KR20130109081A - Manufacturing method and manufacturing apparatus of metal foil - Google Patents

Abstract

PURPOSE: A method for manufacturing a metal film and a manufacturing device are provided to transfer a very thin metal film which is below 5 um smoothly because a cathode and a thin metal layer (a metal film) are transferred until a post process or a later process while the cathode and the thin metal layer are integrated. CONSTITUTION: A device for manufacturing a metal film comprises an anode (12) which is dipped in an electrolyte, a cathode (10), a thin metal layer forming unit, and a mobile unit. The thin metal layer forming unit forms a thin metal layer by extracting a metal on a surface of the cathode due to an electrolysis reaction when an interval between the anode and the cathode is electrified. The thin metal layer forming unit moves the cathode along the anode, and a metal is extracted on a surface of the cathode. In a state of attaching the extracted thin metal layer to the cathode, the mobile unit moves the cathode until a post processing about the thin metal layer. [Reference numerals] (P1,P2,P3) Pump

Description

Manufacturing method and apparatus of metal foil {MANUFACTURING METHOD AND MANUFACTURING APPARATUS OF METAL FOIL}

TECHNICAL FIELD This invention relates to the manufacturing method and manufacturing apparatus of a metal foil. Specifically, It is related with the thing which can manufacture ultra thin metal foil, and can convey easily a metal foil to the post process of processing this. .

Metal foil is a thin film of metal with good malleability. For example, there exists a rolled copper foil and an electrolytic copper foil in copper foil, and a rolled copper foil is produced by repeating rolling and annealing of electric copper normally. Moreover, electrolytic copper foil is manufactured by electrodepositing copper to a rotating drum, and winding this, and there exists an advantage that a crystal structure is dense and uniform. These are used, for example, in a flexible printed wiring board.

By the way, in order to obtain electrolytic foils of iron, copper, chromium, nickel, etc., first, an electrolytic reaction is carried out while supplying a predetermined electrolyte solution containing ions of these metals between an insoluble cathode body and an insoluble anode body. As a result, the target metal is deposited on the surface of the cathode by a desired thickness to form a metal foil layer. Next, it is manufactured by peeling the formed metal foil layer from the surface of a cathode body.

More specifically, for example, the electrolytic copper foil is conventionally manufactured by the drum type manufacturing apparatus 101 as shown in FIG. 3, and in this apparatus 101, the anode body 102 and the cathode body inside a plating bath not shown. (Drum type cathode) 103 is disposed, and the copper sulfate plating solution is filled in the plating bath. In this state, when the cathode body (drum type cathode) 103 is rotated and an electric current flows from the anode body 102 to the drum type cathode 103 using a rectifier (direct current power supply), the so-called electrolytic copper plating method causes titanium. Copper 104 was deposited on the drums 105 to form copper foil.

The precipitated copper 104 is peeled off from the drum-shaped cathode 103 and subjected to rust-proofing or the like in a predetermined post-treatment apparatus, and then wound into a roll shape, or It cut to predetermined dimension with the slitter and obtained the electrolytic copper foil (patent document 1).

As for the copper foil manufactured as described above, when used for a material of a printed wiring board, for example, it is required to have an ultra-thin thickness of less than 5 μm due to the request for higher density, lighter weight, or multilayer of circuits, In recent years, the demand for ultra-thin copper foil products has increased.

However, in manufacture of copper foil, it is necessary to perform surface rust prevention treatment and other post-processing after foil manufacture. In this case, since ultra-thin copper foil whose thickness is 5 micrometers or less has very low mechanical strength, it is not easy to transfer to a post-processing process, without damaging this. Therefore, in fact, about ultra-thin copper foil whose thickness is 5 micrometers or less, realization of efficient manufacture was difficult unless this problem was solved.

Therefore, about the ultra-thin copper foil, the ultra-thin copper foil with a carrier which directly electrodeposited the ultra-thin copper foil layer across the peeling layer is used on one side of the comparatively thick carrier copper foil, in order to avoid the trouble which conveyance is difficult, At the time of use of copper foil, this is peeled from carrier copper foil (patent document 2).

