JP5403535B2 - Method for electrolytic treatment of etching solution - Google Patents

Description

  The present invention relates to an electrolytic treatment method for an etchant containing a manganese salt as an active ingredient.

  As a method of forming an electroplated film on a resin molded body, after degreasing and etching, neutralization and pre-dip are performed as necessary, and then a colloidal solution containing a tin compound and a palladium compound is used. A general method is a method in which an electroless plating catalyst is applied, an activation treatment (accelerator treatment) is performed as necessary, and then electroless plating and electroplating are sequentially performed (Non-Patent Document 1).

  In this case, a chromic acid mixture composed of a mixture of chromium trioxide and sulfuric acid is widely used as the etching treatment liquid. However, the chromic acid mixture contains toxic hexavalent chromium and thus has an adverse effect on the working environment. In addition, in order to treat wastewater safely, it is necessary to neutralize and precipitate hexavalent chromium after reducing it to trivalent chromium ions, and complicated treatment is required for wastewater treatment. For this reason, in consideration of safety at the time of work in the field and the environmental impact of wastewater, an etching treatment liquid not containing chromic acid is desired.

  As a result of repeated research to develop an etching solution that can replace the chromic acid mixture, the present inventors have found at least one component selected from the group consisting of manganese salts, inorganic acids, and perhalogenates and perhalogenates. A novel etching solution containing an active ingredient has been found (see Patent Document 1 below). The etching solution is a highly safe etching treatment solution that does not contain highly harmful components such as chromic acid, and forms a plating film with high adhesion when used in etching treatments for various resin molded products. can do.

  However, when the etching process is continuously performed using the etching solution, the perhalogen acid and the perhalogenate are reduced to the halogen acid and the halogen acid salt, respectively. Accumulation in the layer tends to cause self-decomposition of the etching solution, and the concentration of manganese salt, perhalogenic acid, perhalogenate, etc. rapidly decreases, and the composition of the etching solution cannot be kept constant. In this way, the etching solution in which the concentration of manganese salt, perhalogen acid, perhalogenate, or the like is lowered has a reduced oxidizing action, and eventually etching cannot be continued. For this reason, it is desired to develop a method capable of extending the life of the etching solution containing the above-described manganese salt as an active ingredient by solving the problem of performance degradation due to the self-decomposition of the etching solution.

As a result of repeated research on a method for extending the lifetime of an etching solution containing the above-described manganese salt as an active ingredient, the present inventors have conducted anodic electrolysis when halogen acid and / or halogen acid salt accumulates with use. It has been found that by performing oxidation treatment, the concentration of accumulated halogen acid and halogen acid salt can be reduced, the concentration of perhalogen acid and / or perhalogenate can be increased, and the etching performance can be recovered. A patent application was filed (Japanese Patent Application No. 2008-105547). According to this method, it is possible to extend the life of an etching solution containing a manganese salt as an active ingredient, but it is desired to further improve the treatment efficiency by anodic electrolytic oxidation. There is also a demand for easy maintenance.
WO2007 / 122869A1 Tadao Hayashi, Masao Matsuoka, Hidemi Rope Funa; Electroplating Research Group, “Electroless Plating—Basics and Applications”, Nikkan Kogyo Shimbun (1994), pp. 133

  The present invention has been made in view of the current state of the prior art described above, and its main purpose is to recover or maintain etching performance by anodic electrolytic oxidation of an etching solution containing manganese salt as an active ingredient. An object of the present invention is to provide a method capable of further improving the processing efficiency of an etching solution by electrolytic oxidation treatment and facilitating maintenance of the electrolytic processing apparatus.

