JPWO2012176883A1 - Metal foil manufacturing method and manufacturing apparatus - Google Patents

Abstract

  The present invention provides a metal foil manufacturing method and apparatus capable of efficiently manufacturing an ultrathin metal foil having a thickness of 5 μm or less. A current is passed between the anode body (12) immersed in the electrolytic solution (13) and the cathode body (10) that moves opposite to the anode body, and metal is deposited on the surface of the cathode body (10) by an electrolytic reaction. A thin metal layer is formed. The cathode body (10) is moved to the post-treatment position for the thin metal layer with the deposited thin metal layer attached, and after the predetermined post-treatment, the thin metal layer is removed from the cathode body (10). Peel off.

Description

  The present invention relates to a metal foil manufacturing method and a manufacturing apparatus, and more particularly, to a metal foil capable of making an ultrathin metal foil.

  The metal foil is obtained by thinly extending a metal having good spreadability. For example, the copper foil includes a rolled copper foil and an electrolytic copper foil. Of these, the rolled copper foil is usually produced by repeatedly rolling and annealing electrolytic copper. Further, the electrolytic copper foil is manufactured by electrodepositing copper on a rotating drum and winding it, and has an advantage that the crystal structure is dense and uniform. These are used, for example, for flexible printed wiring boards.

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

  More specifically, for example, electrolytic copper foil is conventionally manufactured by a drum-type foil making apparatus 101 as shown in FIG. 3, and in this apparatus 101, an anode body 102 and a cathode body (drum) are disposed inside a plating tank (not shown). Type cathode) 103 is disposed, and the plating tank is filled with a copper sulfate plating solution. When a current is passed from the anode body 102 to the drum-type cathode 103 using a rectifier (DC power supply) while rotating the cathode body (drum-type cathode) 103 in this state, a drum 105 made of titanium is formed by a so-called electrolytic copper plating method. Copper 104 was deposited thereon to form a copper foil.

  The deposited copper 104 is peeled off from the drum-type cathode 103 and subjected to a rust prevention treatment or the like in a predetermined post-processing apparatus, and then wound into a roll or cut into a predetermined dimension with a slitter. A foil was obtained (Patent Document 1).

  The copper foil manufacturing apparatus disclosed in Patent Document 2 uses an endless belt instead of a drum as the cathode body. A desired metal film is formed on the surface of the cathode body, and this metal film is formed on the endless belt. After peeling from the surface, the peeled metal film copper foil was plated in the next step.

  Regarding the copper foil produced as described above, for example, when used as a material for a printed wiring board, a pole having a thickness of less than 5 μm is required due to demands for high density, light weight, or multilayering of a circuit. The demand for ultra-thin copper foil products has increased dramatically in recent years.

  However, in the manufacture of copper foil, it is necessary to perform surface rust prevention treatment and other post-treatments after foil production. In this case, since the ultrathin copper foil having a thickness of 5 μm or less has extremely low mechanical strength, it is not easy to transfer it to the post-processing step without damaging it. For this reason, in practice, it has been difficult to achieve efficient production of an ultrathin copper foil having a thickness of 5 μm or less unless this problem is solved.

  Therefore, for ultra-thin copper foil, in order to avoid the problem of difficult transfer, with a carrier in which an ultra-thin copper foil layer is directly electrodeposited via a release layer on one side of a relatively thick carrier copper foil An ultrathin copper foil is used, and when the ultrathin copper foil is used, it is peeled off from the carrier copper foil (Patent Document 3). The formation of a metal layer on the surface of the cathode body is disclosed in Patent Document 4, but this relates to plating, and the plating layer formed on the surface of the cathode body is held so as not to peel off. Therefore, it is greatly different from the technique of forming a metal foil.

