JP2019157270A - Cathode drum for electrolytic deposition - Google Patents

Abstract

To provide a cathode drum for electrolytic deposition by which an electrolytic thin plate can be obtained in an electrolytic cell.SOLUTION: In the present invention, a high-density current is applied between a negatively-charged cathode drum and a positively-charged anode electrode via an electrolytic solution of a thin metal plate to be obtained as a medium in an electrolytic cell. Copper in cationic state contained in the electrolytic solution is solidified and precipitated as a solid onto the cathode drum. A cylindrical body and a side plate of the cathode drum are formed of a zirconium material having hardness, strength and corrosion resistance capable of withstanding the electrolytic solution in the electrolytic cell. A composite oxide film is formed on the cylindrical body by an electrolytic solution, and adverse effects on the quality of the electrolytic thin plate which is a precipitate from the cathode drum can thus be prevented.SELECTED DRAWING: Figure 3

Description

  The present invention relates to a cathode drum for electrolytic deposition capable of obtaining an electrolytic thin plate from an electrolytic cell, and more specifically, between a negatively charged cathode drum and a positively charged anode electrode in an electrolytic cell. Applying a high-density current using the electrolyte solution of the metal sheet solution to be used as a medium, so that the copper in the cation state contained in the electrolyte solution can be fused to the cathode drum and solidified and deposited as a solid. In this case, the cylindrical body and the side plate of the cathode drum are formed of a zirconium material having hardness, strength and corrosion resistance that can withstand the electrolytic solution of the electrolytic cell, so that a composite oxide film is formed on the cylindrical body by the electrolytic solution, thereby rotating the cathode. The negative influence on the quality of the electrolytic thin plate, which is a deposit from the drum, can be prevented, and the outer cylinder of the cylindrical body of the cathode drum is placed on both sides of the side plate of the cathode drum. The shape of the support beam that protrudes from both ends can increase the contact area with the electrolyte and increase the width of the metal sheet, while increasing the solidification rate from outside to inside due to contact with the outside air within a short time. The present invention relates to a cathode drum for electrolytic vapor deposition that can be deposited and can maintain the rigidity of the cathode drum by forming a holding ring having a plurality of holding pieces on both sides in the cathode drum.

  Generally, electrical and electronic devices are becoming lighter, thinner, and smaller, and as a result, circuits built in the devices are also miniaturized. Therefore, the circuit formed on the PCB is increasingly made ultra-thin. Thereby, the electrolytic copper foil board is also made ultra-thin, and the importance with respect to a high quality electrolytic copper foil board further increases.

  In order to obtain an electrolytic thin plate of iron, copper, chromium, nickel, etc., the electrolytic thin plate is manufactured by various devices including a cathode drum and an anode electrode stored in the electrolytic cell with a certain interval together with the cathode drum. A metal thin plate is obtained by electrolytically depositing metal on the surface of the cathode material by a target thickness by performing an electrolytic reaction while supplying an electrolytic solution containing metal ions between the insoluble drum-type cathode material and the insoluble anode material. Form. Subsequently, the formed thin metal plate is peeled off from the surface of the cathode material to manufacture.

  That is, the electrolytic thin plate flows an electrolytic solution such as iron, copper, chromium, nickel, etc. between a rotating cathode that is in the form of a drum and a lead-based anode that is disposed to face the rotating cathode drum. Then, copper is deposited on the surface of the rotating cathode drum using an electrolytic reaction, and when the deposited copper is in a foil state, it is manufactured by continuously peeling and winding it from the rotating cathode drum.

  As shown in FIGS. 1 and 2, the electrolytic thin plate manufacturing apparatus rotates with an electrolytic cell 1 to which an electrolytic solution 2 is continuously supplied and a portion of the electrolytic cell 1 immersed in the electrolytic solution 2 of the electrolytic cell 1. It comprises a cathode drum 4 and an anode electrode 3 arranged along the shape of the cathode drum 4.

  For example, the electrolytic solution 2 is a copper sulfate solution containing sulfuric acid, copper ions, and chlorine ions, and has a strongly acidic characteristic. The electrolytic solution 2 is supplied and circulated in the electrolytic cell 1 at a relatively high speed in order to prevent deficiency of copper ions in the vicinity of the cathode drum 4.

