JPH05505645A - Electrolytic regeneration device for etching agents containing chloride and metal ions - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Electrolytic regeneration device for etching agents containing chloride and metal ions. 1. An apparatus for electrolytically regenerating an etching agent containing ions of substances and metals, the apparatus comprising: a first anode; An electrolytic chamber having an array of electrodes and a second cathode is connected to the first anode and the second cathode. and a first DC power source, which controls the electrolytic reaction that occurs in the dark between the first cathode and the first anode. In the meantime, the metal is precipitated from the etching agent at the first cathode, and the etching agent is further removed from the etching agent. In order to adjust the pH value of and an electrolytic regenerator that produces oxygen.

Such a device is known from European Patent No. 0141905. This conventional The disclosure describes the chemical reactions that occur in the etching reaction and electrolytic regeneration of etching agents. and electrophysical reactions, especially in the manufacture of electronic circuit boards. The reactions involved are described in detail. The present invention relates to this detail. In addition, European Patent No. 0 According to No. 141905, a portion of the copper ions reduced during the quenching reaction It is known that when it is scattered in the etching equipment, it is oxidized again by the oxygen in the air. It is being This side reaction causes the pH to rise significantly, leading to an etching reaction and European Patent No. 0141905, which is undesirable because it affects the According to the method, water is decomposed at the anode to produce oxygen during an electrolytic reaction. At this time/ 8 Hydrogen ions remaining in the liquid compensate for changes in pH value again, bringing the pH closer to a constant value. can be done. In this known device, Peng bond η...tight t1 wedge; PA is also used in the electrolytic reaction to precipitate metals. 10-t: E y, the pH value is adjusted to its maximum. It is not done properly.

The problem of the present invention is to keep both the composition of the etching agent and the etching conditions constant. This results in increased electrolytic deposition of metals in the etching agent and an increase in the pH value. The object of the present invention is to enable the development of a device of the aforementioned type in which the adjustment is achieved under optimal conditions.

This assignment is Mokzoeβ1: Yofute. a) a separate second anode and a separate second cathode; and b) a second anode and a second and an independent second DC power supply connected to the second cathode, As a result, during the electrolytic reaction occurring between the second anode and the second cathode, the second The process of producing oxygen at the anode is more specialized.

In addition, according to the present invention, in order to electrolytically generate oxygen useful for adjusting the pH value, Supplying completely independent currents to completely independent pairs of electrodes. In this case, 2 Two separate electrolytic reactions occur, each of which performs only one action; Therefore, the effects of each of the two reactions can be optimally adjusted. european patent No. 0141905 discloses, for example, the current density and the continuity of the electrolytic reaction. must be adapted to the conditions limited by the metal deposition at the cathode.

This narrows the scope for selecting the parameters required for oxygen production and is therefore limited. It is possible to maintain a constant pH value only under certain conditions. By separating into the electrolytic reactions of The etching process can be carried out without considering the increased metal deposition reaction in the etching agent. I can do it.

The second anode is in the form of a number of anode rods electrically connected in parallel, and the second cathode is in the form of a number of anode rods electrically connected in parallel. It is preferable that several cathode rods are electrically connected in parallel. The electrode surface area is relatively large, and the electric field distribution between each electrode rod is good. This second electrode, which requires relatively little space, deposits most of the metal. Therefore, the shape of the electrode should be considered so that it can be rubbed off like the first cathode. There is no need to consider it.

The cathode rods and cathode rods are housed together in an auxiliary electrode assembly so that both sides of the central row of cathode rods are Such an auxiliary electrode arrangement preferably has a row of cathode rods on each side. are preferably arranged side by side like group batteries (depending on the size and capacity of the device). Yes. Although the electrodes can be electrically connected in series, parallel connections are preferred.

In fact, in order to preferably produce oxygen at the second anode, the second anode Both surfaces are made of platinum group metals (platinum, titanium, tantalum, iridium, rubidium). Oxide or mixed oxide is recommended.

In a similar sense, the anode is provided with a gas permeable coating. At this time, for example, polypropylene Ren fabrics, fluorine-based synthetic resins such as PTFE, or carbon fiber fabrics, or or needle felt.

A particular advantage of the invention is that the pH value can be adjusted particularly easily and automatically.

A pH detector is installed, which monitors the pH value of the etching agent and acts on the control circuit. Ru. This circuit controls the second DC power supply to substantially adjust the pH (ii) of the enquenching agent. can be held at a constant value.

The control range of this control circuit is generally the control range of electrolysis where increased metal is deposited. It's completely unrelated.

Next, implementation M of the present invention will be described in more detail with reference to the drawings.

Figure 1 shows T#r of an electrolytic regeneration device for etching agents containing chloride and metal ions. FIG.