  The present inventor has intensively studied to achieve the above-described object. As a result, in the method of extending the life of the etching solution by anodic electrolytic oxidation of the etching solution in which the halogen acid and / or the halogen acid salt is accumulated, the etching solution to be processed by the cation exchange membrane made of a perfluorosulfonic acid resin. According to the method of electrolytic treatment using the electrolytic treatment apparatus having the cathode chamber separated from the cathode, even when the electrolytic oxidation treatment is performed continuously, the contamination of the electrolytic solution in the cathode chamber is reduced and the regeneration efficiency is increased for a long time. It has been found that it becomes possible to maintain. In this method, the cation exchange membrane made of a perfluorosulfonic acid resin used as a diaphragm has high ion exchange efficiency, so that an efficient electrolytic oxidation treatment is possible, and moreover, compared with a ceramic unbaked diaphragm, etc. It was found that the electrolytic solution is less contaminated and the maintenance of the electrolytic treatment apparatus becomes easy. The present invention has been completed as a result of further research based on these findings.

That is, the present invention provides the following electrolytic treatment method for an etching solution.
1. From an aqueous solution containing 20 to 1200 g / L of inorganic acid, 0.01 to 40 g / L of manganese salt, and 1 to 200 g / L of at least one component selected from the group consisting of perhalogenates and perhalogenates. An etching solution electrolytic treatment method comprising:
Using an electrolytic processing apparatus having a cathode chamber separated from an etching solution to be processed by a cation exchange membrane made of a perfluorosulfonic acid resin, an etching solution in which the concentration of halogen acid and / or halogen acid salt is increased by use. An anodic electrolytic oxidation process.
2. Item 2. The method according to Item 1, wherein the etching solution in which the total concentration of the halogen acid and the halogen acid salt is 10 g / L or more is subjected to electrolytic treatment.
3. Item 3. The method according to Item 1 or 2, wherein an insoluble electrode is used as the anode.
4). The method according to any one of the above items 1 to 3 for performing electrolysis in the anodic current density 0.1~20A / dm ^2.
5. The method according to any one of the above items 1 to 4 anodic electrolytic oxidation treatment under stirring.

  Hereinafter, the processing method of the present invention will be specifically described.

Etching solution to be treated The etching solution to be treated in the present invention is selected from the group consisting of 20 to 1200 g / L of inorganic acid, 0.01 to 40 g / L of manganese salt, and perhalogen acid and perhalogenate. It consists of an aqueous solution containing 1 to 200 g / L of at least one component. The etching solution is an etching treatment solution that can replace a chromic acid mixed solution that can form a plating film having good adhesion to various resin molded bodies such as ABS resin. It is a novel etching solution that is high and easy to treat waste water.

  Among the active ingredients in the etching solution, inorganic acids include sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, boric acid, carbonic acid, sulfurous acid, nitrous acid, phosphorous acid, boric acid, hydrogen peroxide, perchloric acid, etc. Can be used. Of these, sulfuric acid, hydrochloric acid and the like are particularly preferable. These inorganic acids can be used singly or in combination of two or more. The content of the inorganic acid is about 20 to 1200 g / L, preferably about 300 to 1000 g / L.

  Of the effective components in the etching solution, permanganate is particularly preferable as the manganese salt. The permanganate may be a salt in an aqueous solution, and specific examples thereof include sodium permanganate and potassium permanganate. Manganese salts can be used singly or in combination of two or more. The manganese salt content is about 0.01 to 40 g / L, preferably about 0.1 to 10 g / L.

  Among the active ingredients in the etching solution, examples of perhalogen acids include perchloric acid, perbromic acid, and periodic acid. As the perhalogenate, the above-mentioned water-soluble salt of perhalogen acid can be used, and for example, sodium perhalogenate, potassium perhalogenate, or the like can be used. Perhalogenic acid and perhalogenate can be used singly or in combination of two or more.

  The content of at least one component selected from the group consisting of perhalogenic acid and perhalogenate is about 1 to 200 g / L, preferably about 10 to 100 g / L.

Electrolytic treatment method of etching solution When the above etching solution is subjected to etching treatment for a long period of time, perhalogen acid and / or perhalogenate in the etchant is reduced to produce halogen acid and / or halogenate, When accumulated in the etchant, decomposition of the etchant proceeds rapidly.

