JP2011149037A - Method for recycling scrap of copper or copper alloy plated with silver - Google Patents
Method for recycling scrap of copper or copper alloy plated with silver Download PDFInfo
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Abstract
Description
本発明は、全面的或いは部分的に銀めっきが施された銅又は銅合金屑から効率良く銀を剥離し、銀めっきが剥離された銅又は銅合金屑を銅又は銅合金の製造用原料として使用するリサイクル方法に関するものである。 The present invention efficiently peels silver from copper or copper alloy scraps subjected to silver plating entirely or partially, and uses the copper or copper alloy scraps from which silver plating is peeled as a raw material for producing copper or copper alloys. It relates to the recycling method used.
従来、ＩＣやＬＳＩなどの半導体装置、各種電子・電気部品に用いられるリードフレーム、端子、コネクタ等に、銅又は銅合金からなる銅条材の表面にニッケル、錫、銅などのめっき層が形成されためっき付銅条材が広く使用されており、半導体チップ搭載部には部分的に銀めっきが施されることが多い。
この様なめっき付銅条材は打抜き成形にて加工して使用されることが多く、打抜き成形時に発生する多量の油が付着した屑は回収され、表面のめっきを剥離して銅又は銅合金の製造用原料として使用することが資源リサイクルの観点から重要となっている。
特に、銀めっきが施された銅又は銅合金屑からの銀の剥離時にはシアン化合物を使用することが多く、取り扱い面において大きな問題となっている。
特許文献１では、脂肪族有機酸及びその塩の少なくとも一種を含有し、必要に応じて補助成分としてノニオン性界面活性剤を含有する銀の電解剥離剤、該電解剥離剤を含有する水溶液からなる銀の電解剥離液並びに該電解剥離液をｐＨ４〜１４とし、これに剥離対象物を浸漬し、該剥離対象物を陽極として、液温１０〜８０℃、電流密度０．５〜１０Ａ／ｄｍ2の操作範囲で電解することを特徴とするシアン化合物を使用しない銀の電解剥離方法を提供している。
Conventionally, plating layers of nickel, tin, copper, etc. have been formed on the surface of copper strips made of copper or copper alloys on lead frames, terminals, connectors, etc. used in semiconductor devices such as IC and LSI, and various electronic and electrical components. The plated copper strips that have been plated are widely used, and silver plating is often performed partially on the semiconductor chip mounting portion.
Such plated copper strips are often used after being processed by punching, and scraps with a large amount of oil generated during punching are collected, and the plating on the surface is peeled off to form copper or copper alloy. From the viewpoint of resource recycling, it is important to use it as a raw material for manufacturing.
In particular, when peeling silver from copper or copper alloy scraps to which silver plating is applied, a cyanide compound is often used, which is a big problem in handling.
In Patent Document 1, a silver electrolytic stripper containing at least one of an aliphatic organic acid and a salt thereof and, if necessary, a nonionic surfactant as an auxiliary component, and an aqueous solution containing the electrolytic stripper are included. The electrolytic stripping solution of silver and the electrolytic stripping solution are adjusted to pH 4 to 14, the stripping object is immersed in this, the stripping object is used as an anode, the liquid temperature is 10 to 80 ° C., and the current density is 0.5 to 10 A / dm 2. The method of electrolytic stripping of silver without using a cyanide, characterized in that electrolysis is performed in the operating range described above.
この特許文献１に開示の方法では、必要部分の銀めっき部分を痛めることなく、不要部分の薄い銀皮膜を剥離することを目的としており、剥離浴もそれに最適な条件とされており、全面的或いは部分的に厚く銀めっきが施された油の付着した多量の銅又は銅合金屑から完全に銀めっきを剥離し、銀めっきが剥離された銅又は銅合金屑を銅又は銅合金の製造用原料として使用するリサイクル方法には適していない。 In the method disclosed in Patent Document 1, the purpose is to peel a thin silver film of an unnecessary part without damaging a silver plating part of a necessary part, and the peeling bath is also an optimum condition for that purpose. Alternatively, the silver plating is completely peeled off from a large amount of copper or copper alloy scraps on which a part of the thickly silver-plated oil adheres, and the copper or copper alloy scraps from which the silver plating has been peeled off are used for producing copper or copper alloys. It is not suitable for the recycling method used as a raw material.
