TW201510285A - Continuous manufacturing method for electrolytic metal foil and continuous manufacturing device for electrolytic metal foil - Google Patents

Abstract

Provided are a continuous manufacturing method and manufacturing device for electrolytic metal foil that can prevent nonuniformity of current caused by lead adhering to insoluble metal positive electrodes, can prevent reductions in quality of the metal foil because of bubbles generated on these positive electrodes, can improve yield, can reduce cell voltage, and can prevent accelerated consumption of insoluble metal positive electrodes by additives. The continuous manufacturing method and device for an electrolytic metal foil, wherein the method, which uses a device having a rotating cylindrical negative electrode drum that is partially immersed in an electrolyte for forming a metal foil and an insoluble metal positive electrode having an arc-like shape and a part facing that drum, is characterized in that the device has a structure such that a barrier film is disposed adhering to the surface of the insoluble metal positive electrode, a negative electrode chamber is formed between the negative electrode drum and the barrier film, and a positive electrode chamber is formed on the back side of the positive electrode, and characterized in that an electrolyte for forming the metal foil is supplied inside the negative electrode chamber, an acid solution supplied within the positive electrode chamber, electrolysis carried out, metal foil that is electrolytically deposited on the surface of the negative electrode drum peeled from the negative electrode drum, and the metal foil manufactured continuously.

Description

Continuous manufacturing method of electrolytic metal foil and continuous manufacturing device of electrolytic metal foil

The present invention relates to a continuous manufacturing method of an electrolytic metal foil suitable for continuous manufacture of various electrolytic metal foils, particularly electrolytic copper foils, and a continuous manufacturing apparatus for electrolytic metal foils.

As an example of a technique for producing various metal foils by continuous electrolysis, which has been known since the prior art, continuous production of an electrolytic copper foil as a base material for manufacturing a printed wiring board has been known. For example, as described in Patent Document 1, a tubular (cylindrical) cathode and a lead alloy electrode using a lead-silver alloy or the like are used as an anode in a conventional electrolytic device for electrolytic copper foil. .

The lead alloy electrode has acid resistance to a high concentration acidic metal salt solution such as a copper sulfate solution. Further, since the lead alloy electrode has a low melting point of lead, which is a constituent component, it has an advantage that it is easy to process the opposite surface of the oppositely curved anode along the shape of the rotating drum surface of the cathode. It is easy to process on site of the electrolyzer. In other words, the lead alloy electrode is widely used because it exhibits good workability and is excellent in workability.

However, as the continuous electrolysis apparatus of the electrolytic copper foil is enlarged, it is difficult to homogenize the alloy composition of the lead alloy electrode in the same plane. Further, in the lead alloy electrode in the acid solution used as the electrolytic solution, the difference in the composition of the alloy and the difference in the crystal structure significantly affect the polarization performance at the time of electrolysis, and it is difficult to manufacture a follow-up technique. High-quality electrolytic copper foil with advanced technology.

Moreover, the lead alloy electrode is likely to cause a change in the shape of the electrode surface due to the large consumption of electrolysis, and the maintenance cost is also increased. The lead component which enters the electrolyte from the electrode which is consumed is sometimes changed to metal lead, lead ion, acid lead. The components such as lead oxide are mixed into the electrolytic copper foil, which causes various products to be defective.

Therefore, in order to solve such problems, in recent years, an insoluble metal electrode has been used in place of a lead alloy electrode, and a surface of a valve metal such as titanium is coated with a conductive electrode material containing a platinum group metal or an oxide thereof.

In the continuous electrolysis method of the conventional electrolytic copper foil using the insoluble metal electrode, as described in the patent document 1, the following metal foil continuous electrolysis method is used, that is, the part is immersed in the electrolyte solution for metal foil generation. a rotating cylindrical cathode drum and an apparatus for facing the cathode drum and surrounding an arc-shaped insoluble metal anode of a portion around the cathode drum, and supplying the metal foil generating electrolyte to the cathode A metal foil is electrically connected to the cathode drum between the drum and the anode, and the metal foil is peeled off from the cathode drum to continuously produce a metal foil. However, the insoluble metal anode used uses a cross-sectional arc-shaped insoluble metal anode surrounding a portion of the periphery of the cathode drum, and has a complicated shape, and replaces the anode with an insoluble metal electrode instead of a conventional lead alloy electrode. At the time, there are problems in that it is difficult to form the electrode and it is difficult to replace the electrode (reactivation treatment).

Therefore, when such an insoluble metal electrode is used as the anode, as shown in Patent Document 2, an insoluble electrode structure is used, that is, a cross-sectional arc shape which is opposite to the cathode drum and surrounds a portion thereof The anode frame or the power supply plate is fixed to the at least one part of the electrolytic action surface of the plate-shaped or curved electrode substrate by a detachable mounting device such as a screw or the like, and the thin plate-shaped insoluble metal anode is formed by electrode coating. The surface of the gantry or the power supply board is formed with an electrode coating on a contact surface with a thin plate-shaped insoluble metal anode of the electrode substrate.

Copper foil is widely used as a printed circuit board in a large amount as an electronic or electrical material. The high performance and high reliability of printed wiring boards are advancing, so the characteristics are required to be complicated and diverse. There is also a strict quality requirement for the copper foil which is one of the constituent materials of the printed wiring board.