FIG. 2 is a plan view of an auxiliary electrode device used in the device of FIG.

FIG. 3 is a sectional view taken along line lll-01 in FIG.

The apparatus shown in FIG. 1 is used in the manufacture of electrical circuit boards. Separated by etching Electrolytic regeneration of chloride-containing etching agents with increased metal ions, especially copper ions. The chemical and electrophysical reactions that occur in this configuration that are useful for life, and the The problems that arise are described in detail in the aforementioned European Patent No. 0141905. Book The invention relates to this.

This device has an electrolytic chamber 2 in a housing 1, and a predetermined mirror 1 is installed in the electrolytic chamber 2. Up to 3, the introduction and discharge of the etching agent fills the etching agent to be regenerated 4. This figure does not include the types and associated control operations, as they are not the subject of this invention. For this, see for example German Patent Publication No. 2650912. I can do it.

The drum has a copper jacket on which a titanium layer 7 is plated. this is, As will be described in more detail below, it acts as a cathode for etchant regeneration electrolysis.

The deposition drum 5 is rotatably mounted on the housing 1 by a shaft 8 and is shown in the figure. Not rotated by electric motor. In addition, the shaft 8 passes through the front wall of the precipitation drum 5. This serves to introduce current into the titanium layer 7, which acts as a cathode.

The anode 14 is in the form of a cage made of parallel rods or fabric and is connected to the deposition drum 5. Surround it with a concentric arc. This is connected to the positive terminal of DC power supply 10 by cable 9. is connected to. Similarly, the shaft 8 of the precipitation drum 5 is connected to the DC power supply 1 by means of a cable 11. Connected to the negative terminal of 0.

A redox electrode 12 is immersed in an etching agent 4 flowing through an electrolytic chamber 2, which During operation, monitor the redox potential of the etching agent. The redox electrode 12 is shown in FIG. 1, it is shown directly inside the electrolytic chamber 2, but in terms of measurement technology, the flow path outside the electrolytic chamber 2, For example, the lower liquid reservoir 2I of the electrolytic chamber 2 and the electrolytic chamber are connected (through a conduit not shown). This electrode, which is preferably located inside, is connected to the control circuit 13, and this circuit Controls the DC power supply to keep negative and divalent copper ion concentrations constant within predetermined limits. hold The measured redox potential indicates the amount of this ion concentration, which is This serves as an indicator of the progress of regeneration of the regenerating agent. Please refer to this gold publication No. 2650912 again. . However, in the configuration of the present invention, the type of control is not a decisive issue; Optimize the metal that is separated from the etching agent by etching and removed from the etching agent. This control is performed only from the perspective of removing In one electrolysis, not only the specific reaction of metal deposition is achieved, but also the in that by limited oxygen production a limited pH value can be achieved again. , which differs markedly from the subject matter of European Patent No. 0141905.

The scraping blade 18 is applied with some pressure and, in some cases, to the outer covering surface of the precipitation drum 5. In parallel, while vibrating, it contacts the titanium layer 7 and scrapes off the deposited copper from there. The copper powder thus obtained is dropped into a dropping device 19, packed into an easy-to-handle container 20, and then leads to reuse equipment.

Inside the housing 1, below the electrolytic chamber 2, there is a liquid reservoir 21, and inside this is the same as before. Then, the etching agent 4 in the liquid reservoir 21 is filled to 1!22. In a controlled process, the copper is increased in etching in a predetermined manner that is not important here. Etching agent is introduced into the electrolytic chamber, or depleted etching agent is discharged from the electrolytic chamber. the By way of example and without limitation, the earlier patent application No. 383 No. 9651.3.

The auxiliary electrode device 23 is immersed in the etching agent 4 in the liquid reservoir 21, as shown in FIG. Beauty! ! 13 to make each part easier to understand.

This auxiliary electrode device 23 includes one row of anode rods 24 and two rows of cathode rods provided on both sides. 25. The arrangement of these rows is particularly easy to understand with reference to FIG. Yang The pole bars 24 are electrically interconnected at their upper ends by conductive strips 26. Against this Accordingly, in FIG. 3, the cathode rods 25 in the left row are So, we will be supplying national current again.

The cathode rod 24 and the cathode rod 25 are mounted on a support plate 2 of electrically insulating material in the above-described device. 9, and this support plate can be fixed to the housing 1 with screws.

The lower end of the cathode rod 25 is screwed to the opposing plate 30, and the lower end of the cathode rod 24 The ends are movable through holes in the opposing plate 30.

It will also be appreciated that the counter plate 30 is made from an electrically insulating material.

