CN115782341A

CN115782341A - Manufacturing system for composite copper foil film

Info

Publication number: CN115782341A
Application number: CN202211111579.XA
Authority: CN
Inventors: 吴培服; 吴迪; 池卫; 周振; 许庚午
Original assignee: Jiangsu Shuangxing Color Plastic New Materials Co Ltd
Current assignee: Jiangsu Shuangxing Color Plastic New Materials Co Ltd
Priority date: 2022-09-13
Filing date: 2022-09-13
Publication date: 2023-03-14

Abstract

The invention discloses a manufacturing system for a composite copper foil film, which comprises a film making device for preparing a polyester film forming a substrate layer, a pre-coating processing device for pre-treating the polyester film and forming metal copper sputtering layers on two sides of the polyester film, and a water electroplating device for forming a metal layer electroplating layer and a protective layer on the outer side of the metal copper sputtering layers. According to the manufacturing system, the three-layer composite polyester film is prepared, the vacuum sputtering process and the water electroplating process are combined, so that excellent electrical performance and adhesive force can be obtained on the premise of not damaging the surface structure of the base material layer, the possibility that the base material layer has the defects such as fusing or scalding is basically eliminated, and the excellent electrical performance and adhesive force can be obtained.

Description

Manufacturing system for composite copper foil film

Technical Field

The application relates to a manufacturing system of a composite copper foil film capable of being used as a negative current collector of a lithium ion battery.

Background

The current collector in the lithium ion battery consists of a metal foil film for conducting electricity, and is mainly used for bearing electrode materials of a positive electrode and a negative electrode, and collecting current and conducting electrons at the same time. The common positive current collector adopts aluminum foil, and the common negative current collector adopts copper foil.

CN 112201389B discloses a conductive film for replacing aluminum foil and a preparation method thereof, the conductive film includes a metal layer, a middle reinforcement layer and a polymer film layer, the middle reinforcement layer is disposed on two sides of the polymer film layer, and the metal layer is disposed on the outer side of the middle reinforcement layer. The middle enhancement layer is formed on two sides of the high-molecular film layer in a magnetron sputtering coating or evaporation coating mode; the metal layer is formed on the outer side of the middle enhancement layer in a vapor deposition coating or magnetron sputtering mode. The conductive film in the prior art needs to evaporate the target material into gas at high temperature and then adhere to the surface of the polymer thin film layer, and the higher the evaporation temperature of the target material is, the more easily the polymer thin film layer has defects such as fusing or scalding. Therefore, the prior art generally produces composite aluminum foil by magnetron sputtering or evaporation, and there are few cases of preparing composite copper foil because the evaporation temperature of copper is higher. The higher the evaporation temperature of the target material is, the higher the operation speed of the polymer film layer is required to be, so that the thinner the formed metal layer is, the correspondingly worse the conductivity of the conductive film is, and the target material is not suitable for being used as a negative electrode current collector of a lithium ion battery. Therefore, the composite aluminum foil prepared in the prior art can only be used as a food packaging material, and the metal layer formed by evaporation has poor adhesion and is very easy to fall off.

Another reason why the metal layer of the composite metal foil is easily detached is that the surface structure of the nonmetallic substrate layer for receiving the metal layer is not uniform, and the adhesion of the metal layer to the substrate layer is insufficient. In order to relieve the influence of long-time high-temperature baking on the surface performance of the base material layer, the base material layer needs to be gradually stacked at intervals to form a metal layer, and the defects of various structural properties of the base material layer can be gradually amplified by the stacked metal layer, so that the conventional composite metal foil and the preparation process thereof are difficult to be applied to the production and preparation of the composite copper foil film capable of being used as a current collector.

In a word, the composite metal foil in the prior art adopts a magnetron sputtering or evaporation method to obtain a very thin metal layer on a substrate, and is easy to fuse or scald and break when operated at high temperature for a long time, so that the conductivity and uniformity of the composite metal foil have fatal defects, and particularly, the composite copper foil film meeting the conductivity and safety requirements of a lithium ion battery is difficult to prepare by the process, and the adhesion of the metal layer can be influenced by the defects of the substrate.

Disclosure of Invention

The technical problem to be solved by the present application is to provide a manufacturing system of composite copper foil film to reduce or avoid the aforementioned problems.