Thereby, the management standard of the foil becomes strict, and the standard of the foil thickness balance becomes strict. Further, various additives are also used for the additive which affects the quality of the copper foil, and the consumption of the catalyst of the insoluble electrode is increased and the life is shortened.

In particular, the demand for suppressing the thickness unevenness in the same surface in the electrolytic copper foil becomes remarkable. In the case of the electrolytic copper foil, it is considered from the viewpoints of the formation of a fine pitch circuit on a printed wiring board manufactured using an electrolytic copper foil, the processing precision of the multilayer printed wiring board, and the like, and the reduction in size and the like. Electrolytic copper foil which is thinner and less uneven in thickness is required.

Therefore, it is desired to have an electrolytic metal foil continuous production apparatus capable of suppressing thickness unevenness in the same plane of the electrolytic metal foil including the electrolytic copper foil, and a thickness unevenness obtained by using the electrolytic metal foil continuous production apparatus. Electrolytic metal foil.

However, when the electrolytic copper foil is produced by the method described in Patent Document 1, the electrolytic chamber is formed only between the cathode drum and the insoluble metal electrode. In the chamber, the electrolyte containing lead is deposited as an oxidation lead on the insoluble metal electrode when the foil is manufactured. The precipitated lead oxide falls off during the operation and becomes a cause of uneven current distribution. In addition, when the lead oxide adhered to the lead is desulfurized as a defective conductor, the current distribution is uneven, and the life of the insoluble metal electrode is shortened.

Further, the adhered lead falls into the electrolytic solution in the state of a lead compound. The lead compound is entangled in the copper foil to cause a decrease in the quality of the foil or pinholes, so that the insoluble electrodes are exchanged.

Further, gelatin is mainly used as an additive, but recently, as an additive for copper foil, a combination of thiourea, HEC (hydroxyethyl cellulose), and the like has been used. Such acceleration of the catalyst consumption of the insoluble electrode is a major cause of shortening the life of the electrode.

Further, the bubbles of oxygen generated on the insoluble metal electrode adhere to the cathode drum and become pinholes.

On the other hand, as a copper plating method for a copper plate for printing, a copper plating for a through-hole of a printed wiring board, and a copper plating technique for an acid-based copper plating bath such as an electrolytic copper foil, Patent Document 3 discloses a method in which a cation is used. The exchange membrane separates the anode chamber from the cathode chamber to perform copper plating.

Patent Document 3 is a method in which an insoluble metal anode and a soluble copper anode are collectively disposed in an anode chamber, and the anode is blocked and separated by a cation exchange membrane, and an anode viscous substance generated from a copper anode is anoded in the anode chamber. The interior dissolves, and the viscous material does not move into the plating solution in the cathode chamber, and the catholyte in the cathode chamber is not contaminated by the anode viscous material, thereby forming a uniform and excellent plating coating.

However, in Patent Document 3, the plating solution containing the additive is not supplied to the anode chamber in which the anode is housed, and copper sulfate/sulfuric acid which is the same component as the plating solution is supplied.

Further, in Patent Document 3, the cation exchange membrane is attached to the wall surface of the cylindrical anode chamber frame, and the cation exchange membrane is provided separately from the anode, and is not directly held on the surface of the anode, so that it is not zero with the insoluble metal anode. Clearance. Therefore, Patent Document 3 has a drawback in that bubbles in the liquid are generated between the anode and the cathode, the solution resistance is increased, and the voltage and electric power are increased.

Further, Patent Document 3 is a technique for manufacturing electrolytic metal in batch form, and cannot be continuously manufactured. Electrolytic metal foil.

In addition, Patent Document 4 is the same as Patent Document 3, and is related to copper plating of a printing roller, copper plating of a through hole of a printed wiring board, and copper plating technology of a copper sulfate bath such as an electrolytic copper foil. A rectangular copper anode is not housed in the anode chamber, and a rectangular anode chamber frame is provided as an anode chamber, and an insoluble metal anode is accommodated therein. As in Patent Document 3, the cation exchange membrane is attached to a rectangular anode. The side wall of the chamber frame is not zero-gap or limited with the insoluble metal anode, and has the same disadvantages as the technique described in Patent Document 3.

Patent Document 5 is not related to a plating apparatus, and is related to an insoluble metal anode for plating. In Patent Document 5, a rectangular anode chamber frame is provided as an anode chamber frame, and an insoluble metal anode is accommodated therein, or An insoluble metal anode is formed on one of the walls thereof. As in Patent Document 3, the cation exchange membrane is attached to the side wall of the rectangular anode chamber frame, but is not gapped or limited with the insoluble metal anode, and has a patent document. The shortcomings of the techniques described in 3 are the same.

Patent Documents 6 and 7 are all related to the method for producing a flexible copper-clad laminate. Although the anode and the cathode are separated by a cation exchange membrane, the structure as a device is not disclosed at all. The configuration in which the anode and the cathode are separated by the cation exchange membrane is also unclear. Of course, the constituent elements for zero-gap or limited the cation exchange membrane and the insoluble metal anode are not described.