  Further, the surface material of the cathode drum 4 is made of titanium which maintains acid resistance with respect to the electrolytic solution 2 and facilitates peeling of the metal thin plate 5. In such a configuration, when a high-density current is applied between the negatively charged cathode drum 4 and the positively charged anode electrode 3 using the electrolytic solution 2 as a medium, it is contained in the electrolytic solution 2. The cationic copper is fused to the cathode drum, and as a result, solidifies and precipitates as a solid.

  The deposited copper is made into a sheet metal electrolytic copper foil plate 5 along the surface of the rotating cathode drum 4, and the formed electrolytic copper foil plate 5 is guided by a guide roll 6. Wound on bobbin 7. Further, it includes a DC power source 11 for supplying electricity by supporting both ends of the rotating shaft 8 with bearings 9 and a ring 10 through which a DC current is conducted.

  The cathode drum 4 has a cylindrical body composed of an inner cylinder and an outer cylinder with a rotating shaft 8 as the center. The inner cylinder is manufactured into a cylindrical shape using iron and a copper alloy, and is mounted after being machined. Then, a titanium rolled plate having a thickness of about 5 to 8 mm is formed into a cylindrical shape and is tightly fitted into the inner cylinder. The surface of the outer cylinder is machined and polished.

  Titanium is difficult to make into a usable material, but it is not easy to process. In the case of cutting, it is classified as a typical difficult-to-cut material, and because of its low thermal conductivity, it may break due to heat during cutting, resulting in lower productivity than steel.

  Also, high elasticity is a problem, but when a cutting blade hits, a phenomenon of returning after being dented like a rubber ball (elastic return) may occur.

  In addition, the accuracy tends to decrease when electric discharge machining is performed. Cold forging or hot forging is not easy. Cold forging may easily break, and hot forging and casting must be performed with a vacuum chamber filled with an inert gas such as magnesium or aluminum. Also, welding is not easy. There is a problem that expensive and difficult welding such as TIG welding has to be performed.

  In particular, titanium formed on the cylindrical body of the cathode drum can maintain a certain degree of hardness, strength and corrosion resistance by the electrolytic solution in the electrolytic cell. However, when used for a long period of time, it forms an oxide film formed on the titanium surface. Due to this, there is a problem of affecting the quality of the thin metal plate that is usually present as a composite oxide film of rutile type and anatase type and deposited from the rotating cathode drum.

Korean Registered Patent No. 10-1630979

  The present invention is to solve such problems, and its purpose is to form the cylindrical body and side plate of the cathode drum with respect to the electrolytic solution of the electrolytic cell with a zirconium material having excellent hardness, strength and corrosion resistance. Thus, an object of the present invention is to provide a cathode drum for electrolytic vapor deposition that can prevent the formation of oxidation such as a composite oxide film by an electrolytic solution on the cathode drum.

  Another object of the present invention is that the hardness of the cylindrical body and side plate of the cathode drum is higher due to zirconium, so that the roughness of the surface polishing of the cathode drum can be greatly increased compared to titanium, so that it is deposited by the cathode drum. An object of the present invention is to provide a cathode drum for electrolytic vapor deposition that can improve the quality of products.

  Another object of the present invention is that the outer cylinder of the cylindrical body of the cathode drum protrudes on both sides of the side plate of the cathode drum so that the thin metal plate produced by electrolysis in the electrolytic cell contacts the electrolyte on the outer peripheral surface of the cathode drum. It is an object of the present invention to provide a cathode drum for electrolytic vapor deposition that can expand the area and the width of a metal thin plate.

  Still another object of the present invention is to increase the solidification rate and shorten the metal sheet within a short time as the protruding portions at both ends of the outer cylinder constituting the cylindrical body of the cathode drum solidify from the outside to the inside by contact with the outside air. It is an object of the present invention to provide a cathode drum for electrolytic vapor deposition that can improve the productivity of a metal thin plate in an electrolytic cell by precipitating.

  Still another object of the present invention is to provide a cathode drum for electrolytic vapor deposition that is held by a plurality of holding pieces on the rotating shaft of the cathode drum, and the side plates on both sides can maintain the rigidity of the cathode drum by holding rings. It is to provide.