In order to solve the technical problem, the application provides a manufacturing system for a composite copper foil film, which comprises a film making device for preparing a polyester film forming a substrate layer, a pre-coating processing device for pre-treating the polyester film and forming metal copper sputtering layers on two sides of the polyester film, and a water electroplating device for forming a metal layer electroplating layer and a protective layer on the outer side of the metal copper sputtering layers; the film making device comprises a mixer and a first extruder, wherein the mixer is used for preparing polyester functional master batch, the polyester functional master batch output from the first extruder and common PET resin input from a common PET resin feed pipe are input into a mixing bin through a pipeline to be uniformly mixed and further input into a second extruder; and respectively inputting the polyester functional master batch melted by the second extruder into the film preparation mechanism through a surface layer pipeline and a bottom layer pipeline to prepare a surface layer A and a bottom layer C of the polyester film, and inputting the common PET resin into the film preparation mechanism through the third extruder and a core layer pipeline to prepare a core layer B of the polyester film.

Preferably, the pre-coating treatment device comprises a corona cavity, an annular vacuum sputtering cavity and a material receiving cavity, wherein the corona treatment is carried out on the surface of the polyester film prepared by the film preparation device to obtain a corona layer; inputting the polyester film subjected to corona treatment into an annular vacuum sputtering cavity from a corona cavity, sputtering the polyester film to form a barrier layer on the outer side of a corona layer through the annular vacuum sputtering cavity, and sputtering the polyester film to form a metal copper sputtering layer on the outer side of the barrier layer; and the polyester film forming the metal copper sputtering layer is conveyed into a material receiving cavity from the annular vacuum sputtering cavity to receive the polyester film into a coil.

Preferably, the water electroplating device comprises a copper electroplating bath and a protection electroplating bath, the polyester film on which the metal copper sputtering layer is formed is input into the copper electroplating bath from the pre-plating treatment device, and the metal copper electroplating layer is formed on the outer side of the metal copper sputtering layer by adopting an electroplating process; the polyester film forming the metal copper plating layer is conveyed from the copper plating tank to a protective plating tank, and a protective layer is formed on the outer side of the metal copper plating layer through a plating process.

Preferably, the annular vacuum sputtering chamber at least comprises a barrier material sputtering chamber arranged at the upstream, and the downstream of the barrier material sputtering chamber at least comprises a copper material sputtering chamber.

Preferably, at least one first infrared heating unit for removing water vapor and baking the input polyester film is arranged on one side of the feeding hole of the annular vacuum sputtering cavity.

Preferably, one side of the discharge hole of the annular vacuum sputtering cavity is provided with at least one second infrared heating unit for heating the material conveying roller, and the material conveying roller further heats the output polyester film.

Preferably, the feeding hole and the discharging hole of the annular vacuum sputtering cavity are both provided with material changing gates for isolating the annular vacuum sputtering cavity from the corona cavity and the material receiving cavity during material changing.

Preferably, the following raw materials in parts by weight are added into the mixer: 30-50 parts of poly (m-xylylene diamide), 1-3 parts of cobalt neodecanoate, 3-5 parts of dibutyl hydroxy toluene, 5-10 parts of 1, 4-diiodobenzene, 20-30 parts of silicon dioxide and 50-100 parts of PET.

According to the manufacturing system, the three-layer composite polyester film is prepared, and the vacuum sputtering process and the water electroplating process are combined, so that excellent electrical performance and adhesive force can be obtained on the premise of not damaging the surface structure of the base material layer, the possibility of fusing or scalding and other defects of the base material layer is basically eliminated, and the excellent electrical performance and adhesive force can be obtained.

Drawings

The drawings are only for purposes of illustrating and explaining the present application and are not to be construed as limiting the scope of the present application.

Fig. 1 shows a schematic structural diagram of a composite copper foil film according to an embodiment of the present application.

Fig. 2 is a schematic diagram showing a structure of a composite copper foil film according to another embodiment of the present application.

Fig. 3 is a schematic diagram of a manufacturing system for a composite copper foil film according to an embodiment of the present application.

Fig. 4 is a schematic structural diagram of a pre-plating treatment device of a manufacturing system for a composite copper foil film according to another embodiment of the present application.

Detailed Description

In order to more clearly understand the technical features, objects, and effects of the present application, embodiments of the present application will now be described with reference to the accompanying drawings. Wherein like parts are given like reference numerals.

As shown in fig. 1-2, the present invention provides a composite copper foil film that can be used as a negative 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, and the conductive layers 2 are mainly composed of metal copper. As described above, since the evaporation temperature of metal copper is high, if it is attached to the surface of the base material layer 1 made of a polymer material by vapor deposition, uniformity of the surface structure of the base material layer 1 is deteriorated, and it is difficult to obtain a thickness necessary for sufficient electrical performance, and the larger the thickness of the stack is, the more easily the powder falls off, and it is not suitable for use as a negative electrode current collector.