As described above, in Patent Documents 3 to 7, an electrolytic method in which an anode chamber and a cathode chamber are separated by a cation exchange membrane is disclosed, but in these methods, a cation exchange membrane is disposed apart from an insoluble metal anode. Further, the cation exchange membrane and the insoluble metal anode are not zero-gap, and it is considered that the current is not able to improve the current unevenness or the insolubilization due to the lead attached to the insoluble metal electrode according to the conventional techniques. The quality of the copper foil caused by the bubbles generated on the electrodes is lowered, and the yield cannot be improved. Moreover, the influence of bubbles or adhesion of lead cannot be prevented, and the battery voltage cannot be lowered. Moreover, it is also impossible to prevent the consumption of the insoluble electrode due to the additive from accelerating.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2001-81592

[Patent Document 2] Japanese Patent Laid-Open No. Hei 5-202498

[Patent Document 3] Japanese Patent No. 3455705

[Patent Document 4] Japanese Patent No. 3903120

[Patent Document 5] Japanese Patent No. 3928013

[Patent Document 6] Japanese Patent Laid-Open Publication No. 2006-316328

[Patent Document 7] Japanese Patent No. 4560726

An object of the present invention is to provide a method and a manufacturing apparatus for continuously manufacturing an electrolytic metal foil, which can solve the problems of the prior art and prevent current unevenness caused by lead attached to an insoluble metal anode or due to insoluble metal. The quality of the copper foil caused by the bubbles generated on the anode is lowered, the yield can be improved, the effect of bubbles or adhesion of lead can be eliminated, the battery voltage can be lowered, and the consumption of the insoluble metal anode caused by the additive can be prevented from being accelerated.

In the first solution of the present invention, in order to achieve the above object, a method for continuously manufacturing an electrolytic metal foil, which is used in a continuous manufacturing method, is provided. An apparatus having a cylindrical cathode drum and an insoluble metal anode having an arcuate cross section, the cylindrical cathode drum having a structure in which a part of the cylindrical cathode drum is immersed in an electrolyte for generating a metal foil, and the section arc The insoluble metal anode is disposed so as to face a portion of the periphery of the cathode drum, and surrounds one of the surrounding portions; and the electrolyte solution for generating metal foil is supplied to the surface of the cathode drum The metal foil is electrically connected to the cathode drum, and the metal foil is peeled off from the cathode drum to continuously manufacture the metal foil. The method for continuously manufacturing the electrolytic metal foil is characterized in that the apparatus has the following structure That is, a separator is disposed on the arcuate surface of the insoluble metal anode in a close contact manner, and a cathode chamber is formed between the cathode drum and the separator, and a back surface side of the insoluble metal anode is formed An anode chamber; and the metal foil is continuously produced by the following method: supplying the metal foil generating electrolyte to the above Chamber, the acid solution is fed to the anode chamber and the electrolysis, the electrolytic deposition will be the surface of the cathode drum of the metal foil to be peeled off from the cathode drum.

In the second solution of the present invention, in order to achieve the above object, a method for continuously producing an electrolytic metal foil is provided, characterized in that the metal foil is a copper foil, and the electrolyte for generating the metal foil is a copper sulfate solution, and The above acid solution is a pure sulfuric acid solution.

In a third solution of the present invention, in order to achieve the above object, a method for continuously producing an electrolytic metal foil according to the present invention is characterized in that the separator is a cation exchange membrane.

In the fourth solution of the present invention, in order to achieve the above object, a method for continuously manufacturing an electrolytic metal foil is provided, characterized in that the separator is an anion Change the film.

In the fifth solution of the present invention, in order to achieve the above object, a method for continuously producing an electrolytic metal foil according to the present invention is characterized in that the separator is a neutral separator.

In the sixth solution of the present invention, in order to achieve the above object, a method for continuously producing an electrolytic metal foil according to the present invention is characterized in that the cation exchange membrane is a perfluorosulfonic acid membrane.

In the seventh solution of the present invention, in order to achieve the above object, an apparatus for continuously producing an electrolytic metal foil which is used for continuously producing a metal foil and having the following portions is provided, that is, The cylindrical cathode drum has a structure in which a part of the anode is immersed in an electrolyte for generating a metal foil, and an insoluble metal anode having an arc-shaped cross section is opposed to a portion around the cathode drum. And surrounding one of the surrounding portions; a device for supplying the metal foil generating electrolyte to the surface of the cathode drum to electrically charge the metal foil on the cathode drum; and an electric metal foil from the above The apparatus for continuously peeling off a cathode drum; the apparatus for continuously manufacturing an electrolytic metal foil characterized by comprising: an electrolysis unit comprising: a separator disposed in close contact with an arc-shaped surface of the insoluble metal anode; a cathode chamber formed between the cathode drum and the separator; and an anode chamber formed on the back of the insoluble metal anode a device for supplying a metal foil generating electrolyte into the cathode chamber; a device for supplying an acid solution into the anode chamber; and a metal foil for electrically analyzing the surface of the cathode drum A device for continuously stripping a metal foil from the above-mentioned cathode drum.

Furthermore, in the present specification, the membrane is in close contact with the insoluble metal cation. The arrangement of the arc-shaped surface of the pole section refers to any state in which the insoluble metal anode and the separator are in close contact with each other or partially (zero-gap state); and the state in which the insoluble metal anode is disposed with a small interval (limited state).

According to the present invention, a cylindrical cathode drum having a structure in which a part thereof is immersed in a metal foil-generating electrolytic solution and an insoluble metal anode having a cross-sectional arc shape disposed opposite to one of the rotating tubes is used. In the conventional technique, by providing a structure in which a new separator is closely attached to the surface of the arc-shaped insoluble metal anode, the following remarkable effects can be obtained.

