from the single-screw extruder F is used as the core layer B. A three-layer composite thick sheet is made through a multi-layer co-extrusion process. The thickness and profile of the thick sheet can be adjusted by the extrusion amount of the extruder, the rotation speed of the casting roll, and the die opening.

[0045] Preheat the above-mentioned thick sheet at a temperature of 50°C - 90°C, enter the infrared heating zone at 300°C - 500°C, and conduct longitudinal stretching at a linear speed of 40 - 150 m / min. The longitudinal stretching ratio is 4.0 to obtain a stretched sheet.

[0046] Preheat the stretched sheet at a temperature of 90°C - 120°C, conduct transverse stretching at a temperature of 100°C - 160°C, and the transverse stretching ratio is 3.8. Then it is shaped at a temperature of 160°C - 240°C and cooled from 100°C to 50°C to obtain the polyester film with the three-layer structure.

[0047] The thickness of the obtained polyester film is 6 - 10 μm, where the thickness of layer A is 1 - 2 μm, the thickness of layer B is 2 - 8 μm, and the thickness of layer C is 1 - 2 μm.

[0048] Examples 1 - 5

[0049] According to the raw material weight part ratios in the following table, polyester functional masterbatch chips are respectively prepared and obtained, and then put into ordinary PET resin to prepare a polyester film with a single-layer structure for composite copper foil film.

[0050] Example 1 Example 2 Example 3 Example 4 Example 5 Polymeta - xylylene diamide 30 35 40 45 50 Cobalt neodecanoate 1 1.5 2 2.5 3 Butylated hydroxytoluene 3 3.5 4 4.5 5 1,4 - Diiodobenzene 5 7 7.5 8 10 Silica 20 22 25 27 30 PET 50 65 75 85 100 Slice amount for preparing single - layer substrate layer 5wt% 10wt% 13wt% 15wt% 20wt% Substrate layer thickness μm 6 7 8 9 10

[0051] Comparative Examples 6 - 10

[0052] According to the same method as in the above examples, polyester films for comparison are prepared according to the raw material weight part ratios in the following table.

[0053] Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 Polymeta - xylylene diamide 0 35 40 45 50 Cobalt neodecanoate 1 0 2 2.5 3 Butylated hydroxytoluene 3 3.5 0 4.5 5 1,4 - Diiodobenzene 5 7 7.5 0 10 Silica 20 22 25 27 0 PET 80 66.5 79 93 130 Slice amount for preparing single - layer substrate layer 5wt% 10wt% 13wt% 15wt% 20wt% Substrate layer thickness μm 6 7 8 9 10

[0054] The performance parameters of each prepared polyester film are respectively tested. At the same time, a film with a thickness of 8 μm prepared from pure PET without adding any functional masterbatch is used for comparison. The performance parameters are shown in the following table.

[0055]

[0056] On both sides of the polyester film described in the above table, metal copper sputtering layers are formed respectively through a vacuum sputtering process. The thickness of the metal copper layers on both sides of the vacuum sputtering is controlled to be 5 nm, and the surface crack parameters of the prepared film are tested.

[0057]

[0058]

[0059] From the performance parameters of the above film layers and the crack conditions of the metal coating, it can be seen that for the polyester film prepared by adding the polyester functional masterbatch of the present application, its performance such as porosity, water absorption rate, oxygen permeability, etc. has been greatly improved, and no obvious crack propagation is seen after forming the metal copper conductive layer.

[0060] Furthermore, the resistivity differences between the metal copper sputtering layers on both sides of the polyester film shown in the above table are tested, as shown in the following table.

[0061]

[0062] For the polyester film prepared by adding the polyester functional masterbatch of the present application, the resistivity difference of the metal copper sputtering layer formed thereon is significantly smaller than that of the film without adding the functional masterbatch, indicating that the structures on both sides thereof have more excellent consistency.

[0063] Furthermore, since the metal copper sputtering layer 21 needs to be formed on the surface of the substrate layer 1 first in the present application, the substrate layer 1 needs to be controlled to operate at a lower temperature during sputtering. Although the improved polyester film of the substrate layer 1 has excellent performance such as porosity, water absorption rate, oxygen permeability, etc., it is still necessary to prevent the problem of water absorption on the surface of the polyester film at low temperature and then the release of water during sputtering, which interferes with the vacuum degree.

