JPH0781190B2 - Plating liquid regeneration device - Google Patents

Plating liquid regeneration device

Info

Publication number
JPH0781190B2
JPH0781190B2 JP16913586A JP16913586A JPH0781190B2 JP H0781190 B2 JPH0781190 B2 JP H0781190B2 JP 16913586 A JP16913586 A JP 16913586A JP 16913586 A JP16913586 A JP 16913586A JP H0781190 B2 JPH0781190 B2 JP H0781190B2
Authority
JP
Japan
Prior art keywords
plating solution
chamber
cathode
electrode
metal mesh
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
JP16913586A
Other languages
Japanese (ja)
Other versions
JPS6326377A (en
Inventor
英夫 本間
健治 小林
広徳 大田
正勝 岸
高雄 佐藤
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
NEC Corp
Kanto Gakuin School Corp
Original Assignee
NEC Corp
Kanto Gakuin School Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by NEC Corp, Kanto Gakuin School Corp filed Critical NEC Corp
Priority to JP16913586A priority Critical patent/JPH0781190B2/en
Publication of JPS6326377A publication Critical patent/JPS6326377A/en
Publication of JPH0781190B2 publication Critical patent/JPH0781190B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1617—Purification and regeneration of coating baths

Landscapes

  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemically Coating (AREA)

Description

【発明の詳細な説明】 〔産業上の利用分野〕 本発明はめっき液の再生装置に関し、詳しくは化学めっ
き液中の化学めっき反応阻害成分を選択的に除去して、
化学銅めっき液を再生する装置に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial application] The present invention relates to an apparatus for regenerating a plating solution, more specifically, by selectively removing a chemical plating reaction inhibiting component in a chemical plating solution,
The present invention relates to an apparatus for regenerating a chemical copper plating solution.

〔従来の技術〕[Conventional technology]