First, according to the present invention, an anode chamber and a cathode chamber are separated by a separator, and an insoluble metal anode is disposed in an anode chamber separated from the cathode chamber by the separator, and a pure acid containing pure sulfuric acid is supplied to the anode chamber. The anolyte of the solution, on the other hand, the cathode is disposed in the cathode chamber separated from the anode chamber by the separator, and the electrolyte for producing a metal foil (cathode liquid) is supplied to the cathode chamber by a copper sulfate solution containing lead or an additive. Therefore, the insoluble metal anode is only in contact with the anolyte containing the pure acid solution, and is not in contact with the catholyte containing the copper sulfate solution containing lead or the additive, so that no lead or the additive is precipitated from the insoluble metal anode.

Moreover, according to the present invention, since there is no case where lead oxide is deposited on the insoluble metal anode at the time of producing the foil, there is no unevenness in current distribution due to the lead compound which has fallen off, and the uniformity of the copper foil is maintained for a long period of time. The insoluble metal anode is not replaced due to the adhesion of lead.

Further, according to the present invention, the catalyst consumption of the insoluble metal anode caused by the additive in the electrolytic solution for producing a metal foil such as a copper sulfate solution is not accelerated, so that the life of the insoluble metal anode can be extended.

Moreover, according to the present invention, the entrapment of the lead compound into the copper foil disappears, and the quality of the foil can be improved and the pinhole can be reduced to improve the yield.

Moreover, according to the present invention, the separator is disposed directly on the surface of the insoluble metal anode, and the anode is disposed in close contact with the separator, so that bubbles generated on the insoluble metal anode are directly discharged from the anode chamber without moving to the cathode chamber, so Electrochemical analysis of the metal foil from the surface of the cathode eliminates pinholes caused by air bubbles. Therefore, according to the present invention, it is possible to prevent the quality of the copper foil caused by the bubbles generated on the insoluble metal anode from being lowered, and the yield can be improved.

1‧‧‧electrolyzer

2‧‧‧Cathode rotating drum

3‧‧‧Insoluble metal anode

4‧‧‧Separator

5‧‧‧Cathode chamber

6‧‧‧Power supply board

7‧‧‧Anode chamber

8‧‧‧Electrolyte supply tube for metal foil generation

9‧‧‧Acid solution supply pipe

10‧‧‧metal foil

11‧‧‧Metal foil take-up rolls

12‧‧‧A rectangular mesh forming an insoluble metal anode 3 formed into a short strip shape

13‧‧‧Power supply

14‧‧‧ countersunk screws

15‧‧‧Flange of the power supply board 6

16‧‧‧ cushion

17‧‧‧Flange

18‧‧‧ countersunk screws

19‧‧‧Cap nut

20‧‧‧Overflow trough

21‧‧‧ copper sulfate solution storage tank

22‧‧‧ copper dissolution tank

23‧‧‧ sulfuric acid solution storage tank

Fig. 1 is a schematic view showing the basic configuration of an apparatus for continuously producing an electrolytic copper foil as an embodiment of the electrolytic metal foil continuous production apparatus of the present invention.

Fig. 2 is a partially cutaway perspective view showing one embodiment of a state in which a separator is disposed on the surface of an insoluble metal anode of the electrolytic metal foil continuous manufacturing apparatus of the present invention.

Figure 3 is a cross-sectional view taken along line C of Figure 2.

Hereinafter, the form of implementation of the present invention will be described together with the drawings.

Fig. 1 is a view showing a basic structure of an apparatus for continuously producing an electrolytic copper foil as an embodiment of an apparatus for continuously producing an electrolytic metal foil according to the present invention. The electrolytic copper foil device is provided with a cylindrical cathode drum 2 made of titanium or nickel in the electrolytic cell 1. The cathode drum 2 has a rotatable structure and is disposed in the electrolytic cell 1 so as to be partially (substantially lower half) immersed in the molten metal generating electrolyte. In addition, an insoluble metal anode 3 having an arcuate cross section is provided so as to surround the lower half of the outer circumference of the cathode drum 2, and the lower half of the outer circumference of the cathode drum 2 is placed opposite to the insoluble metal anode 3. The electrolytic metal foil continuous manufacturing apparatus of the present invention is characterized in that it is designed as follows In the meantime, a certain gap is provided between the cathode drum 2 and the insoluble metal anode 3 on the opposite portion, and the separator 4 is placed in close contact with the arc-shaped surface of the insoluble metal anode 3. In the apparatus of the present invention, a gap is formed between the cathode drum 2 and the separator 4 which is provided in close contact with the surface of the insoluble metal anode 3, and the gap is used as the cathode chamber 5. In the electrolytic metal foil continuous manufacturing apparatus of the present invention illustrated in Fig. 1, the insoluble metal anode 3 is attached to the power supply board 6, and the back side of the insoluble metal anode 3 opposite to the side on which the diaphragm 4 is provided is inside the power supply board 6. The gap of the wall serves as the anode chamber 7. The interval between the gaps described above is not the same as that of the conventional electrolytic metal foil continuous manufacturing apparatus having the same configuration, and may be the same design. It is important in the present invention to provide the separator 4 in close contact with the surface of the insoluble metal anode 3, and further divide into the cathode chamber 5 and the anode chamber 7.