In view of the above, the present application proposes a composite copper foil film, wherein the conductive layer 2 adopts a multi-layer conductive structure, and in the illustrated embodiment, the conductive layer 2 sequentially comprises a metal copper sputtering layer 21, a metal copper electroplating layer 22 and a protective layer 23 from inside to outside. The metal copper sputtering layer 21 is a layer of metal copper with the thickness of 5-15nm, which is formed on the two side surfaces of the base material layer 1 by adopting a vacuum sputtering process, the metal copper electroplating layer 22 is a layer of metal copper with the thickness of 100-500nm, which is formed on the outer surface of the metal copper sputtering layer 21 by adopting a water and electricity plating process, the protective layer 23 is a compact protective layer formed by passivating the outer surface of the metal copper electroplating layer 22 by an electroplating or chemical corrosion process, and preferably, the protective layer 23 is a metal chromium protective layer with the thickness of 5-15nm, which is formed by an electroplating process.

In the composite copper foil film, the compactness and the adhesive force of a metal copper sputtering layer formed by vacuum sputtering are far superior to those of an evaporation process, and the running speed of the base material layer can be fast due to the fact that the required thickness is very thin, so that the possibility that the base material layer has the defects of fusing or scalding and the like is basically avoided. The thickness of the metal copper sputtering layer is very thin, but basic conductive performance can be provided, so that a thicker metal copper layer can be further grown on the surface of the metal copper sputtering layer by means of water electroplating. Through the combination of the vacuum sputtering process and the water electroplating process, the application can obtain excellent electrical performance and adhesive force on the premise of not damaging the surface structure of the base material layer, which will be further explained later.

In addition, in order to avoid the problem of insufficient adhesion of the metal copper layer caused by the uneven surface structure of the substrate layer, the present application also provides an improved substrate layer 1, and 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, and the substrate layer 1 may be a polyester film (fig. 1) with a three-layer structure including a surface layer a, a core layer B and a bottom layer C, to which the polyester functional masterbatch is added on the surface layer and the bottom layer, or a polyester film (fig. 2) with a single-layer structure, to which the polyester functional masterbatch is added.

The polyester referred to in the present invention is a polyester comprising one or more selected from polybasic carboxylic acids containing dibasic acids and their ester-forming derivatives, and one or more selected from polyhydric alcohols containing dibasic alcohols; or polyesters formed from hydroxycarboxylic acids and their ester-forming derivatives; or a polyester formed from a cyclic ester. The polyester can be produced by a conventionally known method. For example, taking the preparation of PET as an example, it can be obtained by: a method of performing polycondensation after esterification of terephthalic acid and ethylene glycol; or a method in which an alkyl ester of terephthalic acid such as dimethyl terephthalate is subjected to ester exchange reaction with ethylene glycol and then subjected to polycondensation. The polyester of the present invention is preferably PET.

In a specific embodiment, the polyester film forming the substrate layer 1 is a single-layer polyester film containing 5 to 20wt% of polyester functional master batch, or is a three-layer polyester film containing a surface layer a, a core layer B and a bottom layer C and containing 5 to 20wt% of polyester functional master batch, and the polyester functional master batch is prepared from the following raw materials in parts by weight: 30-50 parts of poly (m-xylylene diamide), 1-3 parts of cobalt neodecanoate, 3-5 parts of dibutyl hydroxy toluene, 5-10 parts of 1, 4-diiodobenzene, 20-30 parts of silicon dioxide and 50-100 parts of PET.

The polyester functional master batch of the present invention can be prepared in a pellet or chip form, and added to a common polyester in the process of producing a polyester film to prepare the substrate layer 1 of the present invention. For example, 80 to 95wt% of polyester without other components and 5 to 20wt% of the polyester functional masterbatch of the present invention may be melt-blended, and then the substrate layer 1 of a single-layer structure may be produced by a process such as stretching, or the surface layer structure of the substrate layer 1 of the present invention may be obtained by a multilayer co-extrusion process.

The raw material components of the polyester functional master batch can be uniformly mixed in the form of granules, and then the polyester functional master batch can be obtained by extrusion and granulation by using equipment such as an extruder.

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-xylylene diamide), 1-3 parts by weight of powdered cobalt neodecanoate, 3-5 parts by weight of powdered dibutyl hydroxy toluene and 5-10 parts by weight of powdered 1, 4-diiodobenzene are added into a mixer for pre-dispersion and mixing, and the rotation speed is 1500-2000 rpm, and the mixture is mixed for 30-60 minutes to form a mixture. And then carrying out melt extrusion through a double-screw extruder, and then carrying out water-cooling granulation or slicing to obtain the polyester functional master batch.