本発明はこの様な事情に鑑みてなされたものであり、銀めっきが全面的或いは部分的に施された銅又は銅合金屑から安全に効率良く銀を剥離し、銀めっきが剥離された銅又は銅合金屑を銅又は銅合金の製造用原料として使用するリサイクル方法を提供するものである。 The present invention has been made in view of such circumstances, and it is possible to safely and efficiently exfoliate silver from copper or copper alloy scraps which have been subjected to silver plating entirely or partially, and to which silver plating has been exfoliated. Or the recycling method which uses a copper alloy waste as a raw material for manufacture of copper or a copper alloy is provided.
本発明者らは鋭意研究の結果、銀めっき（通常１〜１０μｍ厚）が部分的或いは全面的に施された銅又は銅合金屑からシアン化合物を使用せずに完全に効率良く銀めっきを剥離するには、脂肪族有機酸及びその塩の中から選ばれる少なくとも一種を含有する電解剥離液が入った電解槽中に、表面に銀めっきが施された銅又は銅合金屑を浸漬し、その銅又は銅合金屑に塩化銀標準電極に対して３００〜１１００ｍＶの電位を負荷することが最適であることを見出した。
即ち、電解剥離液中の電流密度の制御ではなく、電解剥離液中の電位を一定に保つことにより、副産物となる銅又は銅合金の電解を最小限とし、目的とする銀めっきを効率よく電解剥離するのである。
更に、表面に銀めっきが施された銅又は銅合金屑に塩化銀標準電極に対して、ポテンシオスタットを使用して、３００〜１１００ｍＶの定電位を負荷することにより、自動運転にて効率的に短時間にて銀めっきを電解剥離することが可能となった。
As a result of diligent research, the present inventors have completely and efficiently stripped silver plating from copper or copper alloy scraps that have been subjected to silver plating (usually 1 to 10 μm thick) without using cyanide. To immerse the copper or copper alloy scrap whose surface is silver-plated in an electrolytic bath containing an electrolytic stripper containing at least one selected from aliphatic organic acids and salts thereof, It has been found that it is optimal to load a copper or copper alloy scrap with a potential of 300 to 1100 mV with respect to a silver chloride standard electrode.
That is, rather than controlling the current density in the electrolytic stripping solution, by keeping the potential in the electrolytic stripping solution constant, electrolysis of the by-product copper or copper alloy is minimized, and the target silver plating is efficiently electrolyzed. It peels off.
Furthermore, it is efficient in automatic operation by loading a constant potential of 300 to 1100 mV using a potentiostat against a silver chloride standard electrode on copper or copper alloy scraps with silver plating on the surface. In addition, the silver plating can be electrolytically removed in a short time.
本発明の銀めっきが施された銅又は銅合金屑のリサイクル方法は、表面に全面的或いは部分的に銀めっきが施された銅又は銅合金屑を、脂肪族有機酸及びその塩の中から選ばれる少なくとも一種を含有する電解剥離液が入った電解槽中に浸漬し、前記銀めっきが施された銅又は銅合金屑に塩化銀標準電極に対して３００〜１１００ｍＶの電位を負荷して銀めっきを電解剥離し、銀めっきが剥離された銅又は銅合金屑を銅又は銅合金屑の製造用原料として使用することを特徴とする。
電位が３００ｍＶ未満では、銅又は銅合金屑の電解がメインで、銀の電解剥離は殆んど起こらず、電位が１１００ｍＶを超えると、銅又は銅合金屑の電解が増加し、銀の電解剥離の妨げとなる。
The recycling method of copper or copper alloy scraps subjected to silver plating according to the present invention is a method of recycling copper or copper alloy scraps whose surfaces are subjected to silver plating entirely or partially from aliphatic organic acids and salts thereof. It is immersed in an electrolytic bath containing an electrolytic stripping solution containing at least one selected, and the silver or copper alloy scrap is loaded with a potential of 300 to 1100 mV with respect to a silver chloride standard electrode, and silver The copper or copper alloy scrap from which the plating is electrolytically peeled and the silver plating is peeled is used as a raw material for producing copper or copper alloy waste.