  According to the present invention, the concentration of the halogen acid and the halogen acid salt can be reduced by performing an anodic electrolytic oxidation treatment on the etching solution having an increased halogen acid and / or halogen acid salt concentration by the method described later. It is possible to maintain good etching performance for a long time.

  In the present invention, it is necessary to perform anodic electrolytic oxidation using an electrolytic processing apparatus having a cathode chamber separated from an etching solution to be processed by a cation exchange membrane made of a perfluorosulfonic acid resin. According to this method, the cathode chamber is separated from the etching solution by the cation exchange membrane made of perfluorinated sulfonic acid resin, so that the contamination of the electrolyte in the cathode chamber is reduced and the regeneration efficiency is maintained for a long time. be able to. In particular, a cation exchange membrane made of a perfluorinated sulfonic acid resin used as a diaphragm can be made thin in order to have sufficient chemical stability and thermal stability, and because the ion exchange efficiency is high, An efficient electrolytic oxidation treatment becomes possible. In addition, when ceramic baked diaphragm is used, if anodic electrolytic oxidation is continued, the etching solution penetrates into the baked diaphragm and metal salts are deposited on the diaphragm, or the electrolyte is gradually contaminated. However, when a cation exchange membrane made of a perfluorosulfonic acid resin is used as a diaphragm, contamination of the electrolyte in the cathode chamber can be prevented. Even if the replacement frequency of the diaphragm, cathode, electrolyte, etc. is reduced, the electrolytic treatment performance can be maintained for a long time. For this reason, maintenance of the electrolytic treatment apparatus becomes easy.

  In the processing method of this invention, the schematic of an example of the processing apparatus used for an electrolytic process is shown in FIG. In the electrolytic treatment apparatus, the cathode chamber is separated from the etching solution to be treated by a cation exchange membrane made of a perfluorosulfonic acid resin.

  The cation exchange membrane comprising a perfluorosulfonic acid resin used as a diaphragm in the present invention is not particularly limited. Trade names: Aciplex-F (Asahi Kasei Co., Ltd.) and the like can be used. As an example of such a perfluorosulfonic acid resin, a resin having the following structural unit can be exemplified.

本発明では、例えば、イオン交換能が０．１〜４ｍｅｑ／ｇ程度の過フッ化スルホン酸樹脂からなるカチオン交換膜を用いることができ、特に、１〜３．５ｍｅｑ／ｇ程度のものを用いることが好ましい。

In the present invention, for example, a cation exchange membrane made of a perfluorosulfonic acid resin having an ion exchange capacity of about 0.1 to 4 meq / g can be used. It is preferable.

  The thickness of the cation exchange membrane is not particularly limited, but is preferably as thin as possible in order to perform the electrolytic oxidation treatment efficiently. However, if the cation exchange membrane is too thin, when the temperature rises, it may easily creep with water and the strength may decrease. Therefore, considering these points, the thickness of the cation exchange membrane is preferably about 0.05 to 0.3 mm.

  The size of the cathode chamber is not particularly limited, and may be sufficient to accommodate the cathode depending on the shape and size of the cathode to be used.

  For example, an aqueous solution of an inorganic acid can be used as the electrolytic solution in the cathode chamber. In this case, it is preferable to use the same inorganic acid as the inorganic acid contained in the etching solution to be processed. The concentration of the inorganic acid used as the electrolytic solution is preferably about 2 to 800 g / L, and more preferably about 50 to 400 g / L, for example.

