JPS639020B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention uses ethylenediaminetetraacetic acid (EDTA)
Regarding a method for regenerating an electroless copper plating bath containing a complexing agent such as EDTA-Cu The present invention relates to a method for regenerating an electroless plating bath supplied as a complex and an apparatus used therein. In electroless plating, whether it is used as a base plating for electroplating or used on its own, copper ions in the plating bath are removed as a result of the reaction. , PH, i.e., hydroxide ion and reducing agent, are reduced, and reaction by-products are generated according to the reduction. This is an unavoidable phenomenon because the electroless plating reaction is an irreversible reaction. On the other hand, the quality of an electroless copper plating film is greatly influenced by the plating bath composition and plating conditions. That is, as the salt concentration due to reaction by-products in the plating bath increases, the properties and quality of the electroless copper plating film deteriorate and the plating reaction rate changes. By the way, in electroless copper plating for printed wiring boards, especially in printed wiring boards produced by semi-additive or full additive methods, the physical properties of the electroless plating film are that most of the circuits are formed by electrolytic copper plating. Compared to the conventional subtractive method, which uses electroless plating for the sole purpose of forming through-holes or conductors, it is required to form a film of much better quality. In other words, unless the physical properties of the electroless copper plating film are similar to those of electrolytic copper plating, such as copper pyrophosphate plating and copper sulfate plating, equivalent printed wiring boards cannot be obtained. In terms of controlling the plating film, controlling the reaction rate of electroless copper plating is also very important. Therefore, the composition of the electroless copper plating bath must be controlled to a constant concentration as much as possible, and reaction by-products must be minimized as much as possible. Conventionally, it decreases with the electroless plating reaction.
Manual or automatic analysis of Cu ²⁺ , OH ^- and reducing agents,
Or, when the concentration of these components in the plating bath reaches a predetermined concentration, estimated from the amount of the object to be plated and the plating time, a separately prepared copper sulfate solution, sodium hydroxide solution and a reducing agent such as formaldehyde are added to the solid state. Alternatively, the bath concentration was adjusted by adding a certain amount of each in the form of an aqueous solution. On the other hand, along with this, sodium sulfate, sodium formate, and alcohols such as methanol and ethanol are accumulated. Therefore, as the amount of these reaction by-products increases, plating defects increase. According to experience, after a certain bath life has been reached, part or all of the bath is discarded and replaced with a new plating bath. However, this method not only increases the cost, but also causes disadvantages such as uneven quality and poor workability, which is a problem especially when a high-quality electroless plating film is required as mentioned above. . Furthermore, there was also a problem in the treatment of waste liquid when the plating liquid was renewed. In other words, detoxification treatment such as COD countermeasures and BCD countermeasures is required for the complexing agent in the waste liquid, which not only increases the cost of detoxification treatment from the point of view of pollution control, but also requires disposal. They are unable to respond to the social situation, which is becoming increasingly difficult. The present invention aims to solve the above-mentioned drawbacks of the prior art, and allows stable electroless plating with less accumulation of reaction by-products, and also solves the problem of waste liquid treatment. The present invention is characterized by using a method of regenerating an electroless plating bath and an apparatus thereof that can reduce the amount of electroless plating bath. That is, the method for regenerating an electroless plating bath of the present invention is characterized by including the following steps (a) to (d). (b) A step of continuously or intermittently taking out part or all of the electroless plating solution from an electroless copper plating bath containing a complexing agent, and separating and removing copper ions in the solution. . (b) A step of acidifying this liquid to precipitate the complexing agent and recovering it. (c) An anode chamber with a copper anode and a cathode chamber with a cathode separated by an ion exchange membrane,
The cathode chamber contains an alkaline solution (if the ion exchange membrane is an anion exchange membrane) or an acidic solution (if the ion exchange membrane is a cation exchange membrane).