When the potential is less than 300 mV, the electrolysis of copper or copper alloy scrap is main, and the electrolytic stripping of silver hardly occurs. When the potential exceeds 1100 mV, the electrolysis of copper or copper alloy scrap increases and the electrolytic stripping of silver It becomes an obstacle.
本発明の銀めっきが施された銅又は銅合金屑のリサイクル方法は、前記脂肪族有機酸又はその塩が、酢酸、乳酸、コハク酸、酒石酸、リンゴ酸、クエン酸、グルコン酸及びグリコール酸並びにそれらのアルカリ金属塩の中の少なくとも１種であることを特徴とし、その中でも、酢酸、酒石酸、クエン酸が特に好適である。 In the recycling method of copper or copper alloy scraps subjected to silver plating of the present invention, the aliphatic organic acid or a salt thereof is acetic acid, lactic acid, succinic acid, tartaric acid, malic acid, citric acid, gluconic acid and glycolic acid, and It is characterized by being at least one of those alkali metal salts, among which acetic acid, tartaric acid and citric acid are particularly preferred.
本発明の銀めっきが施された銅又は銅合金屑のリサイクル方法は、ポテンシオスタットを使用して、前記銀めっきが施された銅又は銅合金屑に塩化銀標準電極に対して３００〜１１００ｍＶの電位を負荷するように制御することを特徴とする。
電解剥離液が入った電解槽中の銀めっきが施された銅又は銅合金屑を作用電極とし、電解槽中のカソードを対極とし、その間にポテンシオスタットを接続し、電解槽中に参照電極をセンサーとして設置し、作用電極と参照電極との間の電位差を３００〜１１００ｍＶの定電位に制御することにより、銀めっきが効率良く剥離され、対極上に堆積、或いは、電解槽中に電解される。
この場合、電解剥離液の脂肪族有機酸又はその塩の含有量を１０〜３００ｇ／ｌとし、電解剥離液のｐＨを４〜１４とし、液温を１０〜８０℃にて電解剥離を行うことが好適である。電解剥離液の脂肪族有機酸又はその塩の含有量がその含有量が１０ｇ／ｌ未満では剥離速度が低くて完全に剥離するまでに時間がかかり、一方、３００ｇ／ｌを超えても飽和して効果の増大は期待できず、不経済である。より好ましい含有量としては１００〜２００ｇ／ｌの範囲とされる。電解剥離液のｐＨを４以上とすることにより、素材の銅又は銅合金をエッチングすることなく安定した剥離を得ることができる。このｐＨの調整剤として、必要に応じて、水酸化ナトリウム、水酸化カリウム等のアルカリ金属等を添加してもよい。液温が１０℃未満であると、温度が低過ぎることから、剥離速度が遅くなり、一方、８０℃を超えると、浴が不安定になり易い。
また、本発明のリサイクル方法において、表面に油が付着した銀めっきが施された銅又は銅合金屑を界面活性剤にて表面処理してから電解槽中に浸漬するとよい。界面活性剤にて表面処理することにより、表面に付着している油分が除去され、表面に銀めっきが施された銅又は銅合金屑間の密着力が弱くなり、次の電解剥離での効率を上げることができる。また、油分を剥離液に持ち込まないので、剥離液の劣化を防止することができる。
The method for recycling copper or copper alloy scraps subjected to silver plating according to the present invention uses a potentiostat, and the silver or copper alloy scraps subjected to silver plating are 300 to 1100 mV with respect to a silver chloride standard electrode. It is characterized in that control is performed so as to load the potential.