JP-A-10-18076 JP-A-54-15435 JP 2010-1000094 A2 Japanese Patent No. 3050819

In the conventional drum type foil making apparatus, when an electrolytic reaction is generated while supplying a predetermined electrolyte between a large drum type cathode and an anode (anode body), the current density is large because the gap between the cathode and the anode is wide. There is a limit to increasing (60 to 70 A / dm ² ), and there is a problem that it takes a relatively long time to produce the foil. Moreover, when an ultrathin copper foil is electrolytically formed at such an electrolytic density, there is a problem that the incidence of pinholes increases.

  On the other hand, since the ultra-thin copper foil with a carrier is a laminate of copper foils having different thicknesses as carriers, the amount of copper used in the production increases, and the production of the ultra-thin copper foil requires labor. Efficiency is reduced. In addition, there is a problem that the cost of the ultrathin copper foil is increased. Furthermore, the carrier copper foil electrodeposited with the ultrathin copper foil is discarded after the ultrathin copper foil layer on the surface is peeled off. Although the discarded copper foil can be recovered and reused, the efficiency of effective use of valuable resources is reduced.

  The present invention has been made in view of such a technical background, and mainly provides a metal foil manufacturing method and a manufacturing apparatus capable of efficiently manufacturing an ultrathin metal foil having a thickness of 5 μm or less. This is a technical issue.

In order to achieve the above object, the present invention is configured as follows. That is, the method for producing a metal foil according to the present invention energizes between an anode body immersed in an electrolytic solution and a cathode body facing the anode body, and deposits metal on the surface of the cathode body by an electrolytic reaction. In the method for producing a metal foil for forming a thin metal layer,
After the cathode body is moved along the anode body to deposit metal on the surface, the deposited thin metal layer is attached to the post-treatment position for the thin metal layer, and includes water washing. The thin metal layer is peeled off from the cathode body after performing the predetermined post-treatment.

Also, a method for producing a metal foil in which a thin metal layer is formed by energizing an anode body immersed in an electrolytic solution and a cathode body facing the anode body to deposit a metal on the surface of the cathode body by an electrolytic reaction In
After the cathode body is moved along the anode body to deposit metal on the surface, the deposited thin metal layer is attached to the post-treatment position for the thin metal layer, and includes water washing. A thin metal layer is peeled off from the cathode body after performing a predetermined post-treatment and a subsequent processing step.

  Here, the post-treatment includes, for example, a water washing step, a rust prevention treatment step, a roughening step, a galvanizing step, a nickel plating step and the like for the thin metal layer. Among these, the rust prevention treatment step is a treatment for subjecting the surface of the metal foil to chromate treatment, zinc chromate treatment or the like in order to prevent oxidative deterioration of the metal foil. The galvanization process is a process that increases the heat resistance by applying galvanization to the surface of the thin metal layer in order to ensure the adhesion between the thin metal layer and the resin substrate even at high temperatures when manufacturing printed wiring board materials. is there. The roughening process is a process for improving the adhesion with a resin substrate or the like.

  As long as the strength of the metal foil after peeling from the cathode body is maintained, the post-treatment method to be applied before peeling the metal thin layer from the cathode body is not particularly limited. As the method, one or more steps selected from the group consisting of a water washing step, a rust prevention treatment step, a roughening step, a galvanization step, and a nickel plating step are preferable, and a water washing step, a rust prevention treatment step, and a galvanization step One or more steps selected from the group consisting of are more preferable, and one or more steps selected from the group consisting of a water washing step and a rust prevention treatment step are more preferable. Even if a metal foil is used for a wide range of purposes, the water washing treatment process and the rust prevention treatment process are usually post-treatments to be performed for maintaining the quality.

  Since these post-treatments can be performed with the deposited metal thin layer attached to the cathode body, even an extremely thin metal foil can be treated without damaging it.

  Moreover, the said cathode body can be moved to the implementation position of the next process which processes this further, in the state in which the metal foil which the post-processing was complete | finished adhered. As the next process, for example, in the production of a printed wiring board material, a lamination process of a metal foil and an insulating resin, a curing process of the insulating resin, and the like can be shown.