The electrolyte solution supply pipe 8 for metal foil generation is connected to the cathode chamber 5, and the insoluble metal anode 3 which is adhered to the surface via the separator 4 is connected to the anode chamber 7 which is separated from the cathode chamber 5 by a pure acid solution supply. Tube 9. In addition, the metal foil generating electrolyte solution such as a copper sulfate solution is introduced into the cathode chamber 5 from the metal foil generating electrolyte tank by the tubes, and a pure acid solution such as sulfuric acid is introduced into the anode chamber 7. An electrolytic solution for generating a metal foil such as a copper sulfate solution overflows from the cathode chamber 5 to the overflow tank 20, for example, in the flow shown in FIG. 1, and is stored in the copper sulfate solution storage tank 21. The copper sulfate solution stored in the copper sulfate solution storage tank 21 is recycled in such a manner that a new copper sulfate solution produced by dissolving metallic copper in the copper dissolution tank 22 is supplied at any time, and the copper component used for electrolysis is supplied. Further, the pure sulfuric acid solution supplied to the anode chamber 7 overflows from the anode chamber 7 and is stored in the sulfuric acid solution storage tank 23 for recycling.

In Fig. 1, 10 is a metal foil to be a product, and 11 is a metal foil take-up roll.

2 is a partial cutaway view of one embodiment of a state in which a separator is disposed on the surface of an insoluble metal anode used in the continuous manufacturing apparatus for electrolytic metal foil of the present invention; FIG. 3 is a cross-sectional view taken along line C of FIG. 2 .

As shown in FIG. 2 and FIG. 3, the insoluble metal anode 3 is assembled in such a manner that a plurality of rectangular mesh-shaped anode sheets 12 formed in a short strip shape are arranged to be circumferentially abutting each other. The surface of the one-fourth arc-shaped power supply plate 6 is detachably fixed to the plurality of power supply bosses 13 by the countersunk screws 14 and along the arc of the power supply plate 6. The power supply plate 6 formed in an arc shape of one quarter of the circumference is provided on both sides of the lower portion of the cylindrical cathode drum 2 via the metal foil generating electrolyte supply pipe 8 and the acid solution supply pipe 9.

The separator 4 is bonded to the surface of the insoluble metal anode 3 assembled as described above, and the four sides of the separator 4 are superposed on the flange portion 15 of the power supply plate 6, and the overlapping portion is covered by the spacer 16, and is placed thereon. Flange 17. Thereafter, the gasket 16 sandwiched between the flange 17 and the flange portion 15 (including the portion overlapping the film) is detachably fastened to the countersunk screw 18 and the flange 17 by the cap nut 19 (to the periphery) Seal welding).

As described above, by pressing the sealing diaphragm 4 on the four sides of the power supply board 6 by using the spacer 16, a flow path (anode chamber 7) of the liquid flowing through the inner wall side of the power supply board 6 is formed.

In the first embodiment of the method for continuously producing an electrolytic metal foil according to the present invention, the case where the metal foil is a copper foil, the electrolyte solution for producing the metal foil is a copper sulfate solution, and the acid solution is a pure sulfuric acid solution will be described.

The cylindrical cathode drum 2 made of titanium or nickel provided in the electrolytic cell 1 is partially (substantially lower half) immersed in a copper sulfate solution which is an electrolytic solution for metal foil production, and is in the state of FIG. Rotate in the direction of the arrow. The copper foil solution for metal foil generation is supplied from the metal foil generating electrolyte supply pipe 8 to the cathode chamber 5 formed between the cathode drum 2 and the separator 4 from below the center portion of the cathode drum 2. The copper sulfate solution contains a large amount of additives such as gelatin for improving the properties of the formed copper foil, and is formed in a cyclic manner. In the middle of the cycle, the metallic copper which is the raw material of the metal foil is dissolved and added to the copper sulfate solution to adjust the concentration of the copper sulfate solution. Further, the acid solution, that is, the pure sulfuric acid solution, flows from the acid solution supply pipe 9 from below the center portion of the cathode drum 2 to the anode chamber 7 formed on the inner wall side of the power supply plate 6 on the back side of the insoluble metal anode 3. The pure sulfuric acid solution is also formed in a cyclic manner. Electrolysis is performed between the cathode drum 2 and the insoluble metal anode 3 via a rectifier (not shown) by applying a predetermined voltage therebetween.

As the cathode drum 2 rotates, the thickness of the copper which is electrolyzed from the copper sulfate solution increases, and when the thickness reaches a certain thickness or more, the metal foil 10, that is, the copper foil, is peeled off and continuously wound up on the metal foil take-up roll 11.

As a result, the present invention is suitable for various electrolytic metal foils, especially electrolysis The continuous production method of the electrolytic metal foil for producing copper foil and the continuous production apparatus for electrolytic metal foil can exert the following effects.

1) The insoluble metal anode 3 can be isolated from the metal foil generating electrolyte such as a copper sulfate solution containing a large amount of additives by the separator 4, and does not remain in contact with the additive and lead ions in the electrolyte to stay in an acid solution such as a pure sulfuric acid solution. As a result, the life of the anode and the like can be improved. Further, since the lead compound is not precipitated on the insoluble metal anode 3, the battery voltage can be expected to be lowered.

2) Even if lead and its fine particles are formed on the surface of the insoluble metal anode 3, it can be blocked by the separator 4, and even if lead or the like falls off, there is no adverse effect on the metal foil such as copper foil formed on the cathode drum. .

3) Even when the Cu-based dendritic crystal grows on the surface of the insoluble metal anode 3, the short-circuit thus generated can be prevented. Further, since lead is not deposited on the insoluble metal anode 3, the current distribution can be made uniform, and the electrode can be filled. As a result, the voltage can be lowered and the electric power can be reduced.