銅イオン，銅イオンの錯化剤，銅イオンの還元剤,pH調
整剤を主成分として含む化学銅めっき液では、長時間の
使用によって、めっき液中に化学めっき反応を阻害する
成分が蓄積される。すなわち、化学めっき反応によって
消費される銅イオンは、その最適濃度を維持ずるため
に、不足分の銅イオンが補給される。この場合、補給さ
れる銅イオンは、銅化合物の水溶液として補給される。
従って、この補給がくり返されると、銅化合物の銅イオ
ンの対陰イオンがめっき液中に蓄積されることになる。
この銅化合物としては、主として硫酸銅が用いられるの
で、硫酸イオンが蓄積される。銅イオンの還元剤として
は，ホルムアルデヒドが用いられるが、この酸化反応生
成物イオンは、ギ酸イオンでありめっき液の長時間使用
による銅イオンの還元剤（ホルムアルデヒド）の補給に
伴って蓄積される。これらの蓄積イオンは、めっき液の
イオン強度を増大し、２価銅イオンを捕捉するので、め
っき液の安定性を損ない、めっき液を分解し、めっき皮
膜の機械的性質を低下させる。めっき液中のこれらの蓄
積イオンを除去し、めっき液を再生する方法及び装置が
アメリカ合衆国特許第4,289,597号（1981年９月15日）
によって提案されている。すなわち同特許によると１つ
の電解槽を２つの陰イオン交換樹脂膜によってアノード
室，めっき液再生室，及びカソード室の３つの部屋に区
切り、それぞれの部屋には、硫酸水溶液，再生するめっ
き液，水酸化ナトリウム水溶液をそれぞれ入れる。アノ
ード室およびカソード室にそれぞれ電極を浸漬し、この
両電極間に直流電圧を印加するとめっき液再生室のめっ
き液中に蓄積している硫酸イオン，ギ酸イオンは陰イオ
ン交換樹脂膜を通過して、アノード室に移動し、めっき
液中の硫酸イオン，ギ酸イオンの濃度は減少してめっき
液が再生される。なおめっき液中の銅イオンの錯化剤
（例えばエチレンジアミン四酢酸塩）は、銅イオンと陰
イオンの錯イオンを形成して存在するが、硫酸イオン，
ギ酸イオンの分子量より大きいため、陰イオン交換樹脂
膜は通過できず、めっき液中からは、硫酸イオン，ギ酸
イオンを選択的に除去できる。Chemical copper plating solutions containing copper ions, copper ion complexing agents, copper ion reducing agents, and pH adjusters as main components accumulate components that inhibit the chemical plating reaction in the plating solution after long-term use. It That is, the copper ion consumed by the chemical plating reaction is supplemented with a shortage of copper ion in order to maintain its optimum concentration. In this case, the supplied copper ions are supplied as an aqueous solution of the copper compound.
Therefore, if this replenishment is repeated, the counter anion of the copper ion of the copper compound will be accumulated in the plating solution.
Since copper sulfate is mainly used as the copper compound, sulfate ions are accumulated. Formaldehyde is used as a reducing agent for copper ions, and the oxidation reaction product ions are formate ions and are accumulated as the reducing agent (formaldehyde) for copper ions is replenished by long-term use of the plating solution. These accumulated ions increase the ionic strength of the plating solution and trap divalent copper ions, so that the stability of the plating solution is impaired, the plating solution is decomposed, and the mechanical properties of the plating film are deteriorated. A method and apparatus for removing these accumulated ions in the plating solution and regenerating the plating solution is disclosed in US Pat. No. 4,289,597 (September 15, 1981).
Have been proposed by. That is, according to the patent, one electrolytic cell is divided into three chambers of an anode chamber, a plating solution regeneration chamber, and a cathode chamber by two anion exchange resin membranes, and in each chamber, an aqueous sulfuric acid solution, a plating solution to be regenerated, Add each of the aqueous sodium hydroxide solutions. When the electrodes are immersed in the anode chamber and the cathode chamber and a DC voltage is applied between these electrodes, the sulfate ions and formate ions accumulated in the plating solution in the plating solution regeneration chamber pass through the anion exchange resin membrane. , To the anode chamber, the concentration of sulfate ions and formate ions in the plating solution is reduced, and the plating solution is regenerated. The copper ion complexing agent (for example, ethylenediaminetetraacetate) in the plating solution exists in the form of a complex ion of copper ion and anion.
Since it is larger than the molecular weight of formate ion, it cannot pass through the anion exchange resin membrane, and sulfate ion and formate ion can be selectively removed from the plating solution.

〔発明が解決しようとする問題点〕[Problems to be solved by the invention]

しかし、上述の従来技術ではめっき液の再生時に、カソ
ード室とめっき液再生室間に介挿した陰イオン交換樹脂
膜のめっき液の接触面に化学銅めっきが析出されやす
く、めっき液中の硫酸イオン，ギ酸イオンの除去効率が
徐々に減少する欠点があった。However, in the above-described conventional technique, when the plating solution is regenerated, chemical copper plating is likely to be deposited on the contact surface of the plating solution of the anion-exchange resin membrane inserted between the cathode chamber and the plating solution regeneration chamber. There is a drawback that the removal efficiency of ions and formate ions gradually decreases.

本発明の目的はかかる従来技術の欠点を除去しためっき
液再生装置を提供することにある。It is an object of the present invention to provide a plating solution reclaiming device that eliminates the above-mentioned drawbacks of the prior art.