On the other hand, the recovered complexing agent is introduced into the anode chamber, and a direct current is passed between the two electrodes. (d) A process of recycling the solution in this anode chamber into an electroless plating bath. Furthermore, the electroless plating bath regeneration device of the present invention includes:
It includes the following devices (a) to (b) as constituent elements. (a) Decompose the copper chelate in the electroless copper plating solution,
A copper precipitation device that precipitates copper components. (b) A complexing agent recovery device that changes the liquid properties of the solution to precipitate and recover the complexing agent. (c) An electrolytic device in which an anode chamber and a cathode chamber are formed by partitioning with an ion exchange membrane, an anode made of copper is disposed in the anode chamber, and a cathode is disposed in the cathode chamber. Hereinafter, the present invention will be described in more detail with reference to the accompanying drawings. FIG. 1 is a flow diagram of the present invention. The electroless plating bath 12 contains copper ions, hydroxide ions (PH adjuster), a reducing agent, a complexing agent, and can further contain various auxiliary agents. As electroless copper plating progresses, copper ions, hydroxide ions, and reducing agents are consumed, while sodium formate, methyl alcohol, etc. (when formaldehyde is used as the reducing agent) are produced as by-products. Furthermore, when copper ions are added as copper sulfate and hydroxide ions are added as sodium hydroxide, sodium sulfate will accumulate. Therefore, the consumption amount is increased from the cycle system and non-cycle system to lines 13 and 1, respectively.
5, and part or all of the plating liquid (including by-products) is continuously or intermittently removed from the plating bath 12. Note that the term "intermittent" as used herein includes cases in which the information is simply taken out discontinuously without a fixed period. Figure 1 shows the case where a portion of the supply overflows and is continuously taken out depending on the supply amount.
The overflowing tamping liquid 12 is led to the copper precipitation device 21 from the supply port via the line 17 and the filter 19 (which may be omitted). In the copper precipitation device 21, copper ions are precipitated and removed. Separation of copper ions is carried out, for example, by decomposing copper chelate and precipitating copper as metallic copper or copper oxide by one or a combination of two or more of the following methods. (1) Add metallic copper such as copper plate, copper foil, copper powder, etc. to the liquid. (2) Add a catalyst such as Pd ²⁺ to the liquid. (3) Maintain the liquid at high temperature and high pH. In addition to these precipitation removal methods, copper removal is also carried out by electrolytic removal. For example, an insoluble anode and a cathode are placed in an electroless copper plating solution, and a direct current is applied to deposit copper on the cathode, thereby removing copper ions in the bath. Therefore, the copper precipitation device 21 can include an input member for copper powder, a Pd ²⁺ alkaline agent, etc. or a heating member, as desired, and can further include a stirring member to quickly carry out the above reaction. . It is also possible to provide an anode and a cathode. The precipitated copper component is appropriately discharged from valve 24. The solution from which the copper ions have been precipitated is led from the outlet to the complexing agent recovery device 27 via the line 23 and the filter 25 (which may be omitted).
Acid can be led to the complexing agent recovery device via line 28, and the complexing agent is precipitated by making the liquid in this device sufficiently acidic for the complexing agent to precipitate. The suitable PH range varies depending on the complexing agent, but for example, in the case of EDTA, the PH range is generally 4.0 or less,
Preferably the pH is 2.0 or less, more preferably PH1.0 or less. General acids are suitable for adjusting the liquid properties. Examples include sulfuric acid and hydrochloric acid. FIG. 2 is a graph showing the relationship between recovery rate and pH when EDTA is used as a complexing agent. liquid
It can be seen that EDTA can be sufficiently recovered by setting the pH to 2.0 or lower, and it is more preferable to set the pH to 1.0 or lower. In addition, in this example, the pH was adjusted with sulfuric acid. In this way, the separation of the complexing agent from the electroless copper plating bath is achieved by decomposing the copper chelating agent and separating the complexing agent by precipitation, but the complexing agent that can be used in this process is EDTA. In addition, there are many known complexing agents for electroless copper plating, such as Lotsiel (sodium potassium tartrate), ethylenediaminetetramine, triethanolamine, and diethanolamine. The precipitated complexing agent passes through line 29 to electrolyzer 3.