In another embodiment, for example, after preparing the chip for obtaining the polyester functional master batch, 5 to 20wt% of the polyester functional master batch is added into 80 to 95wt% of PET particles for uniform mixing, the two are melt blended, and finally the substrate layer 1 with a single-layer structure is produced by a process such as stretching, or the surface layer a and the bottom layer B of the substrate layer 1 with a three-layer structure are obtained by a multilayer co-extrusion process.

The preparation method of the polyester film for the composite copper foil film of the present invention is further described below by taking a single-layer polyester film as an example. The preparation method of the polyester film for the composite copper foil film comprises the following steps:

the components with the following weight ratio: 80-95 wt% of PET resin and 5-20 wt% of polyester functional master batch are respectively metered by an electronic scale and enter a mixing bunker to be mixed to prepare a mixture.

Then the mixture enters an exhaust type double-screw extruder, and the temperature of the double-screw extruder is adjusted to be 270-280 ℃.

After the materials are melted in an extruder, the materials are filtered and extruded to be made into thick sheets. The thickness and the profile of the slab can be adjusted by the extrusion amount of an extruder, the rotating speed of a casting sheet roller and the opening degree of a die head.

Preheating the thick sheet at 50-90 ℃, entering an infrared heating zone at 300-500 ℃, and longitudinally stretching at a linear speed of 40-150 m/min, wherein the longitudinal stretching ratio is 4.0, thus obtaining the stretched sheet.

Preheating the stretched sheet at the temperature of 90-120 ℃, and transversely stretching the sheet at the temperature of 100-160 ℃, wherein the transverse stretching ratio is 3.8. Then the mixture is shaped at the temperature of 160-240 ℃, and then is cooled at the temperature of 100-50 ℃ to obtain the polyester film for the composite copper foil film.

The thickness of the polyester film is 6-10 μm.

The following will further illustrate the preparation method of the polyester film for composite copper foil film of the present invention by taking three-layer polyester film as an example. The preparation method of the polyester film for the composite copper foil film comprises the following steps:

And then the mixture enters an exhaust type double-screw extruder E.

100% of PET resin is put into a pre-crystallizer, pre-crystallized for 15 minutes at the temperature of 160 ℃, and then the PET material enters a drying tower, is dried for 6 hours at the temperature of 160 ℃ and then enters a single-screw extruder F.

The temperature of the twin-screw extruder E and the twin-screw extruder F is adjusted to 270 ℃ to 280 ℃.

After the materials are melted in the two extruders, the materials extruded by the double-screw extruder E are used as a surface layer A and a bottom layer C after being filtered, the materials extruded by the single-screw extruder F are used as a core layer B, and the three-layer composite thick sheet is manufactured through a multi-layer co-extrusion process. The thickness and the profile of the slab can be adjusted by the extrusion amount of an extruder, the rotating speed of a casting sheet roller and the opening degree of a die head.

Preheating the stretching sheet at the temperature of 90-120 ℃, and transversely stretching the stretching sheet at the temperature of 100-160 ℃, wherein the transverse stretching ratio is 3.8. Then the three-layer structure polyester film is prepared by shaping at the temperature of 160-240 ℃ and cooling at the temperature of 100-50 ℃.

The thickness of the prepared polyester film is 6-10 μm, wherein the thickness of the layer A is 1-2 μm, the thickness of the layer B is 2-8 μm, and the thickness of the layer C is 1-2 μm.

Examples 1 to 5

According to the weight parts of the raw materials in the following table, polyester functional master batch chips are respectively prepared and then added with common PET resin to prepare the polyester film with a single-layer structure for the composite copper foil film.

	Example 1	Example 2	Example 3	Example 4	Example 5
						Poly (m-xylylene diamide)	30	35	40	45	50
Cobalt neodecanoate	1	1.5	2	2.5	3
						Dibutylhydroxytoluene	3	3.5	4	4.5	5
1, 4-diiodobenzene	5	7	7.5	8	10
						Silicon dioxide	20	22	25	27	30
PET	50	65	75	85	100
						Amount of slices to prepare a monolayer substrate layer	5wt％	10wt％	13wt％	15wt％	20wt％
Thickness of the substrate layer	6	7	8	9	10

Comparative examples 6 to 10

In the same manner as in the above examples, comparative polyester films were prepared by the following weight parts of raw materials.