  Still another object of the present invention is to extend the life of the rotary cathode drum by changing the surface state of the titanium rotary cathode drum to another material instead of the state in which a normal oxide film is present. It is an object of the present invention to provide a cathode drum for electrolytic vapor deposition that can produce a metal thin plate that has more stable physical properties and better rough surface roughness.

  According to the present invention, a high-density current is applied between a negatively charged cathode drum and a positively charged anode electrode in an electrolytic cell, using the electrolytic solution of a thin metal plate solution to be obtained as a medium. In order that the copper in the cation state contained in can be solidified and deposited as a solid by fusing to the cathode drum, the hardness and strength of the cathode drum cylindrical body and side plate can withstand the electrolytic solution of the electrolytic cell In addition, by forming it with a corrosion-resistant zirconium material, a composite oxide film is formed on the cylindrical body by the electrolytic solution, and the adverse effect on the quality of the electrolytic thin plate that is a deposit from the cathode drum can be prevented. ing.

  In addition, the outer cylinder of the cylindrical body of the cathode drum of the present invention is formed with protruding portions on both sides of the side plate of the cathode drum, and the metal thin plate generated by electrolysis in the electrolytic cell is separated from the electrolyte on the outer peripheral surface of the cathode drum. The contact area can be expanded to increase the width of the metal sheet.

  In addition, on both side surfaces of the cathode drum of the present invention, the inner and outer side plates are fixed to the inner drum in the cathode drum, and the fixing ring is fixed to the circumferential boundary surface of the outer side plate by welding and screws. Thus, the side surface of the cathode drum can be kept airtight.

  Further, in the present invention, the cathode drum is integrally fixed to the rotating shaft and rotated by being held by the plurality of holding pieces on the rotating shaft of the cathode drum, and the side plates on both sides are fixed by the holding rings. Can be done.

  As described above, the present invention provides a high-density current between the negatively charged cathode drum and the positively charged anode electrode in the electrolytic cell, using the electrolytic solution of the thin metal plate solution to be obtained as a medium. In order to allow the cationic copper contained in the electrolyte to be fused to the cathode drum and solidify and deposit as a solid, the cylindrical body and side plate of the cathode drum are used as the electrolyte in the electrolytic cell. By forming it with a zirconium material having a tolerable hardness, strength and corrosion resistance, a composite oxide film is formed on the cylindrical body by the electrolytic solution to prevent adverse effects on the quality of the electrolytic thin plate as a deposit from the rotating cathode drum. In addition, the outer cylinder of the cylindrical body of the cathode drum protrudes on both sides of the side plate of the cathode drum to form a support beam on both ends, widening the contact area with the electrolyte and thinning the metal The holding ring with a plurality of holding pieces on both sides of the cathode drum can be deposited in a short time by increasing the solidification rate from outside to inside by contact with outside air. By forming, the rigidity of the cathode drum can be maintained.

It is a schematic longitudinal cross-sectional view of the apparatus for obtaining an electrolytic metal thin plate. It is a schematic cross-sectional view of the apparatus for obtaining an electrolytic metal thin plate. It is a partial separation perspective view of the cathode drum of the present invention. It is sectional drawing of the cathode drum of this invention. It is sectional drawing of the inner side drum of the cathode drum of this invention. It is sectional drawing of the outer cylinder of the cathode drum of this invention.

  Hereinafter, specific examples of the present invention will be described in detail with reference to the accompanying drawings.

  As shown in FIGS. 3 and 4, the cathode drum 4 of the present invention includes a rotating shaft 8, a holding ring 80 fixed to the rotating shaft, an inner drum 20 fixed to the holding ring 80, and a circle of the inner drum 20. The outer cylinder 40, the inner side plate 50, the outer side plate 60, and the fixing ring 70 are fixed to the periphery and the side.

  As described above, the rotary shaft 8 is formed with the sleeve 12 which can be rotated by the bearings on both sides, and the holding ring 80 is fixed with a gap in the center. In the holding ring 80, holding pieces 81 with respect to the rotating shaft 8 are fixed at equal intervals, and the holding pieces 81 are fixed perpendicularly to the rotating shaft, and a plurality of holding pieces 81 are fixed at equal intervals.