  As the anode, any insoluble electrode can be used without particular limitation. Specific examples of insoluble electrodes include Ti / Pt (Ti coated with platinum coating), Ti / Ir oxide (Ti coated with Ir oxide coating), Ti / Ru (Ti Ru oxide) Coated), Ti / Ir oxide-Ru oxide (coated by mixing Ir oxide and Ru oxide on Ti), Ti / Ir oxide-Ta oxide (Ir on Ti) Oxide and Ta oxide mixed and coated), Ti / Pt / Ir oxide-Ru oxide (Ti / Pt mixed with Ir oxide and Ru oxide and coated) , Ti / Pt / Ir oxide-Ta oxide (Ti / Pt mixed with Ir oxide and Ta oxide and coated), stainless steel, aluminum, lead alloy (Pb-Sn alloy, P -Ag alloy, Pb-Sb alloy), lead oxide (lead monoxide, lead dioxide, lead trioxide, trilead tetraoxide), lead, tin oxide, carbon, diamond electrode (diamond containing nitrogen and boron is silicon And those coated on a substrate such as niobium) and ITO electrodes (indium tin oxide). Among these anodes, lead alloys (Pb—Sn alloy, Pb—Ag alloy, Pb—Sb alloy), lead oxides (lead monoxide, lead dioxide, lead trioxide, trilead tetroxide), lead, etc. Preferably, lead oxide is particularly preferable.

  There is no restriction | limiting in particular as a cathode, Both an insoluble electrode and a soluble electrode can be used. As the insoluble electrode, an electrode similar to the above-described anode can be used. As the soluble cathode, copper, nickel, tin, iron, zinc, brass, aluminum, stainless steel and the like can be used. In particular, as the cathode, lead alloy, lead, Pt / Ti, nickel, copper, brass, stainless steel and the like are preferable.

  The shape of the electrode is not particularly limited, and any shape such as a rod shape, a plate shape, or a mesh shape can be used. The size of the electrode plate is not particularly limited, but the surface area ratio between the anode and the cathode is preferably about anode: cathode = 1: 1 to 100: 1, preferably about 1: 1 to 10: 1. More preferred.

  In the present invention, there is no particular limitation on the timing of performing the anodic electrolytic oxidation treatment, and the anodic electrolytic oxidation treatment may be appropriately performed when accumulation of halogen acid and / or halogen acid salt occurs. In particular, when the total concentration of the halogen acid and the halogen acid salt is about 10 g / L or more, the decomposition of the etching solution proceeds rapidly, and the concentrations of manganese salt, perhalogen acid, perhalogenate and the like tend to decrease remarkably. is there. For this reason, it is preferable to perform an anodic electrolytic oxidation treatment on the etching solution in which the total concentration of the halogen acid and the halogen acid salt is about 10 g / L or more.

  In addition, when performing anodic electrolysis, there is no particular limitation on the concentration of manganese salt, inorganic acid and perhalogen acid in the etching solution to be treated, and anodic electrolysis is performed on an etching solution of any concentration. Can do. Since the concentration of the manganese salt decreases as the etching process proceeds, the manganese salt may not be included in the etching solution when the anodizing process is performed. Such an etching solution can be continuously used by adjusting the concentration of the active ingredient to a predetermined range after the anodic electrolytic treatment.

  In the treatment method of the present invention, first, when a precipitate is contained in the etching solution to be treated, it is preferable to remove the precipitate by a method such as filter filtration.

The conditions of the anodic electrolytic oxidation treatment are not particularly limited. For example, the liquid temperature is about 20 to 70 ° C., preferably about 25 to 70 ° C., and the anodic current density is about 0.1 to 20 A / dm ² , preferably It may be about 1 to 10 A / dm ² .

  The treatment time of the anodic electrolytic oxidation treatment varies depending on the amount of the etching solution to be treated, and is not particularly limited, but until the concentration of the halogen acid and the halide salt contained in the etching solution is sufficiently reduced. Electrolytic treatment may be performed.

  The anodic electrolytic oxidation treatment can be performed with or without stirring the etching solution. In particular, the concentration of the halogen acid and the halogen acid salt can be greatly reduced by performing the anodic electrolytic oxidation treatment with stirring. The stirring method is not particularly limited, and any method such as air stirring, stirring with nitrogen gas, and liquid circulation with a pump can be employed. Further, the etching solution may be stirred by a method of swinging the electrode plate. In particular, methods such as air agitation, agitation with nitrogen gas, and liquid circulation with a pump are preferred. In addition, when the electrolytic treatment is performed using the diaphragm, the electrolytic solution in the diaphragm may be stirred.