4) The insoluble metal anode 3 and the separator 4 are closely arranged, and are zero-gap or limited, so that bubbles in the liquid between the anode and the cathode disappear, the solution resistance can be lowered, and the voltage and power can be reduced.

Further, the method of disposing the separator 4 on the surface of the insoluble metal anode 3 is not particularly limited, and instead of providing the gasket 16, the flange 17, the countersunk screw 18, and the cap nut 19 as described above, the following method may be used. That is, a method of pressing with a micro mesh, a method of pressing with a lateral support, a method of pressing with a PTFE (polytetrafluoroethylene) wire, or the like.

Further, when the separator 4 is bonded to the surface of the insoluble metal anode 3, the separator 4 needs to be placed in close contact with the surface of the insoluble metal anode 3, but as described above, the intimate state may be the insoluble metal anode 3 and the separator. The state in which the whole or part is closely adhered (zero-gap state) may be a state (limited state) that is disposed with a small interval therebetween, and the adjustment may be performed, for example, by changing the thickness of the spacer 16.

As illustrated in FIG. 1 , the insoluble metal anode 3 is not limited to the anode sheet 12 having a plurality of rectangular mesh shapes formed in a short strip shape, and is disposed on the power supply board processed into a curved shape so as to be in contact with each other. The surface of the surface of 6 may be, for example, a plate-like body formed into a circular arc-shaped mesh shape along the shape of the power supply plate 6. Further, the insoluble metal anode 3 is not limited to the method of directly mounting on the power supply board 6 as exemplified above, and may be attached to the power supply board 6 via, for example, an electrode stand processed into a curved shape.

Further, the insoluble metal anode 3 used in the present invention preferably has an electrode substrate formed of a valve metal of titanium and has an electrode coating formed on the surface thereof. The electrode coating at this time can form any electrode coating depending on the purpose of use of the electrode. For example, when a sulfuric acid solution is used as the acid solution, it is preferable to use a coating containing cerium oxide as an electrode coating.

Further, as the separator 4 used in the present invention, a cation exchange membrane, an anion exchange membrane, or a neutral separator can be used. Even if any of the separators were used, as shown in Table 1, the lead particles were not mixed into the copper foil as a product, and there was no significant difference in the quality of the copper foil and the appearance of the copper foil.

Further, as shown in Table 1, in the case where a cation exchange membrane is used as the separator 4, it is better in terms of battery voltage, current efficiency, and anode life as compared with the case of using an anion exchange membrane or a neutral membrane. result. The reason for this is presumed to be that, since the cation exchange membrane is used, the exchange rate of charge to copper ions is restricted by the proton movement in the membrane.

On the other hand, in the case of using an anion exchange membrane, as compared with the case of using a cation exchange membrane, as shown in the following Examples 6 and 7, there is a tendency that the battery voltage is slightly increased and the current efficiency is slightly lowered, but There is no significant difference in the life of the anode, the quality of the copper foil, and the appearance of the copper foil.

Further, in the case of using a neutral separator, as compared with the case of using a cation exchange membrane, as shown in the following Example 8, the life of the anode tends to be slightly shortened, but in battery voltage, current efficiency, and copper foil. There is no big difference in the quality and appearance of the copper foil. In this case, the reason why the life of the anode is slightly shortened can be considered as follows, because in the case of using a neutral separator, the anolyte and the catholyte cannot be completely separated and a part of the mixture is mixed.

[Examples]

Next, the embodiments of the present invention will be described, but the present invention is not limited to the embodiments.

<Example 1> 1) Conditions for the production of insoluble metal anodes (A)

The surface of one type of titanium plate of JIS was subjected to dry blasting treatment using iron sand (#120 size), and then, pickling treatment was performed for 10 minutes in a 20% sulfuric acid aqueous solution (105 ° C), and the electrode substrate was cleaned. The cleaned electrode substrate is placed in an arc ion plating apparatus, and an arc ion plating coating of a pure titanium material is performed. The coating conditions are as follows.

Target: a titanium disc of JIS (water-cooled on the back)

Degree of vacuum: 1.0 × 10 ^-2 Torr (Ar gas substitution introduced)

Access to electricity: 500W (3.0KV)

Substrate temperature: 150 ° C (when arc ion plating)

Time: 35 minutes

Coating thickness: 2 microns (weight gain conversion)

When the X-ray diffraction was measured after the arc ion plating coating, a sharp crystal peak belonging to the substrate main body and a pattern belonging to the sputtering coating were observed, and it was found that the coating was amorphous.

Next, ruthenium tetrachloride and antimony pentachloride are dissolved in 35% hydrochloric acid as a coating liquid, and the coating liquid is brushed on the substrate subjected to the above arc ion plating coating treatment and dried, and then placed in an air circulating electric furnace. (550 ° C, 20 minutes) Thermal decomposition coating was carried out to form an electrode catalyst layer containing a solid solution of cerium oxide and cerium oxide. The coating thickness of the first application of the brushing was set such that the amount of the coating liquid was approximately 1.0 g/m ² in terms of a base metal.

The coating-calcination operation was repeated 12 times. The insoluble metal anode manufactured as described above was subjected to electrolysis using the electrolytic copper foil continuous production apparatus shown in Fig. 1 under the following conditions.