[0064] Therefore, in a specific embodiment, as Figure 2 shown, in order to avoid the problem of water absorption and release of the substrate layer 1 during sputtering, a barrier layer 11 is also sputtered on the outer side of the substrate layer 1 between the conductive layer 2 and the substrate layer 1 to improve the performance of the conductive layer 2. Specifically, a barrier layer 11 composed of silicon dioxide with a thickness of 2 - 3 nm can be deposited on both sides of the substrate layer 1 respectively by means of dual-rotating cathode and medium-frequency reactive magnetron sputtering to form a coating isolation on the surface of the substrate layer 1 and form a hydrophobic structure on the surface of the substrate layer 1.

[0065] Further, since the thickness of the barrier layer 11 is very small, in order to improve the adhesion of the barrier layer 11 to the surface of the substrate layer 1, before sputtering to form the barrier layer 11, it is preferable to perform a corona treatment on the surface of the substrate layer 1 to form a corona layer 10 with a thickness of 1-2 nm on the surface of the substrate layer 1, and the barrier layer 11 is formed on the outer side of the corona layer 10. Corona treatment is an existing technology, and its basic principle is to use high-frequency and high-voltage corona discharge on the surface of the plastic to be treated, making the surface of the substrate layer 1 rough, so as to increase the adhesion ability of the surface of the substrate layer 1 to the barrier layer 11.

[0066] Of course, those skilled in the art should understand that the corona layer 10 and the barrier layer 11 can also be formed on Figure 1 the surface of the substrate layer 1 composed of the polyester film of the three-layer structure shown.

[0067] The following will refer to Figure 3-4 to further illustrate the manufacturing system for the composite copper foil film of the present application.

[0068] As shown in the figure, the manufacturing system for the composite copper foil film of the present application includes a film manufacturing device 100 for preparing the polyester film constituting the substrate layer 1, a pre-coated film treatment device 200 for pre-treating the polyester film and forming a metal copper sputtering layer 21 on both sides thereof, and a hydro-plating device 300 for forming a metal layer electroplating layer 22 and a protective layer 23 on the outer side of the metal copper sputtering layer 21.

[0069] Among them, the film manufacturing device 100 includes a mixer 101 for preparing polyester functional masterbatch and a first extruder 102. As described above, the following raw materials in parts by weight can be added to the mixer 101 at room temperature: 30-50 parts by weight of poly(m-phthaloyldiamine), 1-3 parts by weight of cobalt neodecanoate, 3-5 parts by weight of dibutylhydroxytoluene, 5-10 parts by weight of 1,4-diiodobenzene, 20-30 parts by weight of silicon dioxide, and 50-100 parts by weight of PET. More specifically, 50-100 parts by weight of powdered PET, 20-30 parts by weight of nano-silicon dioxide, 30-50 parts by weight of powdered poly(m-phthaloyldiamine), 1-3 parts by weight of powdered cobalt neodecanoate, 3-5 parts by weight of powdered dibutylhydroxytoluene, and 5-10 parts by weight of powdered 1,4-diiodobenzene can be added to the mixer 101 for pre-dispersion and mixing at a rotation speed of 1500-2000 rpm for 30-60 minutes to form a mixed material. Then, it is melt-extruded through the first extruder 102 (for example, a twin-screw extruder), and then water-cooled granulated or sliced to obtain the polyester functional masterbatch.

[0070] The polyester functional masterbatch output from the first extruder 102 and the ordinary PET resin input through the ordinary PET resin feed pipe 103 are uniformly mixed through a pipeline and then further input into the second extruder 105. As described above, for example, 5-20 wt% of the polyester functional masterbatch obtained from the first extruder 102 and 80-95 wt% of the ordinary PET resin input through the ordinary PET resin feed pipe 103 can be input into the mixing bin 104 to be mixed into a mixture, and then enter the second extruder 105 (for example, the vented twin-screw extruder E).