(Prior art technical literature)

(Patent Literature)

(Patent Document 1) Japanese Unexamined Patent Application Publication No. 10-18076

(Patent Document 2) Japanese Unexamined Patent Publication No. 2010-100942

In the conventional drum type foil manufacturing apparatus, when the electrolytic reaction is generated while supplying a predetermined electrolyte solution between a large drum type cathode and an anode (anode body), the gap between the cathode and the anode is wide, so that the current density is 60 to 70 ASD. Increasing) has a limit and there is a problem that it takes a relatively long time to manufacture the foil. Moreover, when an ultra-thin copper foil is manufactured by electrolytic foil with such an electrolytic density, there exists a problem that the incidence rate of a pinhole becomes high. In addition, it is not easy to peel off the precipitated ultra-thin copper foil from a drum.

On the other hand, since the ultra-thin copper foil with a carrier laminated | stacked copper foil from which the thickness used as a carrier is laminated | stacked, since the usage-amount of copper in manufacture increases and also requires time for manufacture, the manufacturing efficiency of ultra-thin copper foil falls. Moreover, there exists a problem that the cost of ultra-thin copper foil becomes high. In addition, the carrier copper foil in which the ultra-thin copper foil was electrodeposited is discarded after peeling off the layer of the surface ultra-thin copper foil. The discarded copper foil can be recovered and reused, but the efficiency of effective use of precious resources is reduced.

This invention is made | formed in view of such a technical background, and mainly makes it a technical subject to provide the manufacturing method of the metal foil which enabled the efficient manufacture of the ultra-thin metal foil which is 5 micrometers or less, and a manufacturing apparatus.

In order to achieve the above object, the present invention is configured as follows. That is, in the method for producing a metal foil according to the present invention, an anode body immersed in an electrolyte solution and a cathode body opposed thereto are energized, and metal is deposited on the surface of the cathode body by an electrolytic reaction to form a metal foil layer. In the method for producing a metal foil, the cathode body is moved along the anode to precipitate a metal on the surface, and then moved to the post-treatment position of the metal foil layer in a state where the deposited metal foil layer is attached. It is characterized by.

A post-treatment process is a water washing process, a zinc plating process, etc. with respect to a metal foil layer, for example. When manufacturing a printed wiring board material, a zinc plating process is a process which improves heat resistance by performing zinc plating on the surface of a metal foil layer, in order to ensure adhesiveness of a metal foil layer and a resin substrate also at the time of high temperature.

These post-treatment can be performed in the state which the deposited metal foil layer adhered to the cathode body.

Moreover, the said cathode body can be moved to the implementation position of the further process of further processing this, in the state with the metal foil which the post-processing completed. As a subsequent process, the lamination process of metal foil and insulating resin, etc. are mentioned, for example in manufacture of a printed wiring board material.

The treatment in these subsequent steps can be performed in a state where the deposited metal foil layer adheres to the cathode body.

According to this invention, it processes from the foil manufacture to the lamination | stacking process with insulating resin, for example, in the state which the deposited metal foil layer adhered to the cathode body consistently.

Therefore, even an ultra-thin metal foil having a thickness of less than 5 μm can be transported to a place where post-treatment or the like is carried out without damage. As a result, the ultra-thin metal foil having a thickness of less than 5 μm is subjected to necessary treatment or processing. You can do That is, manufacture of the ultra-thin metal foil whose thickness is less than 5 micrometers becomes what was substantially supported.

Moreover, the manufacturing apparatus of the metal foil which concerns on this invention is equipped with the anode body immersed in electrolyte solution, and the cathode body which opposes this, it is energized between these anode bodies and a cathode body, and the said cathode body is carried out by electrolytic reaction. A metal foil manufacturing apparatus for depositing a metal on a surface to form a metal foil layer, wherein the cathode body is moved along the anode to deposit a metal on the surface of the cathode, and the cathode And moving means for moving to the post-treatment process for the metal foil layer in a state where the deposited metal foil layer is attached.

The cathode body may be a belt or a plate body that is movable along the anode body.

Moreover, the said moving means can be made into a conveyor. A conveyor can be made into the belt conveyor apparatus which rotate-drives a continuous belt, or the conveyor which can convey a plurality of separated plate-shaped objects continuously.

Each said component can be combined as much as possible.

In the production method and the production apparatus according to the present invention, by changing the conditions of electrolysis, a raw foil having mechanical properties suitable for each use, such as for printed wiring boards and high-performance digital devices, can be produced. have. A raw foil having such a different characteristic can be produced, for example, in a range of 0.5 µm to 100 µm.