  By performing the above-described anodic electrolytic oxidation treatment, the concentration of the halogen acid and / or the halogen acid salt contained in the etching solution is decreased, and the concentration of the perhalogen acid and / or the perhalogen acid salt is increased. In addition, the manganese salt concentration may slightly decrease. Therefore, after the anodic electrolytic oxidation treatment, the performance of the etching solution can be recovered and reused by adding manganese salt, perhalogen acid, perhalogenate, or the like as necessary.

  According to the etching solution treatment method of the present invention, an anodic electrolytic oxidation is performed on an etching solution containing at least one component selected from the group consisting of inorganic acids, manganese salts, and perhalogenates and perhalogenates as an active ingredient. By this simple method, the concentration of halogen acid and / or halogen acid salt that increases in the etching solution can be reduced.

  Therefore, by adopting the electrolytic treatment method of the present invention, it is possible to maintain the etching performance for a long period of time with respect to a highly safe etching solution containing the above-described manganese salt as an active ingredient.

  In particular, according to the method of the present invention, since the cathode chamber is separated from the etching solution by the cation exchange membrane made of a perfluorosulfonic acid resin, the contamination of the electrolyte solution in the cathode chamber is small. For this reason, even when the anodic electrolytic oxidation process is continuously performed, the regeneration efficiency can be maintained for a long time, and the maintenance of the electrolytic processing apparatus is easy. Moreover, the cation exchange membrane made of perfluorinated sulfonic acid resin used as a diaphragm has sufficient strength even when the film thickness is reduced, and has excellent ion exchange performance, so the rate of electrolytic oxidation treatment The etching solution can be regenerated quickly and efficiently.

  For this reason, the electrolytic treatment method of the present invention can be effectively used as a method for regenerating the etching solution, particularly when the plating treatment is continuously performed on the resin molded body.

  Hereinafter, the present invention will be described in more detail with reference to examples.

Example 1
Using the electrolytic treatment apparatus having the structure shown in FIG. 1, anodic electrolytic oxidation treatment was performed under the conditions shown in Table 1 below. As for the cathode chamber, a cation exchange membrane made of a perfluorosulfonic acid resin (DuPon, trade name: Nafion324) having a thickness of 0.15 mm was fixed using a Ti fixture, and the etching solution was used. separated.

処理対象のエッチング液の組成を下記表２に示す。各エッチング液の液量は、１Ｌとした。

The composition of the etching solution to be processed is shown in Table 2 below. The amount of each etching solution was 1 L.

上記した条件による電解処理後のエッチング液の組成を下記表３に示す。

The composition of the etching solution after electrolytic treatment under the above conditions is shown in Table 3 below.

尚、比較として、過フッ化スルホン酸樹脂製のカチオン交換膜に代えて、セラミック製円筒素焼きの隔膜（Φ50mm × H150mm、厚み4mm）を用いて、エッチング液から陰極室を分離した構造の電解処理装置を用いること以外は、上記した方法と同様にして、表２に記載したエッチング液に対して陽極電解酸化処理を行った。電解処理後のエッチング液の組成を下記表４に示す。

For comparison, electrolytic treatment with a structure in which the cathode chamber is separated from the etching solution by using a ceramic unglazed diaphragm (Φ50mm × H150mm, thickness 4mm) instead of a cation exchange membrane made of perfluorosulfonic acid resin. The anodic electrolytic oxidation treatment was performed on the etching solutions listed in Table 2 in the same manner as described above except that the apparatus was used. The composition of the etching solution after the electrolytic treatment is shown in Table 4 below.

以上の結果から明らかなように、表２に示した各組成のエッチング液について、陽極電解酸化処理を行うことによって、ハロゲン酸またはハロゲン酸塩の濃度を低下させて、過ハロゲン酸又は過ハロゲン酸塩の濃度を上昇させることができる。

As is clear from the above results, the anodic electrolytic oxidation treatment is performed on the etching solutions having the respective compositions shown in Table 2 to reduce the concentration of the halogen acid or the halogen acid salt. The salt concentration can be increased.