[0071] The polyester functional masterbatch melted by the second extruder 105 is respectively input into the film preparation mechanism 108 through the surface layer pipeline and the bottom layer pipeline to obtain the surface layer A and the bottom layer C of the polyester film. The ordinary PET resin is input into the film preparation mechanism 108 through the third extruder 109 (for example, the single-screw extruder F) and the core layer pipeline to obtain the core layer B of the polyester film. As described above, for example, the material extruded by the twin-screw extruder E is used as the surface layer A and the bottom layer C, and the material extruded by the single-screw extruder F is used as the core layer B. A three-layer composite thick sheet is formed through the multi-layer co-extrusion process of the film preparation mechanism 108; the above thick sheet is preheated at a temperature of 50°C to 90°C, enters an infrared heating zone of 300°C to 500°C, and is longitudinally stretched at a linear speed of 40-150 m / min. The longitudinal stretching ratio is 4.0 to obtain a stretched sheet; the stretched sheet is preheated at a temperature of 90°C to 120°C and transversely stretched at a temperature of 100°C to 160°C. The transverse stretching ratio is 3.8; then it is shaped at a temperature of 160°C to 240°C and cooled through a temperature range of 100°C to 50°C to obtain a three-layer structured polyester film.

[0072] Further, as Figure 4 shown, the pre-coated film treatment device 200 includes a corona chamber 201 for corona treatment of the surface of the polyester film prepared by the film manufacturing device 100 to obtain a corona layer 10, an annular vacuum sputtering chamber 202, and a material receiving chamber 203; the polyester film after corona treatment is input from the corona chamber 201 into the annular vacuum sputtering chamber 202. Through the annular vacuum sputtering chamber 202, a barrier layer 11 is sputtered on the outer side of the corona layer 10, and a metallic copper sputtering layer 21 is sputtered on the outer side of the barrier layer 11; the polyester film formed with the metallic copper sputtering layer 21 is input from the annular vacuum sputtering chamber 202 into the material receiving chamber 203 to wind up the polyester film into a roll.

[0073] The corona chamber 201, the annular vacuum sputtering chamber 202, and the material receiving chamber 203 form an integral structure. In order to maintain the vacuum degree of the annular vacuum sputtering chamber 202 during material replacement, material replacement gates 2025 are provided at both the feed port and the discharge port of the annular vacuum sputtering chamber 202, which are used to isolate the annular vacuum sputtering chamber 202 from the corona chamber 201 and the material receiving chamber 203 during material replacement, as shown in the figure. The material replacement gates 2025 are arranged in pairs on the outer sides of the feed port and the discharge port of the annular vacuum sputtering chamber 202, and there is a slit for the polyester film to pass between the material replacement gates 2025. When the gates are closed, the polyester film is clamped in the middle, and the polyester film extending out of the annular vacuum sputtering chamber 202 can be pasted to the ends of a new supply roll and a take-up roll respectively, and then the continuous material replacement is completed.

[0074] Multiple sets of tension rollers are arranged in the corona chamber 201 to maintain the tension of the polyester film during operation. A corona electrode 2011 is arranged inside the corona chamber 201, which is used to form a corona layer 10 on at least one side of the polyester film.

[0075] It can be seen from the structure in the figure that after one operation of the pre-coated film treatment device 200, only the barrier layer 11 and the metal copper sputtering layer 21 can be formed on one side of the polyester film. Therefore, in order to form the barrier layer 11 and the metal copper sputtering layer 21 on both sides of the polyester film, after the sputtering of a roll of polyester film is completed, the take-up roll needs to be reloaded into the corona chamber 201 for sputtering on the other side of the polyester film again. Therefore, only one set of structures of the corona electrode 2011 needs to be arranged in the corona chamber 201, and only the corona layer 10 needs to be formed on the side where sputtering is required, and then it is convenient to form the barrier layer 11 on the corona layer 10.

[0076] A hollow cooling roll 2029 is arranged in the middle of the annular vacuum sputtering chamber 202. During operation, a cooling medium passes through the cooling roll 2029, and the polyester film runs closely on the outer side of the cooling roll 2029. The polyester film is cooled to about minus 20 - 30 degrees Celsius by the cooling roll 2029 to prevent the polyester film from being burned through during sputtering.

[0077] Around the cooling roll 2029, multiple sputtering chambers are arranged in the annular vacuum sputtering chamber 202. A total of seven chambers are shown in the figure. Among them, no sputtering materials are arranged in the middle chamber, and three chambers on each side can be used as sputtering chambers.