〔問題点を解決するための手段〕[Means for solving problems]

本発明のめっき液再生装置は、槽内を２枚の陰イオン交
換樹脂膜によってアノード室，めっき液再生室，カソー
ド室の３つに仕切られた電解槽とカソード室とめっき液
再生室間の陰イオン交換樹脂膜のめっき液再生室面に金
属メッシュを接触配置し、かつアノード室及びカソード
室にそれぞれ配置されたアノード電極とカソード電極間
に直流電圧を印加する電源と、上記金属メッシュと上記
カソード電極の間に金属メッシュをカソード電極より貴
の電位に保持する直流電源とを備えたことを特徴とし、
さらには、めっき液再生液を一定量自動採取し、めっき
液中の所望のイオン濃度を検出する機構をも備えたこと
をも特徴とする。The plating solution regenerator according to the present invention is provided between an electrolytic cell, a cathode room, and a plating solution regenerator, which are partitioned by an anion exchange resin membrane into two parts, an anode chamber, a plating solution regenerator chamber, and a cathode chamber. A metal mesh is placed in contact with the surface of the plating solution regeneration chamber of the anion exchange resin membrane, and a power source for applying a DC voltage between the anode electrode and the cathode electrode respectively disposed in the anode chamber and the cathode chamber, the metal mesh and the above A DC power supply for holding the metal mesh between the cathode electrodes at a nobler potential than the cathode electrodes,
Furthermore, it is also characterized in that it is equipped with a mechanism for automatically collecting a predetermined amount of the plating solution regenerant and detecting a desired ion concentration in the plating solution.

本発明のめっき液再生装置の電解槽の材質としては、ポ
リプロピレン樹脂、塩化ビニル樹脂等のプラスチックを
用いる。アノード電極としては過酸化鉛電極，白金めっ
きチタン電極等を用いる。カソード電極にはステンレス
電極，白金めっきチタン電極等を用いる。金属メッシュ
の材質として、ステンレス，銅，白金めっきチタンを用
いる。As the material of the electrolytic cell of the plating solution regenerator of the present invention, plastics such as polypropylene resin and vinyl chloride resin are used. A lead peroxide electrode, a platinum-plated titanium electrode, or the like is used as the anode electrode. A stainless steel electrode, a platinum-plated titanium electrode, or the like is used as the cathode electrode. Stainless steel, copper, and platinum-plated titanium are used as the material of the metal mesh.

本発明のめっき液再生装置の電解槽のアノード室の電解
液には10〜50g/L濃度の硫酸水溶液または20〜50g/L濃度
の水酸化ナトリウム水溶液が適当である。またカソード
室の電解液には20〜50g/L濃度の水酸化ナトリウム水溶
液が適当である。アノード電極とカソード電極間には10
〜20Vの直流電圧を印加し、またカソード電極と金属メ
ッシュ間には４〜5Vの直流電圧を印加し、化学銅めっき
液を再生することができる。カソード電極と金属メッシ
ュ間の印加電圧が4Vより低い場合には、めっき液の再生
時にカソード室とめっき液再生室間に配設した陰イオン
交換樹脂膜のめっき液接触面側に化学銅めっきを析出す
ることを防止する効果が減少する。またカソード電極と
金属メッシュ間の印加電圧が5Vを超えると金属メッシュ
（例えばステンレス，銅の場合）の溶解及び酸素が発生
し、めっき液の汚染やアノード電極とカソード電極間の
必要印加電圧の増加をもたらす。また、めっき液再生液
中の所望のイオン濃度を検出する機構としてはイオンク
ロマトグラフィーを使用する。イオンクロマトグラフィ
ーによりめっき液再生液中の所望のイオン、例えば硫酸
イオン，ギ酸イオンの濃度が検出され、これらイオン濃
度が所望の濃度以下になると電解槽のアノード電極とカ
ソード電極間の直流電圧の印加を切り、めっき液の再生
を完了する。An aqueous solution of sulfuric acid having a concentration of 10 to 50 g / L or an aqueous solution of sodium hydroxide having a concentration of 20 to 50 g / L is suitable for the electrolytic solution in the anode chamber of the electrolytic cell of the plating solution regenerating apparatus of the present invention. Further, an aqueous solution of sodium hydroxide having a concentration of 20 to 50 g / L is suitable for the electrolytic solution in the cathode chamber. 10 between the anode and cathode electrodes
A direct current voltage of up to 20 V can be applied, and a direct current voltage of 4 to 5 V can be applied between the cathode electrode and the metal mesh to regenerate the chemical copper plating solution. When the applied voltage between the cathode electrode and the metal mesh is lower than 4 V, chemical copper plating is applied to the plating solution contact surface side of the anion-exchange resin membrane placed between the cathode chamber and the plating solution regeneration chamber when the plating solution is regenerated. The effect of preventing precipitation is reduced. When the applied voltage between the cathode electrode and the metal mesh exceeds 5 V, the metal mesh (for example, stainless steel and copper) is dissolved and oxygen is generated, which contaminates the plating solution and increases the required applied voltage between the anode electrode and the cathode electrode. Bring Ion chromatography is used as a mechanism for detecting a desired ion concentration in the plating solution regenerating solution. Ion chromatography detects the concentration of desired ions, such as sulfate ion and formate ion, in the regenerant of the plating solution. When these ion concentrations fall below the desired concentration, a DC voltage is applied between the anode and cathode electrodes of the electrolytic cell. To complete the regeneration of the plating solution.

