KR20120109099A

KR20120109099A - Installation of dissolving tank and use of insolubility anode for making cupric sulfate solution

Info

Publication number: KR20120109099A
Application number: KR1020110026627A
Authority: KR
Inventors: 송호상
Original assignee: 송호상
Priority date: 2011-03-24
Filing date: 2011-03-24
Publication date: 2012-10-08

Abstract

The present invention uses copper-containing copper balls, which are expensive as anodes, for electroplating copper in the surface of a plated roll (Cylinder) for gravure printing and copper in the holes of a printed circuit board (PCB). The phosphorus copper for plating contains phosphorus (P) and oxygen (O), and the phosphorus copper ball in the form of balance consisting of copper and unavoidable impurities is put into the anode tank of the plating tank, and it is inferior in international competitiveness. In order to solve this problem, the manufacturing and installation of melting tank and other equipment to make copper sulfate (CuSO4.5H2O) solution to control copper sulfate concentration at all times during cost reduction and plating.
In addition, the copper plating method uses the copper ball as the anode, and since the distance between the anode (shipping copper ball) and the roll to be rolled is large, the plating current is concentrated at both ends of the roll to be rolled so that the plating thickness is at both ends of the roll to be rolled. In addition to thickening in the vicinity, the grinding wheel can be processed by several kinds of grinding wheels (200, 800, 4000) due to uneven leveling of the overall roll. Therefore, when grinding the grinding wheel, the grinding system is polished a lot near both ends of the plated roll, so there is a problem such as the time required for the grinding wheel processing, and the plating system can make the plating thickness uniform over the entire length of the plated roll. It is necessary to build and the copper phosphorus ball contains inevitable impurities, and the black anode sludge adheres to the surface of the copper phosphorus ball.
The anodic sludge falls out of the ballast copper ball by agitation of the liquid and the melting of the balloid copper ball, which floats in the plating solution and adheres to the surface of the plated roll to cause convex marks (microscopic projections) or concave marks (pinholes). It is becoming. In addition, in order to prevent the copper ion concentration in the plating solution from being excessively high due to too much dissolution of the copper-containing copper ball for plating, maintenance of draining and diluting the plating solution on a regular basis to obtain a suitable copper ion concentration is performed. need.
In particular, in recent years, in order to satisfy the demand for miniaturization and high functionalization of electronic components, very fine ones are required as conductive patterns formed on the surface of the roll to be plated. For example, miniaturization of wiring patterns on PCBs is recommended, and it is required to be smaller than 20 to 30 μm by the inner diameters of through holes and blind via holes, which are accompanied by high integration in multilayer wiring in semiconductor devices. In order to reduce the inter-wire capacitance caused by the miniaturization of the copper wire, the same wiring is used instead of the aluminum wiring.
When plating by the current plating method, the metal structure of the plated inner film of the plated roll is not delicate and works with laser and electronic engraving pattern of fine structure to produce semiconductor products such as MLCC (Multi Layer Ceramaitor) and PCB board. Quality maintenance becomes difficult. When the plated film is formed on the roll to be plated with copper-containing copper balls, plating internal structure defects and film thickness nonuniformity are likely to occur, and it is difficult to maintain good quality of the plated film.
Therefore, the object of the present invention is to manufacture copper sulfate solution which can make good product without non-uniformity of plating thickness to develop the conductive pattern of fine structure. Electric shielding on melting tank equipment and insoluble anode (anode) which can supply The use of a shield device can greatly improve the quality of the product.

Description

Installation of dissolving tank and use of insolubility anode for making cupric sulfate solution}

The field of application of the present invention relates to all copper plating facilities required for copper sulfate solution for copper sulfate printing on the surface of Grovia printed sheet rolls, the production of electrolytic copper foil, and the surface of printed circuit boards. It is to provide a method for recycling the waste scrap (Cu scrap).

In the upper plating tank 1e of FIG. 1, the copper-containing copper ball 1b on the side connected to the positive electrode (+) gradually melts by the electrolysis and Faraday law, and the printing flap roll 1f connected to the negative electrode (-). Copper ions in which metallic copper (Cu) is dissolved are attached. At the positive electrode (copper-containing ball), the electrons of copper are lost to become copper ions, and at the same time, the electrons of the copper ions are given to the negative electrode (the skin roll) to be reduced to copper.