  In particular, as is clear from the comparison between Table 3 and Table 4, when a diaphragm made of a perfluorosulfonic acid resin is used (Table 3), it is compared with a case where a ceramic unbaked diaphragm is used (Table 4). Thus, it can be seen that the decrease in the concentration of the halogen acid or the halogen acid salt is large and the increase amount of the concentration of the perhalogen acid or the perhalogenate salt is large, so that the etching treatment regeneration capability is high. The reason for this is that the cation exchange membrane made of perfluorinated sulfonic acid resin has a high ion exchange performance and a thickness of 0.15 mm, which is much higher than the ceramic baked diaphragm (4 mm). This is considered to be because the ion exchange rate is high due to the thinness, and the efficiency of the electrolytic oxidation treatment is improved.

Example 2
Using an electrolytic treatment apparatus using a cation exchange membrane made of a perfluorinated sulfonic acid resin as a diaphragm and an electrolytic treatment apparatus using a ceramic baked diaphragm, an anodic electrolytic oxidation treatment of an etching solution is performed under the same conditions as in Example 1. It went continuously for a week.

  Then, using the electrolyte solution, the electrode plate, and the diaphragm used for one week, under the same conditions as in Example 1, No. 1 described in Table 2. The etching solution of No. 2 was subjected to an anodic electrolytic oxidation treatment, and the composition of the electrolytic solution after the electrolytic treatment was measured. The results are shown in Table 5 below.

以上の結果から明らかなように、過フッ化スルホン酸隔膜を用いた電解処理装置では、１週間連続して陽極電解酸化処理を行った後であっても、臭素酸の蓄積したエッチング液について、臭素酸の濃度を大きく低下させて、過臭素酸濃度を向上できることが判る。これに対して、セラミック製素焼き隔膜を用いた電解処理装置では、１週間連続して陽極電解酸化処理を行った後では、電解酸化による臭素酸の濃度の低下はわずかであり、電解処理性能の低下が認められる。

As is clear from the above results, in the electrolytic treatment apparatus using the perfluorinated sulfonic acid diaphragm, the etching solution in which bromic acid accumulated was obtained even after the anodic electrolytic oxidation treatment for one week continuously. It can be seen that the concentration of perbromic acid can be improved by greatly reducing the concentration of bromic acid. On the other hand, in the electrolytic treatment apparatus using the ceramic baked diaphragm, after the anodic electrolytic oxidation process was continuously performed for one week, the decrease in the concentration of bromic acid due to electrolytic oxidation was slight. A decrease is observed.

  The etching solution composition after electrolytic treatment when using a perfluorinated sulfonic acid diaphragm is No. shown in Table 3 above. In the electrolytic processing apparatus using the diaphragm made of perfluorinated sulfonic acid, it can be seen that there is little decrease in processing capacity even after continuous use. From this result, it can be seen that in the electrolytic treatment apparatus using the perfluorosulfonic acid diaphragm, the replacement frequency of the diaphragm, the electrolytic solution, and the like can be reduced, and the maintainability is improved.

Example 3
Decomposition resistance test No. 1 used in Example 1. For the etching solution of No. 10, the etching solution before and after the anodic electrolytic treatment by the electrolytic treatment apparatus using a cation exchange membrane made of a perfluorosulfonic acid resin was allowed to stand at 65 ° C. for 48 hours, and then permanganic acid The concentration of each component of potassium, sodium periodate and sodium iodate was measured. In addition, about the etching liquid after anodic electrolytic oxidation treatment, the potassium permanganate was added and the decomposition resistance test was done as 0.5 g / L same as the etching liquid before anodic electrolytic oxidation treatment.

  Table 6 below shows the concentration of each component in the etching solution after standing.