〔実施例〕〔Example〕

以下本発明について図面を用いて説明する。 The present invention will be described below with reference to the drawings.

第１図は本発明の第１実施例を示すめっき液再生装置の
回路図付きの断面図である。図中、10はポリプロピレン
等の合成樹脂製の電解槽、電解槽10は陰イオン交換樹脂
膜40a,40bの仕切り配設により、カソード室50,めっき液
再生室60およびアノード室70の３つの小部屋に分割され
る。カソード室50側に配設された陰イオン交換樹脂膜40
aのめっき液の接触面、すなわちめっき液再生室60側の
面には前述のステンレス等の金属メッシュ３が電極とし
て接触配置される。E1は例えばステンレス電極を使用し
たカソード電極１と過酸化鉛電極等のアノード電極２か
らそれぞれ導出されたリード線４により接続された直流
電源、またE2はカソード電極１と金属メッシュ３間をリ
ード線４で接続された直流電源である。FIG. 1 is a sectional view with a circuit diagram of a plating solution regenerator showing a first embodiment of the present invention. In the figure, 10 is an electrolytic cell made of a synthetic resin such as polypropylene, and the electrolytic cell 10 has three small chambers of a cathode chamber 50, a plating solution regenerating chamber 60 and an anode chamber 70 due to the partition arrangement of the anion exchange resin membranes 40a and 40b. Divided into rooms. Anion exchange resin membrane 40 disposed on the cathode chamber 50 side
On the contact surface of the plating solution a, that is, the surface on the side of the plating solution regeneration chamber 60, the metal mesh 3 of stainless steel or the like is arranged as an electrode. E1 is a DC power source connected by a lead wire 4 derived from a cathode electrode 1 using a stainless steel electrode and an anode electrode 2 such as a lead peroxide electrode, and E2 is a lead wire between the cathode electrode 1 and the metal mesh 3. 4 is a DC power source connected.

次に第１図により本発明のめっき液再生装置の使用方法
を説明する。Next, a method of using the plating solution regenerator of the present invention will be described with reference to FIG.