  The treatment in these next steps can be performed in a state where the deposited thin metal layer is attached to the cathode body.

  According to the present invention, the process from the foil production to the lamination process with, for example, an insulating resin is performed in a state where the deposited thin metal layer is adhered to the cathode body.

  Therefore, even if it is an extremely thin metal foil having a thickness of less than 5 μm, it can be transferred to a place where post-treatment or the like is performed without damaging the foil, and as a result, the thickness is less than 5 μm. Necessary treatment or processing can be applied to the metal foil to obtain a product. That is, the production of an ultrathin metal foil having a thickness of less than 5 μm is substantially supported.

The metal foil manufacturing apparatus according to the present invention includes an anode body immersed in an electrolytic solution and a cathode body facing the anode body, energizing between the anode body and the cathode body, and performing the above-mentioned by an electrolytic reaction. In the metal foil manufacturing apparatus for forming a thin metal layer by depositing metal on the surface of the cathode body,
A metal thin layer forming section for moving the cathode body along the anode body and depositing metal on the surface of the cathode body;
Moving means for moving the cathode body to a post-treatment step for the thin metal layer, with the deposited thin metal layer attached thereto;
Peeling means for peeling the thin metal layer from the cathode body after performing a predetermined post-treatment including water washing;
It is characterized by providing.

  The anode body and the cathode body are both formed in a flat plate shape and can be arranged parallel to each other. In this way, the distance between the electrodes can be closely controlled and precisely controlled, so that the current density can be increased and a thin metal layer can be formed by high-speed electrolysis.

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

  The moving means may be a conveyor. The conveyor can be a belt conveyor device that rotationally drives a continuous belt, or a conveyor that can continuously convey a plurality of separated plates.

  The above components can be combined as much as possible.

  In the manufacturing method and the manufacturing apparatus according to the present invention, by changing the conditions of electrolysis, raw foils having mechanical properties suitable for respective uses such as for printed wiring boards and high-performance digital devices are manufactured. be able to. Such raw foils having different characteristics can be produced, for example, in the range of 0.5 μm to 100 μm.

  As described above, according to the present invention, since the cathode body and the metal thin layer (metal foil) are integrated with each other and move to the subsequent process or the next process, even an ultrathin metal foil of less than 5 μm is impossible. It is possible to transport without.

  In addition, the cathode body to which the thin metal layer is attached is strip-like or plate-like, and it is easy to keep the gap with the anode body narrow and the current density to be supplied can be kept high, so that the foil forming time And an ultrathin metal foil having fine crystals can be obtained.

  Accordingly, it is possible to efficiently manufacture a high-quality ultrathin metal foil having a thickness of substantially 5 μm or less, and to increase the efficiency of manufacturing a product using the same.

1 is an overall schematic view of a metal foil manufacturing apparatus shown in an embodiment of the present invention. It is the whole metal foil manufacturing apparatus schematic using the stainless plate divided | segmented as a cathode body. The perspective view which shows an example of the manufacturing apparatus of the conventional metal foil. It is the whole peeling apparatus schematic.

  Embodiments of a metal foil manufacturing apparatus according to the present invention will be described below in detail with reference to the drawings.

(Embodiment 1)
As shown in FIG. 1, the metal foil manufacturing apparatus 1 according to the present embodiment includes an electrolytic cell 2, a first post-treatment cell 3, a second post-treatment cell 4, a galvanizing electrolytic cell 5, and an antirust treatment. The tank 6 is provided so that it may continue in parallel. A stainless steel endless belt 10 is disposed from the electrolytic layer 2 to the upper portion of the rust prevention treatment tank 6, and continues from the upstream side (right side in the drawing) to the downstream side of the manufacturing apparatus 1, and the belt 10 driving means. 26 are installed so as to be sequentially movable downstream. The moving speed of the endless belt as the cathode body is 1 to 7 m / min. For efficient copper deposition. Is preferably 2 to 5 m / min. Is more preferable.