  The interval between the holding rings 80 is designed to be the width of the design dimension of the cathode drum 4, and the inner drum 20 as shown in FIG. 5 is fixed to the peripheral surface of the holding ring 80.

  The inner drum 20 is formed in a cylindrical shape based on the design dimension of the diameter of the cathode drum 4 and constitutes a base frame on which the outer cylinder 40, the inner side plate 50, the outer side plate 60, and the fixing ring 70 are maintained and fixed. To do.

  Screw holes 21 are formed on both side surfaces of the inner drum 20, and an outer cylinder 40 and an inner side plate 50, which will be described later, are welded and fixed by a fixing ring 70 to keep the cathode drum 4 airtight.

  Further, the holding ring 80 and the inner drum 20 are coupled by an interference fit and fixed by a fixing means such as welding.

  As shown in FIG. 6, the outer drum 40 is made of a cylindrical shape and can be joined by crimping to the outer peripheral surface of the inner drum 20, and the outer cylinder 40 made of zirconium is joined and fixed by means such as hot thinning.

  The diameter of the outer cylinder 40 is a dimension that can be tightly fitted to the outer peripheral surface of the inner drum 20, and the width is larger than the width of the inner drum 20.

  When the cathode drum 4 is formed, a high density is obtained by using the electrolytic solution 2 of the metal sheet solution to be obtained as a medium between the cathode drum 4 charged to a negative potential in the electrolytic cell and the anode electrode charged to a positive potential. Then, the cation-state copper contained in the electrolyte is fused to the cathode drum 4 so that it can be solidified and deposited as a solid.

  In the present invention, a composite oxide film is formed on the cylindrical body by the electrolytic solution by forming the cylindrical body and the side plate of the cathode drum 4 with a zirconium material having hardness, strength and corrosion resistance that can withstand the electrolytic solution of the electrolytic cell. Thus, it is possible to prevent an adverse effect on the quality of the electrolytic thin plate, which is a deposit from the cathode drum 4.

  Zirconium is a glossy off-white solid transition metal that resembles titanium. Zirconium is mainly produced as zircon and has a higher resistance to corrosion than titanium. It is resistant to corrosion and has a small neutron cross section.

  In particular, zirconium has a very high melting point of 1855 ° C. and a boiling point of 4371 ° C., and its electronegativity is 1.33. Among the elements belonging to the d zone, the element has the fourth lowest electronegativity following yttrium, lutetium, and hafnium. At room temperature, it exists in the form of α-zirconium having a hexagonal structure, but when heated to 863 ° C. or higher, it is converted to β-zirconium having a body-centered cubic structure. Zirconium is frequently used not only for metals but also for oxides.

  Zirconium is more expensive than titanium. However, zirconium is far more resistant to corrosion than titanium. At present, the copper foil plate produced by the cathode drum is used in the corrosive environment of copper sulfate solution, but the material of the thin plate with higher strength, such as high strength nickel and iron, can be used with electrolyte as needed. Since the degree of corrosion increases, there is a limit to the use of a conventional titanium cathode drum.

  In particular, the outer cylinder 40 of the cylindrical body of the cathode drum 4 of the present invention can maintain a certain degree of hardness, strength, and corrosion resistance by the electrolytic solution of the electrolytic cell. Since it is possible to prevent the formation of an oxide film or the like, a stable and high-quality metal thin plate can be deposited from the cathode drum 4.

  Further, according to the present invention, the outer cylinder 40 is made of zirconium and formed with portions 41 projecting on both sides of the side plate of the cathode drum 4, and the metal thin plate generated by electrolysis in the electrolytic cell 1 is the cathode drum 4. The width of the thin metal plate can be increased by increasing the area in contact with the electrolyte solution on the outer peripheral surface of the metal plate.

  After all, the outer cylinder 40 of the cylindrical body of the cathode drum 4 protrudes on both sides of the outer side plate 60 of the cathode drum 4, so that the metal thin plate generated by electrolysis in the electrolytic cell 1 is formed on the outer peripheral surface of the cathode drum 4. The width of the metal sheet can be increased by increasing the area in contact with the electrolyte.

  Further, the present invention increases the solidification rate by protruding portions 41 on both sides of the outer cylinder 40 constituting the cylindrical body of the cathode drum 4 in contact with outside air to solidify from the outside to the inside. The productivity of the metal thin plate in an electrolytic cell can be improved by depositing a thin plate.