	Comparative example 6	Comparative example 7	Comparative example 8	Comparative example 9	Comparative example 10
						Poly (m-xylylene diamide)	0	35	40	45	50
Cobalt neodecanoate	1	0	2	2.5	3
						Dibutylhydroxytoluene	3	3.5	0	4.5	5
1, 4-diiodobenzene	5	7	7.5	0	10
						Silicon dioxide	20	22	25	27	0
PET	80	66.5	79	93	130
						Amount of slices to prepare a monolayer substrate layer	5wt％	10wt％	13wt％	15wt％	20wt％
Thickness of the substrate layer	6	7	8	9	10

The performance parameters of each polyester film obtained by preparation are respectively tested, meanwhile, films with the thickness of 8 mu m prepared by pure PET without any functional master batch are compared, and the performance parameters are shown in the following table.

And respectively forming metal copper sputtering layers on the surfaces of the two sides of the polyester film on the upper surface by a vacuum sputtering process, controlling the thickness of the metal copper layers on the two sides of the vacuum sputtering film to be 5nm, and testing the surface crack parameters of the prepared film.

The performance parameters of the film layer and the crack condition of the metal coating are visible, the porosity, the water absorption, the oxygen transmission rate and other performances of the polyester film prepared by adding the polyester functional master batch are greatly improved, and no obvious crack propagation is observed after the metal copper conductive layer is formed.

Further, the resistivity difference of the metal copper sputtered layers on both sides of the polyester film shown in the above table was tested as shown in the following table.

According to the polyester film prepared by adding the polyester functional master batch, the resistivity difference of a metal copper sputtering layer formed on the polyester film is obviously smaller than that of a film without the functional master batch, and the two-side structure of the film is more excellent in consistency.

Further, since the present application requires that the metal copper sputtering layer 21 be formed on the surface of the base material layer 1 first, the base material layer 1 needs to be controlled to operate at a relatively low temperature during sputtering. Although the mylar of the improved substrate layer 1 has excellent properties such as porosity, water absorption, oxygen transmission rate, etc., it is still necessary to prevent the interference of the moisture released when the mylar surface absorbs water at low temperature and then sputters with the vacuum degree.

Therefore, in a specific embodiment, as shown in fig. 2, in order to avoid the moisture absorption and release problem of the substrate layer 1 during sputtering, a barrier layer 11 is further formed by sputtering 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 layer of barrier layer 11 made of 2-3nm silicon dioxide can be deposited on each of the two side surfaces of the substrate layer 1 through a double-rotating cathode and intermediate frequency reactive magnetron sputtering method, so that the surface of the substrate layer 1 is coated and isolated, and a hydrophobic structure is formed on the surface of the substrate layer 1.

Further, since the thickness of the barrier layer 11 is small, in order to improve the adhesion of the barrier layer 11 to the surface of the base material layer 1, it is preferable that the surface of the base material layer 1 is subjected to corona treatment before the formation of the barrier layer 11 by sputtering so as to form a corona layer 10 having a thickness of 1 to 2nm on the surface of the base material layer 1, and the barrier layer 11 is formed outside the corona layer 10. Corona treatment is a prior art, and the basic principle of corona discharge is to roughen the surface of the substrate layer 1 by using high frequency and high voltage to increase the adhesion of the surface of the substrate layer 1 to the barrier layer 11.

Of course, it should be understood by those skilled in the art that the corona layer 10 and the barrier layer 11 may be formed on the surface of the substrate layer 1 made of the polyester film having the three-layer structure shown in fig. 1.

The manufacturing system for the composite copper foil film of the present application is further described below with reference to fig. 3-4.

As shown in the drawing, the manufacturing system for a composite copper foil film of the present application includes a film forming apparatus 100 for preparing a mylar film constituting a base material layer 1, a pre-plating treatment apparatus 200 for pre-treating the mylar film and forming metal copper sputtering layers 21 on both sides thereof, and a water electroplating apparatus 300 for forming a metal layer plating layer 22 and a protective layer 23 on the outer sides of the metal copper sputtering layers 21.