  The electrolytic cell 2 is made of a material having corrosion resistance with respect to the electrolytic treatment solution to be used, for example, FRP (fiber reinforced plastic), and the like.

In the electrolytic cell 2, an insoluble anode body 12 made of, for example, lead or iridium oxide is disposed. The anode body 12 is generally required to have a low oxygen generation potential. For example, a material obtained by coating platinum, iridium oxide, or the like on titanium is used. These can be used in the present invention as long as the anode is made of an insoluble material that can generate oxygen without being rendered non-conductive when energized.
A belt 10 serving as an insoluble cathode body made of stainless steel, chromium-coated stainless steel, or the like is positioned above the electrolytic cell 2. Since the electrolytic bath 2 is filled with a predetermined type and concentration of an electrolytic solution 13 such as a copper sulfate plating solution, the belt 10 is in contact with the electrolytic solution 13. The distance between the anode body and the cathode body is preferably 1 to 50 mm, more preferably 2 to 30 mm, and still more preferably 3 to 10 mm in order to increase the current density.

A well-known thing can be used as a copper sulfate plating solution, and especially the thing containing 10-300 g / l and 10-300 g / l of sulfuric acid as a copper sulfate hydrate is used suitably. Furthermore, the copper sulfate plating solution preferably contains 5 to 200 ppm of chlorine ions (Cl-). The pH of the copper sulfate plating solution is usually adjusted to 2 or less (0 to 2).
Each component other than copper (copper ions) in the copper sulfate plating bath is replenished by a conventionally known method such as addition of a replenisher as necessary, by reducing the components that have been reduced by continuous electrolytic copper plating, Plating can be continued.
The material of the belt 10 serving as the cathode body is preferably a metal that is resistant to sulfuric acid in the electrolyte, such as Pt, Ti, SUS, and more preferably SUS. The width of the belt 10 is preferably 400 to 1800 mm, more preferably 600 to 1200 mm, from the viewpoint of improving the handleability. Moreover, 0.1-0.8 mm is preferable and, as for thickness, 0.2-0.5 mm is more preferable.

  A pump P1 is provided in the vicinity of the electrolytic cell 2, and 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. The pump 13 is driven so that the electrolyte 13 in the electrolytic cell 2 is jetted from the side of the anode body 12. That is, the distal end of the discharge pipe 15 is a distributor (electrolyte outlet) 16 that contacts the side of the anode body 12.

  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 energizes the anode body 12 and the belt 10 with a predetermined current density. The electrolytic reaction proceeds. Then, copper 18 is electrodeposited on the surface of the belt 10 with a predetermined thickness.

Electrolysis conditions are not particularly limited, but in general, an electrolytic solution having a metal ion concentration of 10 g / l or more and 200 g / l or less in the presence of acid or alkali is used, and the current density of the anode is 50 A / liter. The temperature of the electrolytic solution can be 20 to 100 ° C. or less at dm ^{2 to} 600 A / dm ² (preferably 100 A / dm ^{2 to} 400 A / dm ² ).
In the apparatus of this embodiment, high-speed electrolysis can be performed at a current density of 150 A / dm ² or more using a jet, and a copper foil can be generated at high speed.

  A copper foil obtained by such high-speed electrolysis has a finer crystal structure than conventional copper foils, and is less prone to pinholes. The crystal diameter of the anode surface is preferably 30 to 300 nm and more preferably 50 to 200 nm for fine wiring. Further, the ten-point average roughness (Rz) of the anode surface is preferably 0.1 to 3 μm, more preferably 0.2 to 2 μm, and still more preferably 0.3 to 1 μm for fine wiring. Further, the ten-point average roughness (Rz) of the cathode surface is preferably 0.3 to 9 μm, more preferably 0.6 to 6 μm, and still more preferably 0.9 to 3 μm for fine wiring.