1 to the anode chamber 33. At this time, the complexing agent may be washed and further dried if necessary, and the recovered complexing agent may be supplied in a solid state, or it may be dissolved in an alkaline solution in advance and supplied to the electrolytic device 31 in a solution state. It may also be guided to the anode chamber 33. The electrolyzer 31 is partitioned by an ion exchange membrane 37 to form an anode chamber 33 and a cathode chamber 35.
An anode 39 made of copper is disposed in the anode chamber 33, while a cathode 41 is disposed in the cathode chamber 35. As the cathode 41, a material insoluble in the cathode aqueous solution, such as stainless steel or carbon, is preferable. The recovered complexing agent is supplied to the anode chamber 33 in a solid state, liquid state, etc., and the liquid property is maintained at a level in which the complexing agent can be dissolved. For example, in the case of EDTA, the pH is generally 4.0 or higher, preferably PH4.0 or higher.
7.0 or higher. (i) When an alkaline solution is placed in the anode chamber 35, an anion exchange membrane is used as the ion exchange membrane; (ii) When an acidic solution is placed in the cathode chamber 35, a cation exchange membrane is used as the ion exchange membrane. is used. When electrolysis is performed by passing a direct current between the two electrodes, that is, between the anode 39 and the cathode 41, copper is dissolved and copper ions are generated in the anode chamber 33, and these ions are absorbed by the complexing agent supplied via the line 29. and then this copper complex forms line 1
3 is recycled to the electroless plating bath 11. When the liquid in the cathode chamber 35 is alkaline, OH ^- ions pass through the ion exchange membrane 37 (anion exchange membrane) and reach the anode chamber 33 as a result of electrolysis, and as a result, exhausted copper ions are removed from the line 13. (as a complex compound) and hydroxide ions are fed into the plating bath 11. This case is convenient in that hydroxide ions necessary for electroless plating are supplied together with copper ions. If the liquid in the cathode chamber 35 is acidic, the
OH ^- ions are not supplied and must be supplied separately, but this can be supplied as NaOH etc. Thus, copper ions (as a complex compound) or even OH ^- ions are supplied via line 13, and reducing agents etc. are supplied via line 15 or 15'. Above, separation of copper ions,
Although the case has been described in which the recovery of the complexing agent and the elution of copper ions by electrolysis are performed in separate tanks, it is also possible to perform each of the above operations in one tank. FIG. 3 is a graph showing the relationship between current density and anode dissolution efficiency. This was done using the electrolyzer shown in Figure 1, with 0.08 mol of EDTA/4Na in the anode chamber.
Put 0.1 mol of NaOH into the cathode chamber, and use a 0.5 dm ² copper plate as the anode and a 0.5 dm ² 18− as the cathode.
8 stainless steel was used and the liquid temperature was 50°C. Similarly, FIG. 4 is a graph showing the relationship between the concentration ratio R of copper ions and EDTA (R=[EDTA]/[Cu ²⁺ ]) and the anode dissolution efficiency. The same procedure as in FIG. 4 was carried out except that the EDTA concentration was changed. The higher the concentration of EDTA, which is a copper complexing agent,
The complexing agent is dissolved with high current efficiency, and therefore, by keeping the complexing agent at a predetermined concentration or higher, it is possible to efficiently dissolve and replenish the complexing agent. FIG. 5 is a graph showing the relationship between the liquid temperature in the anode chamber and the anode dissolution efficiency. This has the same bipolar chamber composition as in Figure 2, current value 2A, current flow amount 3600 clones,
Anode current density 3A/dm ² , cathode current density 4A/dm ²
I did it at It can be seen that the higher the liquid temperature in the anode chamber, the more efficient the current is in dissolving copper. For example, in electroless plating, such as printed wiring boards, which requires high plating speed and strict physical properties of the plating film, it is ideal to use the plating bath at as high a temperature as possible, making it even more effective. It is. As explained above, according to the present invention, at least a portion of the electroless plating solution is taken out, a complexing agent is recovered from it, and the consumed copper is supplied as a copper complex compound using the complexing agent. By doing so, the accumulation of by-products such as sodium sulfate, sodium formate, or alcohol in the electroless copper plating bath becomes extremely small, and in the extreme, the accumulation of sodium sulfate becomes zero, and the electrolytic bath becomes large. This makes it possible to extend the service life and perform stable high-quality electroless plating. In addition, conventionally, plating waste liquid
Countermeasures against COD and BOD have been a major problem in terms of pollution, but by extending the lifespan of plating baths, there is no need to dispose of baths, and expensive complexing agents such as EDTA can be recovered and used effectively. can. Experimental Example Using a bath composition (bath volume 5) of EDTA・4Na 30g/CuSO ₄・5H ₂ O 6g/paraformaldehyde 7g/PH (adjusted with NaOH) of 11.8 and a temperature of 50°C, a glass epoxy copper-clad laminate was Electrolytic plating was applied.