As described above, according to the present invention, since the cathode body and the metal foil layer (metal foil) move together to the post-treatment or subsequent steps, the ultra-thin metal foil having a thickness of less than 5 µm can be transferred without difficulty.

In addition, the cathode body with the metal foil layer has a band shape or a plate shape, and it is easy to keep the gap with the anode body narrow, and it is possible to keep the current density to be supplied high, so that the foil manufacturing time can be shortened. In addition, ultra-thin metal foil having fine crystals can be obtained.

Therefore, efficient manufacture of high quality ultra-thin metal foil whose thickness is 5 micrometers or less substantially can be implement | achieved, and the efficiency of manufacture of the product using this can also be aimed at.

BRIEF DESCRIPTION OF THE DRAWINGS It is an overall schematic of the manufacturing apparatus of the metal foil shown in embodiment of this invention.
2 is an overall schematic view of an apparatus for producing a metal foil using a stainless steel plate divided as a cathode.
It is a perspective view which shows an example of the conventional manufacturing apparatus of metal foil.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of the manufacturing apparatus of the metal foil which concerns on this invention is described in detail with reference to drawings.

(Embodiment Mode 1)

As the manufacturing apparatus 1 of the metal foil which concerns on this embodiment is shown in FIG. 1, the electrolytic bath 2, the 1st post-processing tank 3, and the 2nd post-processing tank (4), The electrolytic bath 5 for galvanizing and the antirust process tank 6 are provided so that it may continue in parallel. From these electrolytic baths 2, an endless belt 10 made of stainless steel is arranged on the upper portion of the rust-preventing treatment tank 6, and is continuous from the upstream side (right side in the drawing) of the manufacturing apparatus 1 to the downstream side. Thus, the drive means 26 of the belt 10 is provided so as to be able to move downstream.

The electrolytic cell 2 is a tank which consists of a material which has corrosion resistance with respect to the electrolytic treatment liquid to be used, for example, FRP (fiber-reinforced plastics), etc., and whose upper surface is open and a horizontal cross section is rectangular.

In the electrolytic cell 2, the insoluble anode body 12 which consists of lead and iridium oxide, for example is arrange | positioned. Moreover, the belt 10 as an insoluble cathode body which consists of stainless steel, stainless steel of chromium coating, etc. is located in the upper part of the electrolytic cell 2. In the electrolytic cell 2, since the electrolytic solution 13 of predetermined type and concentration, such as a copper sulfate plating liquid, is filled, the said belt 10 contacts this electrolyte solution 13.

In addition, the pump P1 is provided in close proximity to the electrolytic cell 2, a suction pipe 14 is connected to the suction port of the pump P1, and a discharge pipe 15 is connected to the discharge port, respectively. By driving this pump P1, the electrolyte solution 13 in the electrolytic cell 2 is comprised so that it may inject from the side part of the anode body 12. As shown in FIG. That is, the distal end of the discharge tube 15 is a distributor (electrolyte solution outlet) 16 in contact with the side of the anode body 12.

Then, the distributor 16 moves the belt 10 in the direction of the arrow while supplying the electrolyte solution 13 to the gap 17 between the anode body 12 and the belt 10, and the anode body 12 and the anode body 12. The electrolytic reaction is conducted by energizing a predetermined current density between the belts 10. As a result, copper 18 is deposited on the surface of the belt 10 to a predetermined thickness.

In the apparatus of the present embodiment, high-speed electrolysis at a current density of 150 ASD or more is possible by using a jet, and copper foil can be generated at high speed.

The copper foil obtained by such a high speed electrolysis has a finer crystal structure than the existing copper foil, and it is hard to produce pinholes.

Moreover, according to this method, a copper foil with a high tensile strength and flexibility can be obtained with a fine crystal structure.

On the downstream side of the electrolytic cell 2, the first post-treatment tank 3 and the second post-treatment tank 4 adjacent thereto are provided. These first after-treatment tanks 3 and the second after-treatment tanks 4 adjacent thereto are provided with a pump P2 in close proximity, and although not shown, water is supplied to the intake port of the pump P2, while a plurality of discharge ports are provided. Discharge pipe 19 is connected, and the water supplied is sprayed toward copper 18 deposited on the surface of belt 10 by the driving of pump P2.