Moreover, according to this method, a copper foil having high tensile strength and flexibility can be obtained by a fine crystal structure. The tensile strength is preferably from 100 to 800 MPa, more preferably from 200 to 700 MPa, and even more preferably from 300 to 600 MPa for improving handleability. Further, the elongation is preferably 5 to 50%, more preferably 10 to 40%, and still more preferably 15 to 30% for improving the handleability.
In addition, this invention method is applicable also when manufacturing nickel other metal foil other than copper foil by an electrolytic reaction.

  A first post-treatment tank 3 and a second post-treatment tank 4 adjacent to the first post-treatment tank 3 are provided on the downstream side of the electrolytic cell 2. The first post-treatment tank 3 and the second post-treatment tank 4 adjacent to the first post-treatment tank 3 are provided with a pump P2 in close proximity, and water is supplied to the suction port of the pump P2, although not shown, A plurality of discharge pipes 19 are connected, and the pump P2 is driven so that the supplied water is jetted toward the copper 18 deposited on the surface of the belt 10.

  As described above, the water washing process for the copper 18 is performed by passing the belt 10 on which the copper 18 is deposited through the upper part of the first post-treatment tank 3 and the second post-treatment tank 4 adjacent thereto. become.

  Next, when processing the copper 18 as a printed wiring board material, it is preferable that the surface of the copper 18 is subjected to a treatment for improving heat resistance in order to ensure adhesion with the resin substrate at a high temperature. In the present embodiment, zinc smooth electrolytic plating treatment with an appropriate thickness is performed to achieve both adhesion to the resin substrate and heat resistance at high temperatures. In this treatment, the surface of the copper 18 is electroplated with a known metal zinc in the electrolytic bath 5 for zinc plating in which the anode body 23 is installed.

  A pump P3 is provided in the vicinity of the galvanizing electrolytic cell 5, and 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. By driving the pump P3, the electrolytic solution 22 in the galvanizing electrolytic cell 5 is jetted from the side of the anode body 23. The tip of the discharge pipe 21 is a distributor (electrolyte outlet) 24 that contacts the side of the anode body 23.

  Then, while supplying the electrolytic solution 22 to the gap 25 between the anode body 23 and the belt 10 by the distributor 24, the belt 10 is moved in the direction of the arrow, and the anode body 23 and the belt 10 are energized at a predetermined current density. The electrolytic reaction proceeds. Then, zinc is electrodeposited on the surface of the copper 18 with a predetermined thickness.

The bath composition of dissolved zinc for performing electrolytic plating of metallic zinc is not particularly limited as long as it is a soluble zinc compound. The amount of zinc smooth plating deposited is preferably ^2.5 to 4.5 mg / dm ² as metallic zinc. If it is such an adhesion amount range, when manufacturing a copper clad laminated board by laminating | stacking the copper 18 and a resin board by a subsequent lamination process, copper and zinc will be carried out on the heating-pressing press conditions of about 160-240 degreeC. It is brass which is an alloy of. The surface layer made of brass does not impair the high-frequency conduction characteristics.

  A chromate rust preventive may be further applied to the zinc-treated surface 8 by galvanization of the copper surface obtained as described above by dipping treatment in the rust-proof treatment tank 6. In this case, the zinc-treated surface 8 passes through the antirust treatment tank 6 and contacts the chromate antirust agent. In this way, the rust-proofing treatment can be performed after the galvanizing treatment, but this rust-proofing treatment can also be a chromate rust-proofing treatment with a chromic acid solution with emphasis on heat resistance.

  When the post-processing as described above is completed, the copper 18 adhering to the belt 10 is peeled off from the surface of the belt at a portion indicated by an arrow A at the left end in FIG. The copper foil that has been subjected to rust prevention treatment and the like thus obtained can be peeled off from the copper foil adhered to the surface of the belt 10 and wound up with a winder or the like.