At this time, sodium sulfate was added to the bath as shown in Table 1, and its influence was investigated.

[Table] Example 1 Glass epoxy copper clad laminate coated with trisodium phosphate 40
Degrease with 100g/g/ of ammonium persulfate.
After etching with a colloidal solution of palladium and tin and activation with 50 g of sulfuric acid, electroless copper plating was performed using the present method and the conventional method. Bath composition Copper sulfate 10g/EDTA 50g/Formaldehyde 10g/Sodium hydroxide Adjusted to pH 12 Bath temperature 50°C Plating was carried out for 12 days at a load of 1dm ² /.
In the conventional method, copper ions and hydroxide ions were supplemented by adding copper sulfate and sodium hydroxide, resulting in an increase in the concentration of sodium sulfate. In this method, the apparatus plating bath shown in Fig. 1 has the above bath composition, and the cathode chamber of the electrolyzer is filled with NaOH0.1.
A copper plate was used as an anode and a stainless steel plate was used as a cathode, and electricity was applied at a cathode current density of 2.5 A/dm ² and a cathode current density of 4 A/dm ² , and recovered EDTA was replenished into the anode chamber. However, no increase in the concentration of sodium sulfate was observed. To recover EDTA, take out a part of the plating bath and
The pH was adjusted to 14, copper foil was added to precipitate and remove copper ions, and then H ₂ SO ₄ was added to the solution to adjust the pH to 2.0 to quantitatively precipitate EDTA, followed by filtration. The results are shown below.

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【table】 [Brief explanation of the drawing]

FIG. 1 is a flow diagram illustrating the present invention.
FIG. 2 is a graph showing the recovery rate of EDTA.
FIG. 3 is a graph showing the relationship between current density and anode dissolution efficiency. Figure 4 shows copper ions and EDTA
It is a graph showing the relationship between the concentration ratio R and the anode dissolution efficiency. FIG. 5 is a graph showing the relationship between liquid temperature and anode efficiency. 11... Electroless plating bath, 21... Copper precipitation device, 27... Complexing agent recovery device, 31... Electrolyzer, 37... Ion exchange membrane, 39... Anode, 41
……cathode.

Claims (1)

[Claims] 1 (a) Part or all of the electroless plating solution is continuously or intermittently taken out from an electroless copper plating bath containing a complexing agent to remove copper ions from the solution. (b) acidify this liquid to precipitate the complexing agent and recover it; (c) divide it by an ion exchange membrane into an anode chamber with a copper anode and a cathode chamber with a cathode. established,
The cathode chamber contains an alkaline solution (if the ion exchange membrane is an anion exchange membrane) or an acidic solution (if the ion exchange membrane is a cation exchange membrane).
On the other hand, the recovered complexing agent is introduced into the anode chamber, and a direct current is passed between the two electrodes, and (d) the solution in the anode chamber is recycled to the electroless plating bath. Characteristic method for regenerating electroless plating baths. 2 (a) A copper precipitation device that decomposes the copper chelate in the electroless copper plating solution and precipitates the copper component. (b) a complexing agent recovery device that precipitates and recovers the complexing agent by changing the liquid properties of the solution; and (c) an anode chamber and a cathode chamber separated by an ion exchange membrane, the anode chamber containing copper. 1. A regeneration device for an electroless plating bath, comprising an electrolytic device in which an anode is disposed, and a cathode is disposed in the cathode chamber.