Copper or copper alloy scraps with silver plating in an electrolytic cell containing an electrolytic stripper are used as a working electrode, a cathode in the electrolytic cell is used as a counter electrode, a potentiostat is connected between them, and a reference electrode is formed in the electrolytic cell. Is installed as a sensor, and the potential difference between the working electrode and the reference electrode is controlled to a constant potential of 300 to 1100 mV, so that the silver plating is efficiently peeled off and deposited on the counter electrode or electrolyzed in the electrolytic cell. The
In this case, the content of the aliphatic organic acid or salt thereof in the electrolytic stripping solution is 10 to 300 g / l, the pH of the electrolytic stripping solution is 4 to 14, and the electrolytic stripping is performed at a liquid temperature of 10 to 80 ° C. Is preferred. When the content of the aliphatic organic acid or salt thereof in the electrolytic stripping solution is less than 10 g / l, the stripping rate is low and it takes time until complete stripping. On the other hand, when the content exceeds 300 g / l, it is saturated. Therefore, an increase in the effect cannot be expected and it is uneconomical. A more preferable content is in the range of 100 to 200 g / l. By setting the pH of the electrolytic stripping solution to 4 or more, stable stripping can be obtained without etching the raw material copper or copper alloy. As the pH adjuster, an alkali metal such as sodium hydroxide or potassium hydroxide may be added as necessary. If the liquid temperature is less than 10 ° C., the temperature is too low, so the peeling rate is slow. On the other hand, if it exceeds 80 ° C., the bath tends to become unstable.
Further, in the recycling method of the present invention, it is preferable to immerse the copper or copper alloy scraps with silver plating with oil attached to the surface after surface treatment with a surfactant and then into the electrolytic bath. By surface treatment with a surfactant, the oil adhering to the surface is removed, the adhesion between the copper or copper alloy scraps with silver plating on the surface becomes weak, and the efficiency in the next electrolytic stripping Can be raised. Moreover, since oil is not brought into the stripping solution, the stripping solution can be prevented from deteriorating.
本発明のリサイクル方法により、全面的或いは部分的に銀めっきが施された銅又は銅合金屑から安全に効率良く短時間にて銀を剥離し、銀めっきが施された銅又は銅合金屑を銅及び銅合金の製造用原料として使用することが可能となる。 By the recycling method of the present invention, the silver or copper alloy scraps that have been subjected to silver plating are peeled off from the copper or copper alloy scraps that have been subjected to silver plating in a safe and efficient manner in a short time. It can be used as a raw material for the production of copper and copper alloys.
以下に、本発明のリサイクル方法の一実施形態を図面に基づいて説明する。
図１は銀めっき剥離装置の全体構成を示しており、この銀めっき剥離装置１は、電解剥離液Ｅを貯留した電解槽２を備えており、この電解槽２内には、リサイクル対象の銅又は銅合金屑Ｃを入れるドラム籠３と、カソード４とが浸漬され、これらドラム籠３とカソード４との間に、ポテンシオスタット５を介して電源（図示略）が接続されている。
Hereinafter, an embodiment of the recycling method of the present invention will be described with reference to the drawings.
FIG. 1 shows the overall configuration of a silver plating stripping apparatus. The silver plating stripping apparatus 1 includes an electrolytic tank 2 in which an electrolytic stripping solution E is stored. The electrolytic tank 2 contains copper to be recycled. Alternatively, a drum cage 3 containing the copper alloy scrap C and the cathode 4 are immersed, and a power source (not shown) is connected between the drum cage 3 and the cathode 4 via a potentiostat 5.
ドラム籠３はＳＵＳ等により形成され、カソード４はＳＵＳ、Ｃｕ等の金属から構成される。このカソード４は、ろ布又はイオン交換膜からなる袋６に覆われている。電解槽２内には、電解剥離液Ｅを攪拌するための攪拌機７が設けられている。また、ポテンシオスタット５はドラム籠３とカソード４に接続され、ポテンシオスタット５からの参照電極８が電位センサーとして電解剥離液Ｅ中に設置されている。参照電極８としては、塩化銀標準電極が用いられる。
なお、電解剥離液Ｅとドラム籠３内の銅及び銅合金屑Ｃとの接触面積を増すため、電解槽２内でドラム籠３を回転させても良い。
また、電解槽２とは別にタンクを設けて、そのタンクと電解槽２との間で電解剥離液Ｅを循環するなどにより、前述の部分的な攪拌を受け持つ攪拌機７とは別に、全体的に攪拌されるようにしてもよい。
The drum cage 3 is made of SUS or the like, and the cathode 4 is made of a metal such as SUS or Cu. The cathode 4 is covered with a bag 6 made of a filter cloth or an ion exchange membrane. A stirrer 7 for stirring the electrolytic stripping solution E is provided in the electrolytic cell 2. The potentiostat 5 is connected to the drum rod 3 and the cathode 4, and the reference electrode 8 from the potentiostat 5 is installed in the electrolytic stripper E as a potential sensor. As the reference electrode 8, a silver chloride standard electrode is used.