Faraday's law specifies the total amount of material produced in the negative and positive poles by passing a constant amount of electricity, but this is only a theoretical quantity and depends on the situation. Therefore, after plating is completed in the upper plating tank 1e, the plating liquid flows into the lower tank through the drain pipe 1c. The copper sulfate concentration of the plating liquid in the lower tank 1d is continuously increased unless the working time is adjusted. If the copper sulfate concentration is higher than the standard value, it is easy to precipitate copper sulfate crystals over the entire surface of the plating solution and the copper ball basket 1a, and the fine grains and concave marks adhere to the rolled plate roll 1f in which the precipitated crystal grains fall and rotate during plating. In many cases, the copper sulfate plating solution temperature is 45 ° C., and thus the copper sulfate plating solution is used in winter in various PVC pipes 1i and pumps 1j supplied from the lower tank 1d to the upper plating tank 1e. Due to the easy precipitation, the pipe 1i and the pump 1j are frequently replaced, and in order to prevent this, power loss occurs because the plating liquid must be continuously rotated during non-operation. The cost of wastewater treatment is incurred as the plating solution has to be disposed of in wastewater, and the cost up factor and environmental regulations can be applied to form the plating solution.

Since the anode is a soluble phosphorus copper ball (1b), the upper surface of the anode (hamindongdong ball) is a large sphere at the first sound by electrolysis and Faraday's law during plating. Due to the change, the distance between the ballast copper ball 1b and the plated roll 1f is changed and the electric force lines flowing out from the anode are not constant, so that the plating thickness of the plated roll 1f cannot obtain a uniform leveling property. Grinding can sharpen the grindstone, reducing productivity and increasing cost.

In addition, due to the disproportionation reaction, the fine particles of copper phosphorus float in the upper plating tank liquid and adhere to the surface of the plated roll 1f to create convex marks, and the copper phosphorous ball contains inevitable impurities. It is attached to the roll to be plated, PCB, and other products to be plated to cause various plating defects. In addition, the monovalent copper compound produced in the copper phosphorus ball by reaction with the additive and the copper phosphorus ball promotes the decomposition of the additive, thereby increasing the amount of use, reducing the plating quality of the reactant, and causing sludge.

The present invention has been invented to solve the problems with the conventional plating method as described above, the cylinder of the gravure printing machine has to repeatedly perform the plating and peeling the plating layer plated on the surface of the cylinder every time the printing item is changed. will be.

Therefore, after using the expensive copper plating layer once, it was discarded after peeling off, resulting in many economic losses. The size of the cylinder for gravure printing presses is generally on the periphery of more than about 600 (mm) and 900 (mm) in length, and the copper plating layer is about 130 (μm) in this one size cylinder. It is a national loss to dispose of copper with 4,500 ~ 5,000 copper plated per month in one use alone.

Therefore, according to the conventional copper plating method using the copper-containing copper ball as an anode, unavoidable impurities accumulate in the plating liquid, and the unavoidable impurities adhere to the surface of the plated roll, causing convex marks and concave marks.

Adopting the copper plating method using the high purity copper phosphorus ball used for copper sulfate plating in a semiconductor wafer as an anode leads to an increase in plating cost and cannot be adopted. In addition, according to the conventional copper plating method using the copper-containing copper ball as an anode, since the distance between the copper-containing copper ball and the to-be-rolled roll is large, the plating current is concentrated on both ends of the to-be-rolled roll (4a) and the plating thickness as shown in Fig. 4B. Was thickening near both ends of the plated roll. Therefore, when performing grinding wheel grinding, grinding is performed for a long time near both ends of the roll to be rolled, and the grinding wheel grinding device is large, expensive, and has a problem such as time required for processing.

Since the nonuniform plating thickness cannot be polished to be uniform, it is understood that a plating system that can make the plating thickness uniform over the entire length of the roll to be processed is necessary.

In addition, in order to solve the above problems, the use of a method of copper plating the plated roll using an insoluble anode was considered. This method uses an insoluble anode coated with an iridium catalyst on the surface of titanium, makes a copper sulfate solution in a dissolution tank facility as shown in FIG. 3 outside the plating tank, and captures impurities with a filter (3t). In this way, plating is performed using a plating liquid that does not contain impurities, so that anode sludge does not occur. However, there is no example provided in the plating line of the plated roll for gravure printing.