The film making device 100 comprises a mixer 101 for preparing polyester functional master batch and a first extruder 102. As mentioned above, the following raw materials may be added to the mixer 101 at normal temperature in parts by weight: 30-50 parts of poly (m-xylylene diamide), 1-3 parts of cobalt neodecanoate, 3-5 parts of dibutyl hydroxy toluene, 5-10 parts of 1, 4-diiodobenzene, 20-30 parts of silicon dioxide and 50-100 parts of PET. More specifically, 50 to 100 parts by weight of powdered PET, 20 to 30 parts by weight of nano-silica, 30 to 50 parts by weight of powdered poly (m-xylylene diamide), 1 to 3 parts by weight of powdered cobalt neodecanoate, 3 to 5 parts by weight of powdered dibutylhydroxytoluene, and 5 to 10 parts by weight of powdered 1, 4-diiodobenzene may be added to the mixer 101 to be pre-dispersed and mixed at 1500 to 2000rpm for 30 to 60 minutes to form a mixed material. The polyester functional masterbatch is then obtained by melt extrusion through a first extruder 102 (e.g., a twin-screw extruder) followed by water-cooling pelletization or chipping.

The polyester functional masterbatch output from the first extruder 102 and the general PET resin input from the general PET resin feed pipe 103 are uniformly mixed by being input into the mixing silo 104 through a pipe and further input into the second extruder 105. As described above, for example, 5 to 20wt% of the polyester functional masterbatch obtained from the first extruder 102 and 80 to 95wt% of the general PET resin input from the general PET resin input pipe 103 may be input into the mixing bin 104 to be mixed to prepare a mixture, and then the mixture may be input into the second extruder 105 (e.g., the vented twin-screw extruder E).

The polyester functional master batch melted by the second extruder 105 is respectively input to the film preparation mechanism 108 through a surface layer pipeline and a bottom layer pipeline to prepare a surface layer a and a bottom layer C of the polyester film, and the common PET resin is input to the film preparation mechanism 108 through a third extruder 109 (for example, a single screw extruder F) and a core layer pipeline to prepare a core layer B of the polyester film. As mentioned above, for example, the material extruded by the twin-screw extruder E is used as the surface layer a and the bottom layer C, the material extruded by the single-screw extruder F is used as the core layer B, and the three-layer composite thick sheet is manufactured by the multilayer co-extrusion process of the film preparation mechanism 108; preheating the thick sheet at 50-90 ℃, feeding the thick sheet into an infrared heating zone at 300-500 ℃, and longitudinally stretching at a linear speed of 40-150 m/min, wherein the longitudinal stretching ratio is 4.0 to obtain a stretched sheet; preheating the stretching sheet at the temperature of 90-120 ℃, and transversely stretching the stretching sheet at the temperature of 100-160 ℃, wherein the transverse stretching ratio is 3.8; then the polyester film is shaped at the temperature of 160-240 ℃ and cooled at the temperature of 100-50 ℃ to obtain the polyester film with a three-layer structure.

Further, as shown in fig. 4, the pre-coating treatment apparatus 200 includes a corona chamber 201, an annular vacuum sputtering chamber 202 and a material receiving chamber 203, which perform corona treatment on the surface of the polyester film obtained by the film making apparatus 100 to obtain a corona layer 10; inputting the polyester film subjected to corona treatment into an annular vacuum sputtering cavity 202 from a corona cavity 201, sputtering and forming a barrier layer 11 on the outer side of a corona layer 10 through the annular vacuum sputtering cavity 202, and sputtering and forming a metal copper sputtering layer 21 on the outer side of the barrier layer 11; the polyester film forming the metallic copper sputtering layer 21 is fed from the ring-shaped vacuum sputtering chamber 202 into the take-up chamber 203 to take up the polyester film into a roll.

The corona cavity 201, the annular vacuum sputtering cavity 202 and the material receiving cavity 203 are formed into an integral structure, in order to keep the vacuum degree of the annular vacuum sputtering cavity 202 during material changing, material changing gates 2025 are arranged at a feeding port and a discharging port of the annular vacuum sputtering cavity 202, and are used for isolating the annular vacuum sputtering cavity 202 from the corona cavity 201 and the material receiving cavity 203 during material changing, as shown in the figure. The reloading gates 2025 are arranged at the outer sides of the feeding port and the discharging port of the annular vacuum sputtering chamber 202 in pairs, a slit for the polyester film to pass through is reserved between the reloading gates 2025, the polyester film is clamped in the middle when the gates are closed, and the polyester film extending out of the annular vacuum sputtering chamber 202 can be respectively adhered to the end parts of a new feeding roll and a new collecting roll to complete continuous reloading.

Multiple groups of tensioning rollers are arranged in the corona cavity 201 to maintain the tension of the polyester film in the running process. A corona electrode 2011 is arranged in the corona cavity 201 and used for forming a corona layer 10 on at least one side of the polyester film.