In order to increase the contact area between the electrolytic stripping solution E and the copper and copper alloy scrap C in the drum cage 3, the drum cage 3 may be rotated in the electrolytic cell 2.
In addition, by providing a tank separately from the electrolytic cell 2 and circulating the electrolytic stripping solution E between the tank and the electrolytic cell 2, the agitator 7 which is responsible for partial stirring as described above can be used as a whole. You may make it stir.
電解槽２内に貯留される電解剥離液Ｅは、脂肪族有機酸及びその塩の中から選ばれる少なくとも一種を含有してする水溶液であり、具体的には、酢酸、乳酸、コハク酸、酒石酸、リンゴ酸、クエン酸、グルコン酸及びグリコール酸並びにそれらのアルカリ金属塩の中から選択でき、酢酸、酒石酸、クエン酸が特に好適である。電解剥離液Ｅの脂肪族有機酸又はその塩の含有量は１０〜３００ｇ／ｌとし、電解剥離液ＥのｐＨを４〜１４とし、液温を１０〜８０℃にて電解剥離を行うことが好適である。電解剥離液Ｅの脂肪族有機酸又はその塩の含有量が１０ｇ／ｌ未満では剥離速度が低くて完全に剥離するまでに時間がかかり、一方、３００ｇ／ｌを超えても飽和して効果の増大は期待できず、不経済である。より好ましい含有量としては１００〜２００ｇ／ｌの範囲とされる。電解剥離液ＥのｐＨを４以上とすることにより、素材の銅又は銅合金をエッチングすることなく安定した剥離を得ることができる。このｐＨの調整剤として、必要に応じて、水酸化ナトリウム、水酸化カリウム等のアルカリ金属等を添加してもよい。液温が１０℃未満であると、温度が低過ぎることから、剥離速度が遅くなり、一方、８０℃を超えると、浴が不安定になり易い。 The electrolytic stripping solution E stored in the electrolytic cell 2 is an aqueous solution containing at least one selected from an aliphatic organic acid and a salt thereof, specifically, acetic acid, lactic acid, succinic acid, tartaric acid. , Malic acid, citric acid, gluconic acid and glycolic acid and their alkali metal salts, with acetic acid, tartaric acid and citric acid being particularly preferred. The content of the aliphatic organic acid or salt thereof in the electrolytic stripping solution E is 10 to 300 g / l, the pH of the electrolytic stripping solution E is 4 to 14, and the electrolytic stripping is performed at a liquid temperature of 10 to 80 ° C. Is preferred. When the content of the aliphatic organic acid or its salt in the electrolytic stripping solution E is less than 10 g / l, the stripping rate is low and it takes time to completely strip, whereas when it exceeds 300 g / l, it is saturated and effective. It cannot be expected to increase and is uneconomical. A more preferable content is in the range of 100 to 200 g / l. By setting the pH of the electrolytic stripping solution E to 4 or more, stable stripping can be obtained without etching the raw copper or copper alloy. As the pH adjuster, an alkali metal such as sodium hydroxide or potassium hydroxide may be added as necessary. If the liquid temperature is less than 10 ° C., the temperature is too low, so the peeling rate is slow. On the other hand, if it exceeds 80 ° C., the bath tends to become unstable.
次に、このような組成の電解剥離液Ｅを使用して、銅又は銅合金屑Ｃから銀めっきを剥離する方法について説明する。
電解槽２内に、脂肪族有機酸及びその塩の中から選ばれる少なくとも１種の含有量を１０〜３００ｇ／ｌ、ｐＨを４〜１４に調整した電解剥離液Ｅを貯留し、液温を１０〜８０℃とする。攪拌機７を駆動して電解剥離液Ｅを攪拌しておく。
また、リサイクル処理される銅又は銅合金屑Ｃは、そのほとんどがプレス加工による打ち抜き屑であり、加工油が付着しているので、電解剥離液Ｅに浸漬する前に、界面活性剤が添加された水溶液中に浸漬して脱脂処理される。
Next, a method of peeling silver plating from copper or copper alloy scrap C using the electrolytic stripping solution E having such a composition will be described.