  When peeling, a peeling device 40 as shown in FIG. 4 is used. In order to peel the copper 18 adhering to the belt 10, the surface of the belt 10 is polished in advance so as to have a mirror surface, and the contact area with the adhering copper 18 is reduced as much as possible, so that it can be easily peeled off. it can. The peeling device 40 includes a first nip roll 41 in the traveling path of the belt 10, and separates the belt 10 from the copper 18 while pressing the belt 10 with the copper 18 adhered between the upper roll 41a and the lower roll 41b. By guiding in the direction, the copper 18 is peeled from the belt 10. The peeled copper 18 passes between the upper and lower rolls of the second nip roll 43 whose surface is coated with a fluororesin, and is taken up by a winder 42 after being vented. The belt 10 can be wound by the belt winder 44, but the belt 10 is used as it is as a cathode body without being wound from the viewpoint of improving productivity and efficiently producing metal foil. It is preferable to do.

Said peeling apparatus 40 is an example, Comprising: The thing of the other structure provided with the same function may be sufficient.
As described above, an ultrathin copper foil having a thickness of 5 μm or less can be obtained by peeling from the belt 10 after necessary post-processing is performed. In addition, according to the present invention, the current density can be increased, and a metal foil excellent in tensile strength and flexibility can be obtained. Therefore, it can be easily peeled off from the cathode body, and can be easily wound even in the absence of carriers. It becomes possible.

(Embodiment 2)
In the present embodiment, the same parts as those in the first embodiment are denoted by the same reference numerals, and the description thereof is omitted.

  In this manufacturing apparatus 7, as shown in FIG. 2, the electrolytic cell 2, the first post-treatment tank 3, the second post-treatment tank 4, the galvanizing electrolytic tank 5, and the apparatus shown in the above embodiment, Rust prevention tank 6 is provided continuously in parallel. Then, stainless steel plate-like bodies 30 (hereinafter referred to as stainless steel plates) are continuously arranged from the upstream side (right side in the drawing) to the downstream side of the manufacturing apparatus 7, and the stainless steel plate 30 is a driving means such as a conveyor. 31 is detachably mounted, and is provided so as to be sequentially movable downstream.

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

  After the post-treatment, the deposited copper can be sent to the next step while being integrated with the stainless steel plate 30.

  For example, when it is set as the printed wiring board material containing copper foil, it sends to the apparatus in which the lamination process which laminates | stacks copper foil and insulating resin is implemented. In the laminating step, each stainless steel plate 30 to which the copper whose surface is roughened as necessary is attached is placed in a predetermined position, and is applied to copper by a well-known method. An epoxy resin plate, a phenol resin plate and other resin plates are bonded together. In this case, it can be appropriately molded at a predetermined molding temperature, molding pressure, or molding time according to the situation of the printed wiring board material to be manufactured.

  After the various processes in the above steps are completed, the copper foil is peeled off from the stainless steel plate that is the cathode body. The peeled copper foil has been completed up to the step of laminating with a resin board as a printed wiring board material, and a copper foil of 5 μm or less is used.

  In addition, about the post-process and process of copper foil except a foil manufacturing process, the number of processes, an order, etc. can be changed arbitrarily.

In addition, as another post-processing, when a printed circuit board cut out to a work size is subjected to a hole processing process to form a mounting hole and a hole for inserting an electronic component, an antioxidant process for copper can be exemplified.
The copper foil that has been post-processed or processed as described above may be transferred to a resin plate or the like when peeled from the stainless steel plate.

(Example 1)
The copper foil was manufactured using the electrolytic copper foil manufacturing apparatus shown in FIG. The belt made of SUS as the cathode body had a width of 800 mm and a thickness of 0.3 mm. The surface of this belt was buffed and finished into a mirror surface. The belt is sequentially moved in the direction of the electrolytic bath in FIG. Then, copper sulfate: 250 g / l, sulfuric acid: 60 g / l, chlorine: 20 ppm, an electrolyte having a liquid temperature of 50 ° C., current density of 250 A / dm ² , flow rate of 6 m / min. Copper was electrodeposited on the surface of the belt 10 under the conditions described above to form a copper foil layer having a thickness of 4 μm. The distance between the belt and the anode was 9 mm.