The present inventors install an insoluble anode as in the plating tank of FIG. 2, and install a plating apparatus facility for making copper sulfate plating solution in the melting tank facility of FIG. 3 and sending it to the lower tank 2d of FIG. 2 via a supply tank (3m). In addition, when the insoluble anode 2a provided in the plating tank of FIG. 2 is manufactured and installed, it is possible to perform plating of uniform thickness over the entire length without causing convex or concave marks on the roll to be plated. Was studied. As a result, in the process of sending the plating liquid from the plating liquid supply tank 3m of FIG. 3 to the plating tank of FIG. 2, it was found that the plating without convex or concave marks can be performed by capturing and removing the unavoidable impurities contained in the plating liquid. Then, the insoluble anode was plated with a shield (4c) device to close the electricity to the plated roll so as to have a distance of 20 (mm) to 30 (mm), and plating current flowed at both ends of the roll. By entering, no effect of current concentration occurs, and plating with a uniform thickness (4d) is performed over the entire length of the roll. As the plating roll is plated, the copper ion concentration is insufficient in the lower tank (2d) of FIG. Therefore, the system for automatically supplying the metering pump 3o as much as necessary in the plating liquid supply tank 3m was devised. The aim is to improve and improve all these problems.

As described above, according to the present invention, the copper (copper) peeled from the waste wire and the recovered flap roll (cylinder) is collected and dissolved in a dissolution tank to be recycled in place of the copper ball to avoid wasting precious and expensive copper. Therefore, the waste of precious natural resources of the country can be prevented, and companies can obtain the effect of reducing production costs by recycling expensive copper (copper) over and over again. Therefore, the insoluble anode can be used because the plating solution is made in the dissolution tank at low cost, and has various effects as follows.

The copper sulfate plating solution supplied to the plating tank (FIG. 2) passes the primary filter (3t) in the process of dissolving waste wires and defective copper plating defective products in the melting tank facility (FIG. 3) and sending them to the lower tank (2d) of FIG. In addition, in the process of supplying the lower tank 2d to the upper plating tank 2b, the plating solution is supplied to the upper plating tank 2b by completely removing the impurities causing the concave marks with the secondary filter 2h. Since it was possible to do this, favorable copper sulfate plating which did not produce concave and convex marks was able to be performed.

In addition, since the distance between the copper ball 1b and the plated plate 1f is large and different in the related art, the plating current is concentrated at both ends of the plated roll 4a so that the plated thickness is near both ends of the plated roll. 4b, and because of this, the cylindrical polishing is also polished for a long time in the vicinity of both ends of the to-be-rolled roll; Since the plating was carried out, the plating current was maintained at a uniform density over the entire length of the plated roll, and plating 4d having a uniform thickness could be performed.

When the plated roll diameter before plating is precisely processed over the entire length, the plated roll diameter after plating is also maintained at a uniform precision over the entire length, thereby greatly reducing the time taken by the grinding wheel.

In addition, since the plating current density can be increased, the plating time can be shortened. Since the distance between the anode and the cathode (the flap roll) is short, the voltage is reduced, the power consumption is reduced, and the plate roll is plated. The rotating energized portion of the adapter reduces heat and reduces the time it takes to replace the cone in front of the adapter to repair it.

In addition, after the plating tank was improved, the plated in the facility (FIG. 7B) showed an increase in yield and a defect rate near zero. By constantly controlling copper sulfate solution and supplying it to a plating tank through a filter, the structure of the plating film is stabilized and delicate, so that the MLCC and RFID of electrical devices are developed through the development of fine line width and high resolution pattern, the core technology of gravure e-printing for the electronics industry. Electronic tags) and the like. As a result, we are now engraving and delivering patterns on the rolls of flap plates that can produce MLCC in S Electric.

1 shows a side view of a copper sulfate plating facility before improvement.
Figure 2 shows a side view of copper sulfate plating equipment after the improvement.
3 shows a dissolution tank installation diagram for producing a copper sulfate plating solution.
Figure 4 shows the plating state of the roll to be plated during plating with a phosphorus ball and an insoluble anode (anode).
FIG. 5 shows a side view of the shape, thickness and separation distance of the plated roll, and separation distance of the anode and the plating liquid supply nozzle when the insoluble anode is installed.
Fig. 6 shows a plan view and dimensions of an insoluble anode for chromium plating (four mounted on the front and rear busbars inside the plating tank).
FIG. 7 shows a top plating tank installation of a phosphorus ball anode (before improvement) and an insoluble anode (after improvement).

It will be understood with reference to the accompanying drawings, a method for installing a dissolution tank for preparing a copper sulfate solution which can be copper (copper) plated on a roll to be coated according to the present invention.