As described above, the belt 10 in which copper 18 is precipitated passes through the upper portion of the first after-treatment tank 3 and the second after-treatment tank 4 adjacent thereto. The water washing treatment for 18) is performed.

Next, when processing copper 18 as a printed wiring board material, in order to ensure adhesiveness with the resin substrate at the time of high temperature, it is preferable to perform the process which raises heat resistance on the surface of copper 18. In this embodiment, the zinc smooth electrolytic plating process of a suitable thickness is performed, and the adhesiveness with a resin substrate and heat resistance at the time of high temperature are made compatible. This treatment is to perform electrolytic plating of well-known metal zinc on the surface of the copper 18 in the electrolytic bath 5 for zinc plating provided with the anode body 12.

In addition, a pump P3 is provided in close proximity to the electrolytic bath 5 for galvanizing, a suction pipe 20 is connected to the suction port of the pump P3, and a discharge pipe 21 is connected to the discharge port, respectively. By driving this pump P3, the electrolyte solution 22 in the zinc plating electrolytic cell 5 is comprised so that it may be injected from the side part of the anode body 23. As shown in FIG. The distal end of the discharge tube 21 is a distributor (electrolyte solution outlet) 24 in contact with the side of the anode body 23.

Then, the distributor 24 moves the belt 10 in the direction of the arrow while supplying the electrolyte solution 22 to the gap 25 between the anode body 23 and the belt 10, and the anode body 23 and the anode body 23. The electrolytic reaction is conducted by energizing a predetermined current density between the belts 10. As a result, zinc is deposited on the surface of the copper 18 to a predetermined thickness.

The bath property of the molten zinc which electrolytic-plats metal zinc will not be specifically limited if it is a soluble zinc compound. It is preferable that the adhesion amount of the smooth plating of zinc shall be 2.5-4.5 mg / dm <2> as metal zinc. If it is such an adhesion amount range, when copper 18 and a resin plate are laminated | stacked and a copper foil laminated board is manufactured in a subsequent lamination process, it will become brass which is an alloy of copper and zinc under heat-pressing press conditions about 160-240 degreeC. The brass layer does not impair high frequency conduction properties.

You may make it apply | coat the chromate rust inhibitor to the zinc process surface by zinc plating of the surface of copper obtained by the above-mentioned by the immersion process in the antirust process tank 6. In this case, copper 18 passes through the antirust treatment tank 6 and contacts the chromate rust preventive agent. In this way, the antirust treatment may be performed after the galvanizing treatment. However, the antirust treatment may be made to be chromate antirust treatment with a chromic acid dissolving solution or the like, with an emphasis on heat resistance.

When the post-processing as described above is finished, the copper 18 attached to the belt 10 is peeled off from the surface of the belt at the portion indicated by arrow A at the left end in FIG. 1. The copper foil obtained in this way can be wound by a winder etc. through the guide roller which is not shown in figure.

(Embodiment 2)

In this embodiment, the same code | symbol is attached | subjected to the same part as Embodiment 1 mentioned above, and description is abbreviate | omitted.

In this manufacturing apparatus 7, as shown in FIG. 2, like the apparatus shown in the said embodiment, the electrolytic cell 2, the 1st after-treatment tank 3, the 2nd after-treatment tank 4, and zinc plating The electrolytic bath 5 and the rust prevention treatment tank 6 are provided in parallel in succession. And the plate-shaped object 30 (henceforth a stainless steel plate) made from stainless steel is continuously arrange | positioned toward the downstream side from the upstream side (right side in drawing) of the manufacturing apparatus 7, and the stainless steel plate 30 is a conveyor. It is detachably attached to the drive means 31, such as these, and is provided so that it can move to a downstream side sequentially.

In the apparatus according to this embodiment, instead of the belt, the stainless steel plates 30 are continuously arranged, held and conveyed on the conveyor 31, and the copper is deposited on the surface using the cathode as a cathode.

After the post-treatment, the precipitated copper can be sent to a subsequent step while being integral with the stainless steel plate 30.