まずカソード室50に40g/L濃度の水酸化ナトリウム水溶
液11を入れ、アノード室70に20g/L濃度の硫酸水溶液12
を入れる。次いでエチレンジアミン四酢酸30g/L,硫酸銅
（CuSO4・5H2O）10g/L,硫酸ナトリウム（Na2SO4）20g/
L,ギ酸ナトリウム（HCOONa）30g/L、ホルムアルデヒド2
g/Lを含むpH＝12の化学銅めっき液13をめっき再生室60
に入れ、直流電源E1によりアノード電極２とカソード電
極１の間に直流電圧17Vを印加する。また直流電源E2に
よりカソード電極１と金属メッシュ３間に金属メッシュ
３側がアノード（貴な電位）になるように直流電圧4.5V
を印加して化学銅めっき液13を10時間再生する。なお陰
イオン交換樹脂膜40a,40bには徳山曹達株式会社製の陰
イオン交換樹脂膜ACLE−5Pを使用し陰イオン交換樹脂膜
の化学銅めっき液13の接地面積は600cm2、陰イオン交換
樹脂膜の電流密度は10mA/cm2、化学銅めっき液13の体積
は6Lとした。化学銅めっき液13を12時間再生後の化学銅
めっき液13中の硫酸イオン（SO4 2-）の濃度減少は10.6g
/L、ギ酸イオン（HCOO-）の濃度減少は6.6g/Lでありほ
ぼ100％の電流効率で化学銅めっき液13中から硫酸イオ
ン及びギ酸イオンを除去することができる。また金属メ
ッシュ３の接触している陰イオン交換樹脂膜40aには化
学銅めっきの析出が起こらず、本発明の実用性が立証さ
れた。First, 40 g / L concentration sodium hydroxide aqueous solution 11 is put in the cathode chamber 50, and 20 g / L concentration sulfuric acid aqueous solution 12 is put in the anode chamber 70.
Put in. Next, ethylenediaminetetraacetic acid 30 g / L, copper sulfate (CuSO 4 .5H 2 O) 10 g / L, sodium sulfate (Na 2 SO 4 ) 20 g / L
L, sodium formate (HCOONa) 30g / L, formaldehyde 2
Plating regenerator 60 with chemical copper plating solution 13 containing g / L at pH = 12
Then, a DC voltage 17V is applied between the anode electrode 2 and the cathode electrode 1 by the DC power supply E1. In addition, a DC voltage of 4.5 V is applied between the cathode electrode 1 and the metal mesh 3 by the DC power supply E2 so that the metal mesh 3 side becomes an anode (noble potential).
Is applied to regenerate the chemical copper plating solution 13 for 10 hours. The anion exchange resin membranes 40a, 40b are made of Tokuyama Soda Co., Ltd. anion exchange resin membrane ACLE-5P, and the chemical copper plating solution 13 of the anion exchange resin membrane has a grounding area of 600 cm 2 , anion exchange resin. The current density of the film was 10 mA / cm 2 , and the volume of the chemical copper plating solution 13 was 6 L. After the chemical copper plating solution 13 was regenerated for 12 hours, the concentration of sulfate ion (SO 4 2- ) in the chemical copper plating solution 13 decreased by 10.6 g.
/ L, formate ions (HCOO -) concentration decreased may remove sulfate ions and formic acid ions in the chemical copper plating solution 13 with nearly 100% current efficiency was 6.6 g / L. Further, the deposition of chemical copper plating did not occur on the anion exchange resin film 40a in contact with the metal mesh 3, demonstrating the practicality of the present invention.