[0078] Among them, the annular vacuum sputtering chamber 202 includes at least one barrier material sputtering chamber 2021 arranged upstream. Downstream of the barrier material sputtering chamber 2021, there are at least one copper material sputtering chamber 2022. For example, the first two sputtering chambers upstream of the operation of the polyester film can be set as the barrier material sputtering chamber 2021, and two oppositely rotating rod materials for forming a silicon dioxide barrier layer can be arranged therein. When sputtering, the rod materials serve as the raw material supply source, and under the action of high pressure, barrier materials such as silicon dioxide are sputtered onto the polyester film. The oppositely rotating rod materials can form a more uniform sputtering layer structure. The other four sputtering chambers downstream of the barrier material sputtering chamber 2021 can be set as copper material sputtering chambers 2022, and oppositely rotating copper rod materials are arranged in the first two sputtering chambers. According to actual needs, only the first sputtering chamber upstream can be used as the barrier material sputtering chamber 2021, the subsequent three sputtering chambers can be used as copper material sputtering chambers 2022, and single copper rod materials can be arranged in the last two sputtering chambers to form a metal copper sputtering layer 21 distributed in the same direction on the outermost side, so as to keep the production speed of the copper layer consistent during subsequent electroplating with water.

[0079] In order to avoid the interference of water vapor on the surface of the polyester film with sputtering, at least one first infrared heating unit 2023 for dehumidifying and baking the input polyester film is arranged on one side of the feed port of the annular vacuum sputtering chamber 202.

[0080] Furthermore, since the polyester film operates at a very low temperature during sputtering, it is very easy for the low-temperature polyester film to form condensed water when it enters the take-up chamber 203. Therefore, at least one second infrared heating unit 2024 for heating the conveying roller is arranged on one side of the discharge port of the annular vacuum sputtering chamber 202, and the conveying roller further heats the output polyester film. The indirect heating of the conveying roller is adopted because the temperature of the polyester film is very low, and direct heating will result in an uneven temperature field, which is likely to burn through or have inconsistent heating temperatures. Therefore, the heating by the indirect heating method is more uniform and the efficiency of increasing the temperature of the polyester film is also higher.

[0081] Back to Figure 3 , the electroplating device 300 with water includes a copper electroplating tank 301 and a protective electroplating tank 302. The polyester film formed with the metal copper sputtering layer 21 is input into the copper electroplating tank 301 from the pre-coating treatment device 200, and a metal copper electroplating layer 22 is formed on the outside of the metal copper sputtering layer 21 by electroplating process; the polyester film formed with the metal copper electroplating layer 22 is input into the protective electroplating tank 302 from the copper electroplating tank 301, and a protective layer 23 is formed on the outside of the metal copper electroplating layer 22 by electroplating process.

[0082] As described above, although the thickness of the metal copper sputtering layer is very thin, it can provide basic electrical conductivity. Therefore, after the polyester film is processed by the pre-coating treatment device 200, a metal copper sputtering layer 21 is formed on its surface. Then, using the traditional and well-known electroplating process, a metal copper electroplating layer 22 and a protective layer 23 can be formed in the copper electroplating tank 301 and the protective electroplating tank 302 respectively. For example, an electrolyte mainly composed of copper sulfate can be added to the copper electroplating tank 301, and an electrolyte mainly composed of chromic anhydride and sulfuric acid can be added to the protective electroplating tank 302. The thickness of the coating can be controlled by controlling the running speed of the polyester film and the length of the electroplating tank.

[0083] Using the polyester films prepared in Examples 1-5 as the base layers, after corona treatment, sputtering of the barrier layer, sputtering of the metal copper sputtering layer, electroplating of the metal copper electroplating layer, and electroplating of the protective layer respectively, composite copper foil films with the following parameters are prepared.

[0084]

[0085] From the measured parameters, it can be seen that the composite copper foil film of the present application has excellent electrical properties, and the adhesion of the conductive layer is extremely strong. Almost no peeling of the conductive layer will occur during normal use.

[0086] Those skilled in the art should understand that although the present application is described in the form of multiple embodiments, not every embodiment only contains an independent technical solution. Such a description in the specification is only for clarity. Those skilled in the art should understand the specification as a whole and consider the technical solutions involved in each embodiment as ways that can be combined with each other to form different embodiments to understand the protection scope of the present application.