2) Diaphragm

The cation exchange membrane described below was used to adhere to the insoluble metal anode to have a zero gap.

a: Nafion 117 (registered trademark of DuPont)

b: Nafion 551 (registered trademark of DuPont)

c: Nafion 424 (registered trademark of DuPont)

3) Electrolysis conditions

Current density: 60A/dm ²

Electrolysis temperature: 60 ° C

Catholyte composition: copper sulfate solution

Copper concentration: 70g/L

Sulfuric acid concentration: 100g/L

Gelatin: 20ppm

Lead concentration: 20ppm

Anode liquid composition: pure sulfuric acid solution

Sulfuric acid concentration: 100g/L

As a result, as shown in Table 1, good results were obtained in all aspects of battery voltage, foil current efficiency, anode life, copper foil quality, and copper foil appearance.

<Example 2> 1) Conditions for the production of insoluble metal anodes (B)

The surface of one type of titanium plate of JIS was subjected to dry blasting treatment using iron sand (#120 size), followed by pickling treatment in a 20% sulfuric acid aqueous solution (105 ° C) for 10 minutes, and cleaning treatment of the electrode substrate. The antimony pentachloride and titanium tetrachloride were dissolved in 35% hydrochloric acid, applied as a coating liquid to the cleaned electrode substrate, and thermally decomposed and coated in an air circulating electric furnace (550 ° C, 20 minutes). Form an intermediate layer.

Then, antimony tetrachloride and antimony pentachloride were dissolved in 35% hydrochloric acid as a coating liquid, which was applied to the substrate on which the intermediate layer was formed and dried, and then placed in an air circulating electric furnace (550 ° C). 20 minutes) Thermal decomposition coating was carried out to form an electrode catalyst layer containing a solid solution of cerium oxide and cerium oxide. The coating thickness of the first application of the brushing was set such that the amount of the coating liquid was approximately 1.0 g/m ² in terms of a base metal.

The coating-calcination operation was repeated 12 times. The insoluble metal anode manufactured as described above was subjected to electrolysis using the electrolytic copper foil continuous production apparatus shown in Fig. 1 under the following conditions.

2) Diaphragm

The same cation exchange membrane as in Example 1 was used, and the insoluble metal anode was adhered to each other to have a zero gap.

3) Electrolysis conditions

The same electrolysis conditions as in Example 1 were used.

As a result, as shown in Table 1, good results were obtained in all aspects of battery voltage, foil current efficiency, anode life, copper foil quality, and copper foil appearance.

<Example 3> 1) Conditions for the production of insoluble metal anodes

It was produced under the same conditions (A) as in Example 1.

2) Diaphragm

The same cation exchange membrane as in Example 1 was used, and the insoluble metal anode was adhered to each other to have a zero gap.

3) Electrolysis conditions

The same electrolysis conditions as in Example 1 were used except that the current density was changed to 30 A/dm ² .

As a result, as shown in Table 1, good results were obtained in all aspects of battery voltage, foil current efficiency, anode life, copper foil quality, and copper foil appearance.

<Example 4> 1) Conditions for the production of insoluble metal anodes

It was produced under the same conditions (A) as in Example 1.

2) Diaphragm

The same cation exchange membrane as in Example 1 was used, and the insoluble metal anode was adhered to each other to have a zero gap.

3) Electrolysis conditions

The same electrolysis conditions as in Example 1 were used except that the current density was changed to 80 A/dm ² .

As a result, as shown in Table 1, good results were obtained in all aspects of battery voltage, foil current efficiency, anode life, copper foil quality, and copper foil appearance.

<Example 5> 1) Conditions for the production of insoluble metal anodes

It was produced under the same conditions (A) as in Example 1.

2) Diaphragm

The following cation exchange membrane was used in close contact with the insoluble metal anode, but it was not zero-gap, but was limited.

Nafion 117 (registered trademark of DuPont)

3) Electrolysis conditions

The same electrolysis conditions as in Example 1 were used.

As a result, as shown in Table 1, good results were obtained in all aspects of battery voltage, foil current efficiency, anode life, copper foil quality, and copper foil appearance.

<Example 6> 1) Conditions for the production of insoluble metal anodes

It was produced under the same conditions (A) as in Example 1.

2) Diaphragm

The anion exchange membrane described below was used to adhere to the insoluble metal anode to have a zero gap.

Neosepta A-0300 (registered trademark of ASTOM Corporation)

3) Electrolysis conditions

The same electrolysis conditions as in Example 1 were used.

As a result, as shown in Table 1, the battery voltage slightly increased, and the foil-forming current efficiency was slightly lowered, but the anode life, the quality of the copper foil, and the appearance of the copper foil were good.

<Example 7> 1) Conditions for the production of insoluble metal anodes

It was produced under the same conditions (B) as in Example 2.

2) Diaphragm

The anion exchange membrane described below was used to adhere to the insoluble metal anode to have a zero gap.

Neosepta A-0300 (registered trademark of ASTOM Corporation)

3) Electrolysis conditions

The same electrolysis conditions as in Example 1 were used.

As a result, as shown in Table 1, the battery voltage slightly increased, and the foil-forming current efficiency was slightly lowered, but the anode life, the quality of the copper foil, and the appearance of the copper foil were good.

<Example 8> 1) Conditions for the production of insoluble metal anodes

It was produced under the same conditions (A) as in Example 1.