第２図は本発明の第２実施例を示すめっき液再生装置の
回路図付断面図である。図中10はポリプロピレン等の合
成樹脂製の電解槽、20はめっき液槽、30は純水槽であ
る。電解槽10は陰イオン交換樹脂膜40a,40bの仕切り配
設によりカソード室50、めっき液再生室60およびアノー
ド室70の３つの小部屋に分割される。カソード室50側に
配設された陰イオン交換樹脂膜40aのめっき液の接触
面、すなわちめっき液再生室60側の面には前述のステン
レス等の金属メッシュ３が電極として接触配置される。
E1は例えばステンレス電極を使用したカソード電極１と
過酸化鉛電極等のアノード電極２からそれぞれ導出され
たリード線４により接続された直流電源、またE2はカソ
ード電極１と金属メッシュ３間をリード線４で接続され
た直流電源である。電解槽10とめっき液槽20は配管５に
よりポンプP1,P2に連結され、また、Ｂはイオンクロマ
トグラフで純水槽30及びめっき液槽20にそれぞれポンプ
P3,P4を介して配管５に連結される。Ｃは制御装置であ
りイオンクロマトグラフＢ及びポンプP3,P4に接続され
る。FIG. 2 is a sectional view with a circuit diagram of a plating solution regenerator showing a second embodiment of the present invention. In the figure, 10 is an electrolytic cell made of synthetic resin such as polypropylene, 20 is a plating solution tank, and 30 is a pure water tank. The electrolytic cell 10 is divided into three small chambers, a cathode chamber 50, a plating solution regeneration chamber 60 and an anode chamber 70, by partitioning the anion exchange resin membranes 40a and 40b. On the contact surface of the anion exchange resin film 40a arranged on the cathode chamber 50 side with the plating solution, that is, on the surface of the plating solution regeneration chamber 60 side, the metal mesh 3 of stainless steel or the like is arranged as an electrode.
E1 is a DC power source connected by a lead wire 4 derived from a cathode electrode 1 using a stainless steel electrode and an anode electrode 2 such as a lead peroxide electrode, and E2 is a lead wire between the cathode electrode 1 and the metal mesh 3. 4 is a DC power source connected. The electrolysis tank 10 and the plating solution tank 20 are connected to pumps P1 and P2 by a pipe 5, and B is an ion chromatograph for the pure water tank 30 and the plating solution tank 20, respectively.
It is connected to the pipe 5 through P3 and P4. C is a controller, which is connected to the ion chromatograph B and pumps P3 and P4.

次に第２図により本発明のめっき液再生装置の使用方法
を説明する。Next, a method of using the plating solution regenerator of the present invention will be described with reference to FIG.

まずカソード室50に40g/L濃度の水酸化ナトリウム水溶
液11を入れ、アノード室70に20g/L濃度の硫酸水溶液12
を入れる。次いでエチレンジアミン四酢酸30g/L,硫酸銅
（CuSO4・5H2O）10g/L,硫酸ナトリウム（Na2SO4）20g/
L,ギ酸ナトリウム（HCOONa）30g/L、ホルムアルデヒド2
g/Lを含むpH＝12の化学銅めっき液21をめっき液槽20に
入れ、ポンプP2によりめっき液再生室60に送り、直流電
源E1によりアノード電極２とカソード電極１の間に直流
電圧17Vを印加する。また直流電源E2によりカソード電
極１と金属メッシュ３間に金属メッシュ３側がアノード
（貴な電位）になるように直流電圧4.5Vを印加して、化
学銅めっき液13,21を再生しながらポンプP1,P2によりめ
っき液槽20との間を循環させた。化学銅めっき液21は制
御装置ＣによりポンプP4で一定量自動採取されポンプP3
で純水31により500倍に希釈されイオンクロマトグラフ
Ｂに入り硫酸イオン濃度とギ酸イオン濃度が自動測定さ
れる。なお陰イオン交換樹脂膜40a,40bには徳山曹達株
式会社製の陰イオン交換樹脂膜ACLE−5Pを使用し陰イオ
ン交換樹脂膜の電流密度は10mA/cm2、化学銅めっき液1
3,21の体積は6Lとした。イオンクロマトグラフＢでの化
学銅めっき液21中の硫酸イオン及びギ酸イオン濃度の分
析値（めっき液中の濃度換算）がそれぞれ4.85g/L、及
び11.9g/Lになった時点（再生時間12時間）でアノード
電極２とカソード電極１間の直流電圧を切り、化学銅め
っき液13,21の再生を終了した。First, 40 g / L concentration sodium hydroxide aqueous solution 11 is put in the cathode chamber 50, and 20 g / L concentration sulfuric acid aqueous solution 12 is put in the anode chamber 70.
Put in. Next, ethylenediaminetetraacetic acid 30 g / L, copper sulfate (CuSO 4 .5H 2 O) 10 g / L, sodium sulfate (Na 2 SO 4 ) 20 g / L
L, sodium formate (HCOONa) 30g / L, formaldehyde 2
A chemical copper plating solution 21 of pH = 12 containing g / L is placed in the plating solution tank 20 and sent to the plating solution regeneration chamber 60 by the pump P2, and a DC voltage of 17V is applied between the anode electrode 2 and the cathode electrode 1 by the DC power supply E1. Is applied. In addition, a DC voltage of 4.5 V is applied between the cathode electrode 1 and the metal mesh 3 so that the metal mesh 3 side becomes the anode (noble potential) by the DC power source E2, and the pump P1 is regenerated while regenerating the chemical copper plating solutions 13 and 21. , P2 to circulate through the plating solution tank 20. A certain amount of the chemical copper plating solution 21 is automatically sampled by the controller P by the pump P4 and the pump P3.
Then, it is diluted 500 times with pure water 31 and enters the ion chromatograph B, and the sulfate ion concentration and the formate ion concentration are automatically measured. The anion exchange resin membranes 40a, 40b use anion exchange resin membrane ACLE-5P manufactured by Tokuyama Soda Co., Ltd., the current density of the anion exchange resin membrane is 10 mA / cm 2 , chemical copper plating solution 1
The volume of 3,21 was 6L. When the analytical values of sulfate ion and formate ion in the chemical copper plating solution 21 (converted to the concentration in the plating solution) on the ion chromatograph B became 4.85 g / L and 11.9 g / L, respectively (regeneration time 12 The DC voltage between the anode electrode 2 and the cathode electrode 1 was cut off at (time) to complete the regeneration of the chemical copper plating solutions 13 and 21.