  As a post-treatment, galvanization was not performed, and rust prevention treatment with water washing and chromate (chromic acid) was performed.

  The obtained copper foil has an anode surface crystal diameter of 100 nm and a 10-point average roughness (Rz) of 0.5 μm. On the other hand, the cathode surface has a surface roughness of 1 without roughening treatment. It was a smooth surface capable of forming fine wiring at 0.0 μm. Moreover, since it has a fine crystal structure, it was flexible with a tensile strength of 400 MPa and an elongation of 17%.

(Example 2)
The copper foil was manufactured using the electrolytic copper foil manufacturing apparatus shown in FIG. A stainless steel plate made of SUS as a cathode body, having a width of 800 mm and a thickness of 0.3 mm was used. The surface of this stainless steel plate was buffed and finished into a mirror surface.
The stainless steel plate is sequentially moved in the direction of the electrolytic bath of FIG. Then, copper sulfate: 250 g / l, sulfuric acid: 60 g / l, chlorine: 20 ppm, an electrolyte having a liquid temperature of 50 ° C., current density of 250 A / dm ² , flow rate of 6 m / min. Copper was electrodeposited on the surface of the belt 10 under the conditions described above to form a copper foil layer having a thickness of 4 μm. The distance between the belt and the anode was 9 mm.

The copper foil layer was washed with pure water for 20 seconds, and subjected to a drying treatment for 10 seconds in a high temperature atmosphere at 150 ° C.
Next, galvanization was performed on the surface of the copper foil layer. The traveling speed of the copper removal foil in the plating solution is 3 m / min. One lot of 10 m was processed at a current density of 0.5 A / dm ² and a current density of 0.5 A / dm ² .
Processed.

  The copper foil on which the surface galvanization was completed was washed with pure water for 20 seconds, and was subjected to a drying treatment for 10 seconds in a high-temperature atmosphere at 150 ° C.

  The obtained copper foil has an anode surface crystal diameter of 100 nm and a 10-point average roughness (Rz) of 0.5 μm. On the other hand, the cathode surface has a surface roughness of 1 without roughening treatment. It was a smooth surface capable of forming fine wiring at 0.0 μm. Moreover, since it has a fine crystal structure, it was flexible with a tensile strength of 400 MPa and an elongation of 17%.

As described above, according to the present invention, it is possible to produce an ultrathin copper foil that does not require a relatively thick copper foil (carrier) to be laminated, has no pinholes, and has a thickness of 0.1. The thing of 5-5 micrometers is obtained.
Since copper foil used for printed wiring board materials and the like needs to form fine wiring, the lower the Ra value of the copper crystal, the more advantageous. The Ra of the copper foil obtained with this foil making apparatus is close to 50% compared to the Ra of the conventional copper foil.
In the manufacturing method and apparatus according to the present invention, there is an advantage that it is possible to manufacture a foil in a small lot as compared with the manufacture of a copper foil using a conventional very expensive drum-type foil manufacturing apparatus, which is suitable for small-scale production. It can be manufactured with inexpensive equipment.

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

  Therefore, when manufacturing a printed wiring board, it is easy to install a continuous copper foil manufacturing line before a printed wiring board manufacturing line without using a separately manufactured copper foil.

  Furthermore, the ultra-thin copper foil obtained by the present invention can be used to easily produce ultra-fine wiring by laminating with an ultra-thin prepreg in which fibers and a binder or a primer (adhesive) are preliminarily used in the production of printed wiring boards. A base material that can be applied with a high yield can be easily obtained.