2) Diaphragm

The following neutral separator was used to adhere to the insoluble metal anode and zero gap.

Yumicron Y9201T (registered trademark of Yuasa Membrane System)

3) Electrolysis conditions

The same electrolysis conditions as in Example 1 were used.

As a result, as shown in Table 1, the anode life was slightly lowered, but the battery voltage, the foil current efficiency, the anode life, the copper foil quality, and the appearance of the copper foil were excellent.

<Comparative Example 1> 1) Conditions for the production of insoluble metal anodes

It was produced under the same conditions (A) as in Example 1.

2) Diaphragm

Set to no diaphragm.

3) Electrolysis conditions

The same electrolysis conditions as in Example 1 were used. However, only the catholyte is used and the anolyte is not used.

As a result, as shown in Table 1, the anode life was greatly reduced.

<Comparative Example 2> 1) Conditions for the production of insoluble metal anodes

It was produced under the same conditions (B) as in Example 2.

2) Diaphragm

Set to no diaphragm.

3) Electrolysis conditions

The same electrolysis conditions as in Example 1 were used. However, only the catholyte is used and the anolyte is not used.

As a result, as shown in Table 1, the anode life was greatly reduced.

(industrial availability)

According to the present invention, it is possible to prevent the unevenness of the current caused by the lead attached to the insoluble metal anode generated by the manufacturing method of the conventional device, or the quality of the copper foil caused by the bubble generated on the insoluble metal anode. Reduced, can improve the yield of metal foil products, and can eliminate the influence of bubbles or attached lead, reduce the battery voltage, and prevent the consumption of insoluble metal anodes caused by additives, so that the quality can be efficiently and continuously manufactured. A good electrolytic metal foil is used in the field of manufacturing various other electrolytic metal foils other than electrolytic copper foil, and thus it is expected to be widely used.

1‧‧‧electrolyzer

2‧‧‧Cathode rotating drum

3‧‧‧Insoluble metal anode

4‧‧‧Separator

5‧‧‧Cathode chamber

6‧‧‧Power supply board

7‧‧‧Anode chamber

8‧‧‧Electrolyte supply tube for metal foil generation

9‧‧‧Acid solution supply pipe

10‧‧‧metal foil

11‧‧‧Metal foil take-up rolls

20‧‧‧Overflow trough

21‧‧‧ copper sulfate solution storage tank

22‧‧‧ copper dissolution tank

23‧‧‧ sulfuric acid solution storage tank

Claims (7)

A method for continuously producing an electrolytic metal foil, which comprises a device having a cylindrical cathode drum and an insoluble metal anode having a circular arc shape, the cylindrical cathode drum having a part of being immersed in an electrolyte for producing a metal foil And a rotating structure, wherein the arc-shaped insoluble metal anode is disposed so as to face a portion of the periphery of the cathode drum, and surrounds one of the surrounding portions; and the electrolyte for generating the metal foil Supplying to the surface of the cathode drum, electrically discharging the metal foil on the cathode drum, and peeling off the electroplated metal foil from the cathode drum, thereby continuously manufacturing the metal foil; the electrolytic metal foil continuous manufacturing method The device has a structure in which a separator is disposed in close contact with an arcuate surface of the insoluble metal anode, and a cathode chamber is formed between the cathode drum and the diaphragm. And an anode chamber is formed on the back side of the insoluble metal anode; and the metal foil is continuously produced by the following method, : A metal foil to produce the cathode chamber is supplied with an electrolyte, an acid solution is supplied to the anode chamber and the electrolysis, the electrolytic deposition will be the surface of the cathode drum of the metal foil to be peeled off from the cathode drum. The method for continuously producing an electrolytic metal foil according to the first aspect of the invention, wherein the metal foil is a copper foil, the electrolyte for generating the metal foil is a copper sulfate solution, and the acid solution is a pure sulfuric acid solution. The method for continuously producing an electrolytic metal foil according to claim 1 or 2, wherein the separator is a cation exchange membrane. A method for continuously manufacturing an electrolytic metal foil according to claim 1 or 2, In the above, the separator is an anion exchange membrane. The method for continuously producing an electrolytic metal foil according to claim 1 or 2, wherein the separator is a neutral separator. The method for continuously producing an electrolytic metal foil according to claim 1 or 2, wherein the separator is a cation exchange membrane, and the cation exchange membrane is a perfluorocation exchange membrane. An apparatus for continuously producing an electrolytic metal foil, which is used for continuously producing a metal foil, and has a cylindrical cathode drum having a part of being immersed in an electrolytic solution for producing a metal foil. a rotating structure; an arc-shaped insoluble metal anode that is opposite to a portion of the periphery of the cathode drum and surrounded by a portion thereof; and the electrolyte for generating metal foil is supplied to the cathode drum a device for electrically driving a metal foil on the cathode drum; and a device for peeling off the electroplated metal foil from the cathode drum; the electrolytic metal foil continuous manufacturing device characterized by comprising: an electrolysis portion; The method includes: a separator disposed on the arcuate surface of the insoluble metal anode in a close contact manner; a cathode chamber formed between the cathode drum and the separator; and an anode chamber formed in the insoluble property a back side of the metal anode; a device for supplying a metal foil generating electrolyte into the cathode chamber; for supplying an acid solution to The anode chamber of said apparatus; and will for the electrolytic deposition of the surface of the cathode drum of the metal foil to be peeled off from the cathode drum means of a metal foil wound continuously.