As can be seen from the structure in the figure, the pre-coating treatment device 200 can form the barrier layer 11 and the sputtered layer of metal copper 21 on only one side of the mylar film after one operation, so that in order to form the barrier layer 11 and the sputtered layer of metal copper 21 on both sides of the mylar film, it is necessary to reload the winding roll into the corona chamber 201 to sputter again on the other side of the mylar film after sputtering of one of the mylar films is completed. Therefore, only one set of structures needs to be arranged on the corona electrode 2011 in the corona cavity 201, only the corona layer 10 needs to be formed on one side needing sputtering, and then the barrier layer 11 is conveniently formed on the corona layer 10.

The middle part of the annular vacuum sputtering cavity 202 is provided with a hollow cooling roller 2029, a cooling medium is filled in the cooling roller 2029 during operation, the polyester film is tightly attached to the outer side of the cooling roller 2029 to run, and the polyester film is cooled to minus 20-30 ℃ by the cooling roller 2029 so as to prevent the polyester film from being scalded during sputtering.

Around the chill roll 2029, a plurality of sputtering chambers, seven chambers in total being shown in the figure, are provided in the ring-shaped vacuum sputtering chamber 202, wherein the middle chamber is not provided with sputtering material, and three chambers on both sides can be used as sputtering chambers.

The annular vacuum sputtering chamber 202 at least includes an upstream barrier sputtering chamber 2021, and the downstream of the barrier sputtering chamber 2021 at least includes a copper sputtering chamber 2022. For example, the first two sputtering chambers upstream of the polyester film run may be provided as a barrier material sputtering chamber 2021, in which two counter-rotating rods of material, for example, forming a silica barrier layer, may be provided. During sputtering, a bar material is used as a raw material supply source, and a barrier material such as silicon dioxide is sputtered on the polyester film under the action of high pressure. 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 may be provided as copper sputtering chambers 2022, wherein the first two sputtering chambers are provided with counter-rotating copper rod material. According to actual needs, only the first sputtering chamber at the upstream can be used as the barrier material sputtering chamber 2021, the subsequent three sputtering chambers can be used as the copper material sputtering chambers 2022, and the last two sputtering chambers can be provided with a single copper bar material to form the metal copper sputtering layers 21 distributed in the same direction at the outermost sides, so that the production speed of the copper layers during the subsequent water electroplating can be kept consistent.

In order to avoid the interference of the moisture on the surface of the mylar film to the sputtering, at least one first infrared heating unit 2023 for dehydrating and baking the input mylar film is arranged on one side of the feed inlet of the annular vacuum sputtering chamber 202.

Further, since the mylar is kept running at an extremely low temperature during sputtering, the low-temperature mylar entering the receiving cavity 203 will easily form condensed water thereon, and therefore, at least one second infrared heating unit 2024 for heating the feeding roller is disposed at one side of the discharge port of the annular vacuum sputtering cavity 202, and the feeding roller further heats the output mylar. The indirect heating is carried out on the material conveying roller by adopting the method, because the temperature of the polyester film is very low, the direct heating temperature field is not uniform, the polyester film is easy to scald or the heating temperature is inconsistent, the heating by the indirect heating mode is more uniform, and the efficiency of improving the temperature of the polyester film is higher.

Returning to fig. 3, the water-electric plating apparatus 300 includes a copper plating tank 301 and a protective plating tank 302, and the polyester film on which the metallic copper sputtering layer 21 is formed is transferred from the pre-plating treatment apparatus 200 to the copper plating tank 301, and the metallic copper plating layer 22 is formed on the outer side of the metallic copper sputtering layer 21 by a plating process; the mylar film forming the metal copper plating layer 22 is carried from the copper plating tank 301 to the protective plating tank 302, and the protective layer 23 is formed on the outer side of the metal copper plating layer 22 by a plating process.

As described above, the thickness of the sputtered layer of metallic copper is thin, but basic conductivity is provided, and thus the polyester film after being processed by the pre-plating treatment apparatus 200 is formed with a sputtered layer of metallic copper 21 on the surface thereof, and thereafter the plated layer of metallic copper 22 and the protective layer 23 can be formed in the copper plating bath 301 and the protective plating bath 302, respectively, by a conventionally known water plating process. For example, an electrolyte solution mainly containing copper sulfate may be added to the copper plating tank 301, an electrolyte solution mainly containing chromic anhydride and sulfuric acid may be added to the protective plating tank 302, and the plating thickness may be controlled by controlling the running speed of the polyester film and the length of the plating tank.

The polyester films prepared in examples 1 to 5 were used as a base material layer, and were subjected to corona treatment, sputtering of a barrier layer, sputtering of a metal copper sputtering layer, electroplating of a metal copper plating layer, and electroplating of a protective layer, respectively, to prepare a composite copper foil film having the following parameters.