化学銅めっき液13,21の再生効率はほぼ100％でありまた
金属メッシュ３の接触している陰イオン交換樹脂膜40a
には化学銅めっきの析出が起こらず、本発明の実用性が
立証された。The regeneration efficiency of the chemical copper plating solutions 13 and 21 is almost 100%, and the anion exchange resin film 40a in contact with the metal mesh 3 is used.
No chemical copper plating was deposited on the steel, demonstrating the practicality of the present invention.

〔発明の効果〕〔The invention's effect〕

以上本発明により、化学銅めっき液中の蓄積イオン（SO
4 2-,HCOO-）が長時間効率良く除去することができる効
果がある。As described above, according to the present invention, accumulated ions (SO
4 2-, HCOO -) is effective which can be prolonged efficiently removed.

【図面の簡単な説明】[Brief description of drawings]

第１図および第２図は、本発明のめっき液再生装置の第
１および第２実施例及びその使用方法を示す断面図であ
る。 １……カソード電極,2……アノード電極， ３……金属メッシュ,4……リード線,5……配管， 10……電解槽,11……水酸化ナトリウム水溶液， 12……硫酸水溶液,13……化学銅めっき液， 20……めっき液槽,21……化学銅めっき液， 30……純水槽,31……純水， 40a,40b……陰イオン交換樹脂膜， 50……カソード室,60……めっき液再生室， 70……アノード室,E1,E2……直流電源， P1,P2,P3,P4……ポンプ， Ｂ……イオンクロマトグラフ,C……制御装置。1 and 2 are cross-sectional views showing first and second embodiments of the plating solution regenerator of the present invention and a method of using the same. 1 …… Cathode electrode, 2 …… Anode electrode, 3 …… Metal mesh, 4 …… Lead wire, 5 …… Piping, 10 …… Electrolyzer, 11 …… Sodium hydroxide aqueous solution, 12 …… Sulfuric acid aqueous solution, 13 …… Chemical copper plating solution, 20 …… Plating solution tank, 21 …… Chemical copper plating solution, 30 …… Pure water tank, 31 …… Pure water, 40a, 40b …… Anion exchange resin membrane, 50 …… Cathode chamber , 60 ... plating solution regeneration room, 70 ... anode room, E1, E2 ... DC power supply, P1, P2, P3, P4 ... pump, B ... ion chromatograph, C ... control device.