DESCRIPTION OF SYMBOLS 1, 7 Metal foil manufacturing apparatus 2 Electrolytic tank 3 First post-treatment tank 4 Second post-treatment tank 5 Electrolytic tank for galvanizing 6 Anti-rust treatment tank 8 Zinc-treated surface 10 Belt (cathode body)
DESCRIPTION OF SYMBOLS 11 Anode 12 Anode body 13 Electrolyte 14 Suction pipe 15 Discharge pipe 16 Distributor 17 Gap 18 Copper 19 Discharge pipe 20 Suction pipe 21 Discharge pipe 22 Electrolyte 23 Anode body 24 Distributor (electrolyte outlet)
25 Gap 26, 31 Drive means 30 Plate body (stainless steel plate)
40 Peeling device 41 First nip roll 42 Winder 43 Second nip roll 44 Belt winder

Claims (13)

In the method for producing a metal foil, a current is passed between an anode body immersed in an electrolytic solution and a cathode body facing the anode body, and a metal is deposited on the surface of the cathode body by an electrolytic reaction to form a thin metal layer.
After the cathode body is moved along the anode body to deposit metal on the surface, the deposited thin metal layer is attached to the post-treatment position for the thin metal layer, and includes water washing. A metal foil manufacturing method, wherein a thin metal layer is peeled off from a cathode body after performing a predetermined post-treatment. In the method for producing a metal foil, a current is passed between an anode body immersed in an electrolytic solution and a cathode body facing the anode body, and a metal is deposited on the surface of the cathode body by an electrolytic reaction to form a thin metal layer.
After the cathode body is moved along the anode body to deposit metal on the surface, the deposited thin metal layer is attached to the post-treatment position for the thin metal layer, and includes water washing. A method for producing a metal foil, wherein a thin metal layer is peeled off from a cathode body after performing a predetermined post-treatment and a subsequent processing step.   The moving speed of the cathode body is 1 to 7 m / min. The method for producing a metal foil according to claim 1, wherein the metal foil is a metal foil.   The method for producing a metal foil according to any one of claims 1 to 3, wherein a distance between the anode body and the cathode body is 1 to 50 mm. 5. The method for producing a metal foil according to claim 1, wherein energization between the anode body and the cathode body is 50 A / dm ^{2 to} 600 A / dm ² . An anode body immersed in an electrolytic solution and a cathode body facing the anode body, and a current is passed between the anode body and the cathode body, and metal is deposited on the surface of the cathode body by an electrolytic reaction to form a thin metal layer. In the metal foil manufacturing apparatus for forming
A metal thin layer forming section for moving the cathode body along the anode body and depositing metal on the surface of the cathode body;
Moving means for moving the cathode body to a post-treatment step for the thin metal layer, with the deposited thin metal layer attached thereto;
An apparatus for producing a metal foil, comprising: peeling means for peeling the thin metal layer from the cathode body after performing predetermined post-treatment including water washing.   The metal foil manufacturing apparatus according to claim 6, wherein the anode body and the cathode body are both formed in a flat plate shape and arranged in parallel to each other.   The metal foil manufacturing apparatus according to claim 7, wherein the cathode body is an endless belt or a plate-like body that is movable along the anode body.   9. The metal foil manufacturing apparatus according to claim 6, wherein the moving means is a conveyor.   The moving speed of the cathode body is 1 to 7 m / min. The metal foil manufacturing apparatus according to any one of claims 6 to 9, wherein the apparatus is a metal foil manufacturing apparatus.   11. The apparatus for producing a metal foil according to claim 6, wherein a distance between the anode body and the cathode body is 1 to 50 mm. The metal foil manufacturing apparatus according to any one of claims 6 to 11, wherein the energization between the anode body and the cathode body is 50 A / dm ^{2 to} 600 A / dm ² .   The thickness of the said cathode body is 0.1-0.8 mm, The manufacturing apparatus of the metal foil of any one of Claims 6-12 characterized by the above-mentioned.

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