Therefore, 4.5 (㎥) sized dissolution tank is made of SUS 316L to not dissolve the phosphorus copper balls. Fill the dissolution tank (3h) with water (2 (㎥)) and add sulfuric acid to 70 (g / ℓ). The liquid temperature was 75 (filled with the copper tank, which peeled off the plated film of the clean roll and used in the gravure printing machine, and the oxygen was injected through the loose blower (3a). The plating liquid is continuously rotated by the pump 3l through the heat exchanger until the temperature of

As shown in Figure 3, the air bubbles rising from the bottom of the dissolution tank have a higher contact speed with the waste wires and copper (copper) shells, so that the dissolution rate proceeds faster. Thus, the copper sulfate solution can be appropriately prepared, and the gate valve 3b. By adjusting the air volume, the concentration of copper sulfate (CuSO4.5H2O) can be controlled.

The chemical reaction for melting copper (Cu) in the dissolution tank is as follows. Cu + H2SO4 + 5H2O + 1 / 2O2 → CuSO4.5H2O + H2O

In the upper plating tank (2b), the amount of copper (Cu) deposited during the daily plating should be calculated, and a closed wire (Cu scrap) or peeled copper shell should be added to the melting tank. In addition, a mesh net should be installed to prevent large foreign objects from flowing over the pipe overflowing from the upper part of the melting tank to the supply tank, and an automatic valve (3r) is provided in the steam pipe (3p) line to always set the melting tank temperature to 75 ° C. Install.

When organic impurities are observed in the dissolution tank, the plating solution is removed by passing through the carbon filter (3n) line, and the well-formed copper sulfate solution is removed from the supply tank (3m) by the metering pump (3o). The copper plating is sent to the lower tank (2d) via, the copper plating upper tank (2b) is good to install an insoluble anode as shown in FIG.

1a: copper ball basket 1b: copper copper ball (anode) 1c: drain pipe 1d: lower tank 1e: upper plating tank 1f: flap roll 1g: plating solution nozzle 1h: filter 1i: PVC pipe 1j: pump 2a: insoluble anode 2b: Upper plating tank 2c: Plating solution OUT 2d: Lower tank 2e: Plated roll 2f: Plating solution nozzle 2g: Plating solution IN 2h: Filter 2i: PVC piping 2j: Pump 3a: Loose blower 3b: Gate valve 3c: Air piping 3d: Closed copper wire 3e: Copper shell 3f: Air bubble 3g: Net mesh 3h: Melting tank 3i: Thermometer 3j: Overflow piping 3k: Plating solution in FIG. 2 OUT LINE 3l: FRP pump 3m: Supply tank 3n: Carbon filter 3o: Metering pump 3p: Steam piping 3q: Heat exchanger 3r: Automatic valve 3s: Plating solution as shown in FIG. 2 IN LINE 3t: Cartridge filter
4a: Current concentration during copper ball plating 4b: Plated roll state coated with copper ball 4c: Shielding device for electric shielding on insoluble anode 4d: Plated roll state coated with insoluble anode 4e: Copper ball 4f, 4h 4j, 4m: Rolled roll 4g, 4l: Copper plated state 4i: Insoluble anode 4k: Shielding device 5a, 5f: 20 to 30 (mm) 5b: 3 (mm) 5c: Copper bus bar 5d: Insoluble anode 5e: Flap plate Roll 5g: 50 (mm) 5h: 60 (mm) 5i: Liquid nozzle 6a: 570 (mm) 6b: 280 (mm) 6c: East bus bar 6d: R viewpoint 6e: 13 pie * 15 6f: 10 (mm) 6g : 63 (mm) 7a: Upper plating tank before improvement 7b: Upper plating tank after improvement 7c: Copper ball 7d: Insoluble anode 7e: Shielding device

Claims

A copper plating method characterized in that copper plating is performed by supplying a plating liquid to a plating tank equipped with a dissolution tank facility, a peripheral device, and an insoluble anode for plating copper sulfate on a plated roll.

The distance between the side and the bottom of the insoluble anode and the to-be-rolled roll installed in the plating tank of FIG. 2 is 20 to 30 (mm), and the nozzles for supplying the plating liquid from the bottom of the anode are spaced apart by a distance of 60 (mm). Copper and chromium plating method of the gravure printing to-be-printed roll.

The insoluble anode used for copper plating and chromium plating on the plated roll is as shown in Figs. 5 and 6, and a gravure printing plated roll, which is manufactured by coating an iridium catalyst 25 to 30 times on a titanium surface. Copper and chrome plating method.

Copper plated gravure printing plated roll, characterized in that the shield is installed in the upper tank (2b) of Figure 2 in PVC (20 mm) from both ends to the center of the plated roll in front of the insoluble anode as shown in Figure 4c Way.