In the electrolytic cell 2, the electrolytic stripping solution E in which the content of at least one selected from aliphatic organic acids and salts thereof is adjusted to 10 to 300 g / l and the pH is adjusted to 4 to 14 is stored, and the liquid temperature is set. 10-80 ° C. The agitator 7 is driven to stir the electrolytic stripping solution E.
Also, most of the copper or copper alloy scrap C to be recycled is stamped scraps by press working, and since processing oil is attached, a surfactant is added before dipping in the electrolytic stripping solution E. It is degreased by dipping in an aqueous solution.
そして、脱脂処理された銅又は銅合金屑Ｃをドラム籠３内に収容し、電解槽２内にドラム籠３とカソード４とを浸漬した状態でこれらの間に電源から参照電極８を電位センサーとしてポテンシオスタット５を介して電流を流すことにより、ドラム籠３に接触している銅又は銅合金屑Ｃから銀を溶解して剥離する。
即ち、ドラム籠３内の脱脂処理された銅又は銅合金屑Ｃを作用電極とし、カソード４を対極とし、参照電極８を電位センサーとし、ポテンシオスタット５を使用して、作用電極に塩化銀標準電極に対して３００〜１１００ｍＶの定電位を負荷することにより、副産物となる銅又は銅合金の電解を最小限とし、目的とする銀めっきを短時間にて効率よく対極上に堆積、或いは、電解槽中に電解するのである。
負荷電位が３００ｍＶ未満では、銅又は銅合金屑の電解がメインとなり、銀の電解剥離は殆んど起こらず、電位が１１００ｍＶを超えると、銅又は銅合金屑の電解が増加し、銀の電解剥離の妨げとなる。
The degreased copper or copper alloy scrap C is accommodated in the drum cage 3, and the drum cage 3 and the cathode 4 are immersed in the electrolytic cell 2, and the reference electrode 8 is connected to the potential sensor from the power source between them. As the current flows through the potentiostat 5, the silver or copper alloy scrap C in contact with the drum cage 3 is dissolved and peeled off.
That is, the degreased copper or copper alloy scrap C in the drum basket 3 is used as a working electrode, the cathode 4 is used as a counter electrode, the reference electrode 8 is used as a potential sensor, and a potentiostat 5 is used. By applying a constant potential of 300 to 1100 mV to the standard electrode, electrolysis of copper or copper alloy as a by-product is minimized, and the target silver plating is efficiently deposited on the counter electrode in a short time, or Electrolysis takes place in the electrolytic cell.
When the load potential is less than 300 mV, the electrolysis of copper or copper alloy scrap becomes main, and the electrolytic peeling of silver hardly occurs. When the potential exceeds 1100 mV, the electrolysis of copper or copper alloy scrap increases and the electrolysis of silver This will prevent peeling.
以上のようにして、ドラム籠３を電解剥離液Ｅ内に浸漬してから所定時間後にドラム籠３とカソード４との間のポテンシオスタット５の通電を中止すると、ドラム籠３内の銅又は銅合金屑Ｃの銀めっきは溶解して剥離された状態となる。また、カソード４を覆っている袋６内には、銀粒子が捕集されている。
この銀めっきが剥離された銅又は銅合金屑は、その後、エッチング処理等を経ることなく、銅又は銅合金の溶解鋳造等の原料としてそのまま使用することができる。
また、袋６内に溜まった銀粒子は、銀精錬工場へ送られ、銀精錬の原料として利用される。
As described above, when the energization of the potentiostat 5 between the drum rod 3 and the cathode 4 is stopped after a predetermined time from immersing the drum rod 3 in the electrolytic stripping solution E, the copper in the drum rod 3 or The silver plating of the copper alloy scrap C is dissolved and peeled. Silver particles are collected in the bag 6 covering the cathode 4.
The copper or copper alloy scrap from which the silver plating has been peeled can then be used as it is as a raw material for copper or copper alloy melting and casting without undergoing an etching process or the like.