  As shown in FIGS. 3 and 4, both side surfaces of the cathode drum 4 are fixed to the inner drum 20 in the cathode drum 4 with inner and outer side plates 50 and 60, and the circumferential boundary between the outer side plates. Since the fixing ring 70 is fixed to the surface by welding and the screw 71, the side surface of the cathode drum 4 can be kept airtight.

  The inner side plate 50 made of iron and the outer side plate 60 made of zirconium are fixed to the side surfaces of the both-side holding rings 80 of the cathode drum 4, and the circumferential boundary surface of the outer side plate 60 is shown in FIG. A fixing ring 70 in which screw holes 72 are formed at equal intervals is fastened by a screw 71, and the fixing ring 70 is fixed to the outer side surface plate 60 by fixing means such as welding in order to maintain airtightness. The

  Since the outer side surface plate 60 is made of zirconium, it is possible to prevent the electrolyte solution and the like from flowing into the cathode drum 4 and to prevent corrosion due to the electrolyte solution.

  Further, according to the present invention, the holding ring 80 is held on the rotating shaft of the cathode drum 4 by a plurality of holding pieces 81, the side plates 50 and 60 on both sides are fixed by the holding ring 80, and the cathode drum 4 is turned on the rotating shaft 8. It can be fixed and rotated integrally.

  That is, the holding ring 80 serving as the basic frame of the cathode drum 4 is held by the plurality of holding pieces 81 with respect to the rotating shaft 8 of the cathode drum 4, and the holding pieces 81 are integrally fixed to the side plates on both sides. Since it is held by the holding ring 80, the inner drum 20 and the inner / outer side plates 50, 60, which are the main components of the cathode drum 4, firmly maintain the cylindrical body. In addition, a large number of holes 82 are provided at equal intervals on the circumferential surface of the holding ring 80 that is integrally formed orthogonal to the holding piece 81, so that the weight of the holding ring 80 is minimized and the cathode drum 4 is rotated. Has the advantage of facilitating

DESCRIPTION OF SYMBOLS 1 Electrolysis tank 2 Electrolyte 3 Anode electrode 4 Cathode drum 5 Metal thin plate 6 Guide roll 7 Bobbin 8 Rotating shaft 9 Bearing 10 Ring 11 DC power supply 12 Sleeve 20 Inner drum 21 Screw hole 40 Outer cylinder 41 Projected part 50 Inner side plate 60 Outer side plate 70 Fixing ring 71 Screw 72 Screw hole 80 Holding ring 81 Holding piece 82 Hole

Claims (4)

A high-density current is applied between the negatively charged cathode drum and the positively charged anode electrode in the electrolytic cell, using the electrolytic solution of the metal sheet solution to be obtained as a medium, and is contained in the electrolytic solution. A cathode drum used in an apparatus for producing an electrolytic thin plate in which the copper in a cation state is fused to a cathode drum and can be solidified and deposited as a solid,
A cathode drum for electrolytic deposition, wherein the cylindrical body and the side plate are made of a zirconium material having hardness, strength, and corrosion resistance that can withstand the electrolytic solution of the electrolytic cell.   The outer cylinder of the cylindrical body of the cathode drum protrudes on both sides of the side plate of the cathode drum, and the area where the metal thin plate produced by electrolysis in the electrolytic cell contacts the electrolyte on the outer peripheral surface of the cathode drum is widened. The cathode drum for electrolytic vapor deposition according to claim 1, wherein the width of the metal thin plate can be increased.   Both side surfaces of the cathode drum are fixed to the inner drum in the cathode drum by the inner side plate and the outer side plate, and the fixing ring is fixed to the circumferential boundary surface of the outer side plate by welding and screws. The cathode drum for electrolytic vapor deposition according to claim 1, wherein airtightness can be maintained on a side surface of the drum. The holding ring is held on the rotating shaft by a plurality of holding pieces, and the inner side plate and the outer side plate on both sides are fixed to the holding ring, so that the cathode drum is integrally fixed to the rotating shaft and rotates. The cathode drum for electrolytic deposition according to claim 3, wherein the cathode drum is capable of being formed.

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