[0087] The above description is only a schematic specific embodiment of the present application and is not intended to limit the scope of the present application. Any equivalent changes, modifications, and combinations made by those skilled in the art without departing from the concept and principle of the present application shall fall within the protection scope of the present application.

Claims

1. A manufacturing system for a composite copper foil film, characterized in that, The manufacturing system includes a film-making device (100) for preparing a polyester film that constitutes the base material layer (1), a pre-coating treatment device (200) for pre-treating the polyester film and forming a metal copper sputtering layer (21) on both sides thereof, and a hydro-plating device (300) for forming a metal layer electroplating layer (22) and a protective layer (23) on the outer side of the metal copper sputtering layer (21); wherein, the film-making device (100) includes a mixer (101) for preparing a polyester functional masterbatch and a first extruder (102). The polyester functional masterbatch output from the first extruder (102) and the ordinary PET resin input through the ordinary PET resin feed pipe (103) are input into the mixing bin (104) through a pipeline for uniform mixing and further input into the second extruder (105); the molten polyester functional masterbatch is respectively input into the film preparation mechanism (108) through the surface layer pipeline and the bottom layer pipeline to obtain the surface layer A of the polyester film and the bottom layer C, and the ordinary PET resin is input into the film preparation mechanism (108) through the third extruder (109) and the core layer pipeline to obtain the core layer B of the polyester film; the pre-coating treatment device (200) includes a corona chamber (201) for corona-treating the surface of the polyester film prepared by the film-making device (100) to obtain a corona layer (10), an annular vacuum sputtering chamber (202), and a material receiving chamber (203); the polyester film after corona treatment is input from the corona chamber (201) into the annular vacuum sputtering chamber (202). Through the annular vacuum sputtering chamber (202), a barrier layer (11) is sputtered and formed on the outer side of the corona layer (10), and a metal copper sputtering layer (21) is sputtered and formed on the outer side of the barrier layer (11); the polyester film formed with the metal copper sputtering layer (21) is input from the annular vacuum sputtering chamber (202) into the material receiving chamber (203) to wind up and collect the polyester film into a roll; the hydro-plating device (300) includes a copper electroplating tank (301) and a protective electroplating tank (302). The polyester film formed with the metal copper sputtering layer (21) is input from the pre-coating treatment device (200) into the copper electroplating tank (301), and a metal copper electroplating layer (22) is formed on the outer side of the metal copper sputtering layer (21) by an electroplating process; the polyester film formed with the metal copper electroplating layer (22) is input from the copper electroplating tank (301) into the protective electroplating tank (302), and a protective layer (23) is formed on the outer side of the metal copper electroplating layer (22) by an electroplating process.

2. The manufacturing system according to claim 1, characterized in that, The annular vacuum sputtering chamber (202) at least includes a barrier material sputtering chamber (2021) provided upstream, and at least one copper material sputtering chamber (2022) is included downstream of the barrier material sputtering chamber (2021).

3. The manufacturing system according to claim 2, wherein At least one first infrared heating unit (2023) for baking the input polyester film to remove moisture is provided on one side of the feed port of the annular vacuum sputtering chamber (202).

4. The manufacturing system according to claim 3, characterized in that, At least one second infrared heating unit (2024) for heating the material conveying roller is provided on one side of the discharge port of the annular vacuum sputtering chamber (202), and the material conveying roller further heats the output polyester film.

5. The manufacturing system according to claim 3 or 4, characterized in that, The feeding port and the discharging port of the annular vacuum sputtering chamber (202) are both provided with material-changing gates (2025) for isolating the annular vacuum sputtering chamber (202) from the corona chamber (201) and the material receiving chamber (203) during material change.

6. The manufacturing system according to claim 1, wherein The following raw materials in parts by weight are added to the mixer (101): 30-50 parts by weight of poly(m-phenylene isophthalamide), 1-3 parts by weight of cobalt neodecanoate, 3-5 parts by weight of dibutylhydroxytoluene, 5-10 parts by weight of 1,4-diiodobenzene, 20-30 parts by weight of silicon dioxide, and 50-100 parts by weight of PET.

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