For example, when using it as the printed wiring board material containing copper foil, it is sent to the apparatus in which the lamination process of laminating | stacking copper foil and an insulating resin is performed. In the lamination | stacking process, each stainless steel plate 30 with which the surface roughened copper was attached to a predetermined position as needed, and an epoxy resin board and a phenol resin board with respect to copper by a well-known method And other resin plates are integrally bonded. In this case, it can shape | mold suitably at predetermined shaping | molding temperature, shaping | molding pressure, or shaping | molding time according to the situation of the printed wiring board material manufactured.

After the various processes in the above process are complete | finished, copper foil is isolate | separated from the stainless steel plate which is a cathode body. The separated copper foil is finished to the lamination process with the resin plate as a printed wiring board material, and the copper foil of 5 micrometers or less is used.

Moreover, the number of processes, order, etc. of the post-processing of copper foil except foil manufacture can change arbitrarily.

In addition, as another post-process, when performing a hole processing process on the printed circuit board cut out to the work size, and forming a mounting hole and the hole for electronic component insertion, copper oxidation prevention process etc. can be illustrated.

According to this invention, the ultra-thin copper foil which does not require the comparatively thick copper foil (carrier) laminated can be manufactured, and it can obtain that there is no pinhole and thickness is 0.5-5 micrometers.

In addition, the copper foil obtained by this invention has a crystal diameter of 80-200 nm and ten-point average roughness (Rz) of 0.5 micrometer, for example, The surface where the cathode surface does not give a roughening process to the surface, for example. It was 1.5 micrometers or less in roughness, and it was the smooth surface which can form fine wiring. In addition, because of having a fine crystal structure, the tensile strength was high (for example, 400 MPa) and flexible (for example, 17% elongation).

In the production method and apparatus according to the present invention, there is an advantage that a small lot of foil can be manufactured, compared with the production using a conventionally expensive drum type foil production apparatus, and can be produced by an inexpensive facility suitable for small quantity production.

Moreover, compared with the ultra-thin copper foil which laminated | stacked the carrier copper foil, foil manufacturing cost is remarkably low.

Therefore, in manufacture of a printed wiring board, it is easy to provide the manufacturing line of the copper foil continuous to this in front of the manufacturing line of a printed wiring board, without using the copper foil manufactured separately.

In addition, when the ultra-thin copper foil obtained by the present invention is laminated with an ultra-thin prepreg in which fiber and a binder or a primer (adhesive agent) are mixed in advance in the manufacture of a printed wiring board, ultra-fine wiring can be easily and easily performed in good yield. A base material can be obtained easily.

1, 7: Metal foil manufacturing apparatus
2: electrolytic cell
3: first aftertreatment tank
4: second aftertreatment tank
5: electrolytic cell for zinc plating
6: antirust treatment tank
10: belt (cathode body)
11: anode
12: anode
13: electrolyte
14: suction pipe
15 discharge tube
16: Distributor
17: gap
18: copper
19: discharge tube
20: suction pipe
21: discharge tube
23: anode
24: Distributor (electrolyte outlet)
25: gap
26, 31: drive means
30: plate body (stainless steel plate)

Claims (5)

In the manufacturing method of the metal foil which energizes between the anode body immersed in electrolyte solution, and the cathode body which opposes this, and deposits a metal on the surface of the said cathode body by electrolytic reaction, and forms a metal foil layer,
After moving the said cathode body along the anode body to precipitate metal on the surface, it moves to the implementation position of the post-treatment with respect to a metal foil layer in the state which the deposited metal foil layer adhered to. Manufacturing method of metal foil.
The method of claim 1,
A method for producing a metal foil, wherein the cathode body is further moved to a position where the subsequent step of processing the metal foil layer after the post-treatment is finished in a state where the deposited metal foil layer is attached.
A metal foil comprising an anode body immersed in an electrolyte solution and a cathode body opposed thereto, and energized between these anode bodies and the cathode body to deposit metal on the surface of the cathode body by an electrolytic reaction to form a metal foil layer. In the manufacturing apparatus of
A metal foil layer forming portion for moving the cathode body along the anode body to deposit metal on the surface of the cathode body;
Transfer means for moving the cathode body to the post-treatment process for the metal foil layer in a state where the deposited metal foil layer is attached
An apparatus for producing a metal foil, comprising:
The method of claim 3, wherein
The cathode body is an endless belt or plate-like body which is movable along the anode body.
The method according to claim 3 or 4,
The moving means is a manufacturing apparatus of a metal foil, characterized in that the conveyor.

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