以上の結果から明らかなように、陽極電解酸化処理を行っていないエッチング液については、６５℃で４８時間放置後に、過マンガン酸カリウムと過ヨウ素酸ナトリウムの濃度が急激に低下して、ヨウ素酸ナトリウム量が増加しており、エッチング液の分解が進行したことが判る。これに対して、陽極電解酸化処理を行ったエッチング液については、放置後にも濃度変化は認められず、良好な安定性を有することが判る。

As is clear from the above results, the etching solution that was not subjected to the anodic electrolytic oxidation treatment was allowed to stand at 65 ° C. for 48 hours, and then the concentrations of potassium permanganate and sodium periodate were drastically decreased. It can be seen that the amount of sodium has increased and the decomposition of the etching solution has progressed. On the other hand, it can be seen that the etching solution subjected to the anodic electrolytic oxidation treatment does not change in concentration even after being left and has good stability.

Etching performance test Using the etching solution before the decomposition resistance test and the etching solution after the decomposition resistance test by the above-described method, a flat plate (10 cm) of ABS resin (trade name: Psycolac 3001M, manufactured by UMG ABS Co., Ltd.) Electroless plating was performed in the processing steps shown in Table 7 below using x5 cm x 0.3 cm, surface area of about 1 dm ² ) as an object to be plated.

上記した方法で無電解めっき皮膜を形成した後、試料表面における無電解めっき皮膜の形成された割合を測定して、無電解めっきの析出性を評価した。

After the electroless plating film was formed by the above-described method, the ratio of the electroless plating film formed on the sample surface was measured to evaluate the depositability of the electroless plating.

Subsequently, using a copper sulfate plating bath, electroplating treatment was performed for 120 minutes at a current density of 3 A / dm ² and a temperature of 25 ° C. to form a copper plating film having a thickness of 70 μm.

  The sample thus obtained was dried at 80 ° C. for 120 minutes and left to reach room temperature, and then a 10 mm wide cut was made in the plating film, and a tensile tester (manufactured by Shimadzu Corporation, Autograph SD). −100-C), the plating film was pulled perpendicular to the resin, and the peel strength was measured.

  The above results are shown in Table 8 below.

以上の結果から明らかなように、陽極電解酸化処理を行う前のエッチング液については、６５℃で４８時間放置した場合に、エッチング性能が大きく低下して、無電解めっきの析出性及びめっき皮膜の密着性が大きく低下することが判る。これに対して、陽極電解酸化処理を行ったエッチング液については、放置試験後においても良好なエッチング性能を維持しており、エッチング液の安定性が大きく向上したことが判る。

As is clear from the above results, the etching solution before the anodic electrolytic oxidation treatment, when left at 65 ° C. for 48 hours, greatly deteriorates the etching performance, and the electroless plating deposition properties and the plating film It can be seen that the adhesion is greatly reduced. On the other hand, it can be seen that the etching solution subjected to the anodic electrolytic oxidation treatment maintained good etching performance even after the standing test, and the stability of the etching solution was greatly improved.

Schematic of an example of the electrolytic treatment apparatus for enforcing the electrolytic method of this invention.

Claims (5)

From an aqueous solution containing 20 to 1200 g / L of inorganic acid, 0.01 to 40 g / L of manganese salt, and 1 to 200 g / L of at least one component selected from the group consisting of perhalogenates and perhalogenates. An etching solution electrolytic treatment method comprising:
Using an electrolytic processing apparatus having a cathode chamber separated from an etching solution to be processed by a cation exchange membrane made of a perfluorosulfonic acid resin, an etching solution in which the concentration of halogen acid and / or halogen acid salt is increased by use. An anodic electrolytic oxidation process. The method according to claim 1, wherein an etching solution having a total concentration of halogen acid and halogen acid salt of 10 g / L or more is subjected to electrolytic treatment. The method according to claim 1 or 2, wherein an insoluble electrode is used as the anode. The method according to claim 1 for performing electrolysis in the anodic current density 0.1~20A / dm ^2. The method according to any one of claims 1 to 4 anodic electrolytic oxidation treatment under stirring.

Images