According to the measurement parameters, the composite copper foil film has excellent electrical performance, the adhesive force of the conducting layer is extremely strong, and the conducting layer can hardly be peeled off in conventional use.

It should be appreciated by those skilled in the art that while the present application is described in terms of several embodiments, not every embodiment includes only a single embodiment. The description is thus given for clearness of understanding only, and it is to be understood that all matters in the embodiments are to be interpreted as including all technical equivalents which are encompassed by the claims and are to be interpreted as combined with each other in a different embodiment so as to cover the scope of the present application.

The above description is only an exemplary embodiment of the present disclosure, and is not intended to limit the scope of the present disclosure. Any equivalent alterations, modifications and combinations that may be made by those skilled in the art without departing from the spirit and principles of this application shall fall within the scope of this application.

Claims

1. A manufacturing system for a composite copper foil film, characterized by comprising a film-making device (100) for preparing a mylar film constituting a base material layer (1), a pre-plating treatment device (200) for pre-treating the mylar film and forming metal copper sputtering layers (21) on both sides thereof, and a water plating device (300) for forming a metal layer plating layer (22) and a protective layer (23) on the outer sides of the metal copper sputtering layers (21); the film making device (100) comprises a mixer (101) for preparing polyester functional master batch and a first extruder (102), wherein the polyester functional master batch output from the first extruder (102) and common PET resin input from a common PET resin feed pipe (103) are input into a mixing bin (104) through a pipeline to be uniformly mixed and further input into a second extruder (105); the polyester functional master batch melted by the second extruder (105) is respectively input into the film preparation mechanism (108) through a surface layer pipeline and a bottom layer pipeline to prepare a surface layer A and a bottom layer C of the polyester film, and the common PET resin is input into the film preparation mechanism (108) through the third extruder (109) and a core layer pipeline to prepare a core layer B of the polyester film.

2. The manufacturing system according to claim 1, wherein the pre-coating treatment device (200) comprises a corona chamber (201) for performing corona treatment on the surface of the polyester film obtained by the film making device (100) to obtain a corona layer (10), an annular vacuum sputtering chamber (202) and a material receiving chamber (203); inputting the polyester film subjected to corona treatment into an annular vacuum sputtering cavity (202) from a corona cavity (201), sputtering and forming a barrier layer (11) on the outer side of a corona layer (10) through the annular vacuum sputtering cavity (202), and sputtering and forming a metal copper sputtering layer (21) on the outer side of the barrier layer (11); the polyester film forming the metal copper sputtering layer (21) is conveyed into a material receiving cavity (203) from an annular vacuum sputtering cavity (202) to be received into a roll.

3. The manufacturing system according to claim 2, wherein the water plating apparatus (300) includes a copper plating tank (301) and a protective plating tank (302), the polyester film on which the metallic copper sputtering layer (21) is formed is fed from the pre-plating treatment apparatus (200) to the copper plating tank (301), and the metallic copper plating layer (22) is formed on the outer side of the metallic copper sputtering layer (21) by a plating process; the polyester film forming the metal copper plating layer (22) is transferred from the copper plating tank (301) to the protective plating tank (302), and the protective layer (23) is formed on the outer side of the metal copper plating layer (22) by a plating process.

4. The manufacturing system according to claim 2 or 3, wherein the annular vacuum sputtering chamber (202) comprises at least one barrier material sputtering chamber (2021) arranged upstream, and wherein the barrier material sputtering chamber (2021) comprises at least one copper sputtering chamber (2022) downstream.

5. The manufacturing system according to claim 4, wherein the feed inlet side of the ring-shaped vacuum sputtering chamber (202) is provided with at least one first infrared heating unit (2023) for steam-baking the fed mylar.

6. The manufacturing system according to claim 5, wherein the discharge side of the annular vacuum sputtering chamber (202) is provided with at least one second infrared heating unit (2024) for heating a feed roller, which in turn heats the outgoing mylar film.

7. The manufacturing system according to claim 5 or 6, wherein the feeding port and the discharging port of the annular vacuum sputtering chamber (202) are 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 changing.

8. A manufacturing system according to any one of claims 1 to 3, characterized in that the following raw materials are added to the blender (101) in parts by weight: 30-50 parts of poly (m-xylylene diamide), 1-3 parts of cobalt neodecanoate, 3-5 parts of dibutyl hydroxy toluene, 5-10 parts of 1, 4-diiodobenzene, 20-30 parts of silicon dioxide and 50-100 parts of PET.