───────────────────────────────────────────────────── フロントページの続き (72)発明者 大田 広徳 東京都港区芝５丁目33番１号 日本電気株 式会社内 (72)発明者 岸 正勝 東京都港区芝５丁目33番１号 日本電気株 式会社内 (72)発明者 佐藤 高雄 東京都港区芝５丁目33番１号 日本電気株 式会社内 (56)参考文献 特開 昭62−280373（ＪＰ，Ａ) 特開 昭56−108868（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hironori Ota 5-33-1, Shiba, Minato-ku, Tokyo Inside NEC Corporation (72) Inventor Masakatsu Kishi 5-33-1, Shiba, Minato-ku, Tokyo Japan In-stock company (72) Inventor Takao Sato 5-33-1 Shiba, Minato-ku, Tokyo In-house company (56) Reference JP 62-280373 (JP, A) JP 56- 108868 (JP, A)

Claims (2)

【特許請求の範囲】[Claims] 【請求項１】槽内を陰イオン交換樹脂膜によって仕切ら
れたアノード室，めっき液再生室，カソード室からなる
電解槽と前記カソード室とめっき液再生室間に介挿され
た陰イオン交換樹脂膜のめっき液再生室面側に接触配置
した金属メッシュと前記アノード室及びカソード室にそ
れぞれアノード電極とカソード電極を配置し、かつ前記
両電極間に直流電圧を印加する直流電源と、前記金属メ
ッシュと前記カソード電極の間に金属メッシュをカソー
ド電極より貴の電位に保持する直流電源とを備えたこと
を特徴とするめっき液再生装置。1. An electrolytic cell comprising an anode chamber, a plating solution regeneration chamber, and a cathode chamber whose interior is partitioned by an anion exchange resin membrane, and an anion exchange resin interposed between the cathode chamber and the plating solution regeneration chamber. A metal mesh disposed in contact with the surface of the plating solution regeneration chamber of the film, a DC power source for arranging an anode electrode and a cathode electrode in the anode chamber and the cathode chamber, respectively, and a DC voltage applied between the electrodes, and the metal mesh. And a direct current power source for holding a metal mesh at a nobler potential than the cathode electrode between the cathode electrode and the cathode electrode. 【請求項２】前記めっき液再生装置において、めっき液
再生液を一定自動採取し、めっき液中の所望のイオン濃
度を検出する機構をさらに追加したことを特徴とする特
許請求の範囲第（１）項記載のめっき液再生装置。2. The plating solution reclaiming apparatus further comprising a mechanism for automatically collecting the reclaimed solution of the plating solution at a constant level and detecting a desired ion concentration in the plating solution. ) The plating solution regenerator described in the item.
JP16913586A 1986-07-17 1986-07-17 Plating liquid regeneration device Expired - Lifetime JPH0781190B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP16913586A JPH0781190B2 (en) 1986-07-17 1986-07-17 Plating liquid regeneration device

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP16913586A JPH0781190B2 (en) 1986-07-17 1986-07-17 Plating liquid regeneration device

Publications (2)

Publication Number Publication Date
JPS6326377A JPS6326377A (en) 1988-02-03
JPH0781190B2 true JPH0781190B2 (en) 1995-08-30

Family

ID=15880931

Family Applications (1)

Application Number Title Priority Date Filing Date
JP16913586A Expired - Lifetime JPH0781190B2 (en) 1986-07-17 1986-07-17 Plating liquid regeneration device

Country Status (1)

Country Link
JP (1) JPH0781190B2 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05306471A (en) * 1991-05-17 1993-11-19 Hitachi Kasei Techno Plant Kk Method and device for forming copper electroless plating solution

Also Published As

Publication number Publication date
JPS6326377A (en) 1988-02-03

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