In this way, the width of the liquid reservoir 21, that is, the dimension perpendicular to the plane of the paper in FIG. A large number of auxiliary electrode devices 23 are distributed, which are electrically connected in a row, but in parallel. All anodes of the auxiliary electrode arrangement 23, which are preferably connected in a row, are connected to the cable 3 1 to the positive terminal of the second DC power supply 32, and correspondingly connects the auxiliary electrode bag 22 to the positive terminal of the second DC power supply 32. All cathodes of 3 are connected to the negative pole of a DC power supply 32 by a cable 33.

The pt+-detector 34 is distributed into the etching agent 4 in the liquid reservoir 21. clear This may be done in the conduit supplying the etching agent 4 or at any other suitable location, such as It can also be placed in The pH detector 34 detects the pH value of the etching agent 4. Therefore, a signal is always sent to the second control circuit 35, and this circuit controls the second straight groove power supply 32. Control. The control process is basically the same as the method described in European Patent No. 0141905. is done in a similar way. In particular, the etching agent in the etching equipment is oxidized in the air. When the pH value increases beyond the expected value of 2.0, for example, the pH detector 34 Check this. The control circuit 35 operates the second DC chamber 532 to provide assistance. A European special model that causes an electrolytic reaction between the anode FIJ 24 of the electrode device 23 and the cathode rod 25. Voltages, current strengths and uses opposite to those described in Patent No. 0141905 The surface condition of the electrode (see below for this) should be adjusted for the purpose of re-adjusting the pH value. can be adapted independently of others. The control process is controlled on the one hand. In the circuit 35 it is carried out to adjust the pH value and on the other hand it is regenerated in the control circuit 13. This is done to adjust the redox potential of the etching agent 4, but these are completely different from each other. is unrelated.

European Patent No. 0141905, which has already been mentioned many times, claims that the , to shift the simultaneous production of chlorine gas and oxygen gas in the direction of oxygen production. implied that it could be done. Based on this, we have described herein (see Figure 3 ) In the device, the anode 24 is also provided with a coating 36 preferably made of a polypropylene knitted fabric. use. Type of knitted fabric and winding method (tension and gap between each winding) The extent to which oxygen is generated in the anode rod 24 of the auxiliary electrode device 23 can be controlled over a wide range. can be limited to Under this condition, chlorine gas is generated undesirably. It is actually possible to eliminate this completely.

To achieve a similar effect, the material forming the cathode rod 24 is also useful, here are (at least on the surface) platinum metals (platinum, titanium, tantalum, iridium, rubidium). Place the oxide or mixed oxide of um).

, -1-1+1 3 I abstract It has properties that make it compatible, and is adjusted).

international search report -1 noodles, 11^-1 thing-m, PCT/EP 91100340 international investigation report

Claims (10)

[Claims] 1. An electrolytic regeneration device for an etching agent containing chloride and metal ions, comprising: an electrolytic chamber in which a first anode and a second cathode are arranged; a first anode and a second cathode; a first DC power source connected to the During the reaction, metal is deposited from the etchant at the first cathode and further etched. In order to adjust the pH value of the quenching agent, water is anodicly split, thereby producing hydrogen ions. 1. An electrolytic regeneration device for producing oxygen and oxygen comprising: a) a separate second anode; 4) and an independent second cathode (25); b) an independent second straight line connected to the second anode (24) and the second cathode (25); a current power source (32); This causes electrolytic reaction to occur between the second anode (24) and the second cathode (25). an etch characterized by producing oxygen at the second anode (24) during the reaction; Electrolytic regeneration device for cleaning agents. 2. The anode has a form in which many anode rods (24) are electrically connected in parallel, and the cathode has many cathode rods (25) are electrically connected in parallel. The device according to claim 1. 3. The anode rod (24) and the cathode rod (25) are housed together in the auxiliary electrode device (23). In addition, rows of cathode rods (25) are arranged on both sides of the row of anode rods (24) in the center. Ru 3. The device according to claim 2. 4. The second anode (24) has at least a surface made of platinum metal (platinum, titanium, titanium). consisting of oxides or mixed oxides of metals such as metal, iridium, and rubidium Apparatus according to any one of claims 1 to 3. 5. Any one of claims 1 to 4, wherein the anode (24) has a gas permeable coating (36). The device described. 6. 6. Device according to claim 5, characterized in that the covering (36) is a polypropylene fabric. 7. The covering (36) is a woven fabric of fluorine-based synthetic resin, such as PTFE. Apparatus according to claim 5. 8. 6. Device according to claim 5, characterized in that the covering (36) is a carbon fiber fabric. 9. 6. Apparatus according to claim 5, wherein the covering (36) is needle felt. 10. It has a pH detector (34) and a control circuit (35), and the pH detector (34) monitors the pH value of the etching agent (4) and acts on the control circuit (35). A circuit controls a second DC power source (32) to substantially equalize the pH value of the etchant. 10. The device according to claim 1, wherein the device maintains a constant value.