The silver particles collected in the bag 6 are sent to a silver smelting factory and used as a raw material for silver smelting.
この一連のリサイクル処理において、毒性の強いシアン化合物を使用せずに、全面的或いは部分的な比較的厚肉（１〜１０μｍ）の銀めっきを下地の銅又は銅合金から短時間にて完全に剥離し、その銅又は銅合金と、貴金属である銀とをそれぞれ回収して新たな原料として利用することが可能となる。 In this series of recycling processes, the entire or partial relatively thick (1-10 μm) silver plating can be completely removed from the underlying copper or copper alloy in a short time without using highly toxic cyanide compounds. The copper or copper alloy and the noble metal silver can be recovered and used as new raw materials.
本発明の方法による効果の検証を行った。
図１に示すものと同様の剥離装置１を用い、電解剥離液Ｅとして、酒石酸を１５０ｇ／ｌ、ポリエチレングリコールを１５ｇ／ｌ含有し、ｐＨを８に調整したものを用いた。浴温は５０℃に設定した。銅又は銅合金屑Ｃのサンプルとして５μｍの厚さの銀めっきが両面に施された銅合金屑を用い、これを２ｋｇドラム籠３に入れて、電解剥離液Ｅに浸漬した。
ドラム籠３を電解剥離液Ｅに浸漬させ、参照電極５を電解剥離液Ｅ中に設置し、ポテンシオスタット５にて、参照電極８に対してドラム籠３に７００ｍＶの電位を印加し、ドラム籠３とカソード４の間に通電した。ドラム籠３は、ＳＵＳ製のものを使用し、カソード４にもＳＵＳ電極を用いた。ドラム籠３は電解剥離液Ｅ中にて所定速度で回転させた。ポテンシオスタット５は、北斗電工社製 ＨＺ−５０００ ポテンシオ−ガルバノスタットを使用した。
The effect by the method of the present invention was verified.
A stripping apparatus 1 similar to that shown in FIG. 1 was used, and an electrolytic stripping solution E containing 150 g / l of tartaric acid and 15 g / l of polyethylene glycol and having a pH adjusted to 8 was used. The bath temperature was set to 50 ° C. As a sample of copper or copper alloy scraps C, copper alloy scraps having a silver plating thickness of 5 μm on both sides were used, put in a 2 kg drum cage 3 and immersed in an electrolytic stripping solution E.
The drum rod 3 is immersed in the electrolytic stripping solution E, the reference electrode 5 is placed in the electrolytic stripping solution E, and a potential of 700 mV is applied to the drum rod 3 with respect to the reference electrode 8 by the potentiostat 5. Electricity was supplied between the cage 3 and the cathode 4. The drum cage 3 was made of SUS, and a SUS electrode was also used for the cathode 4. The drum 3 was rotated in the electrolytic stripping solution E at a predetermined speed. As the potentiostat 5, HZ-5000 potentio-galvanostat manufactured by Hokuto Denko Co., Ltd. was used.
ドラム籠３を電解剥離液Ｅ内に浸漬してから１０分後にドラム籠３とカソード４との間のポテンシオスタット５の通電を中止し、サンプルをドラム籠３内より取り出し、ＳＥＭにて銅又は銅合金屑Ｃの表面を観察したところ、銀が完全に剥離されているのを確認した。
また、銀めっきが剥離された銅又は銅合金屑表面をＥＰＭＡにて分析したところ、硫黄（Ｓ）等の残存によるコンタミも無かった。この銀めっきが剥離された銅又は銅合金屑を銅合金製造用原料の一部として溶解鋳造に使用し、熱間圧延後の銅合金板を目視にて調べたところ割れは生じていなかった。
一方、カソード４を囲っている袋５内には、４５ｇの銀が得られ、ＩＰＣで分析したところ、Ｃｕ含有量１００ｐｐｍ以下で、他の金属元素は検出されなかった。
Ten minutes after immersing the drum 3 in the electrolytic stripper E, the energization of the potentiostat 5 between the drum 3 and the cathode 4 is stopped, and the sample is taken out from the drum 3 and copper is removed by SEM. Or when the surface of the copper alloy waste C was observed, it was confirmed that silver was completely peeled off.
Moreover, when the copper or copper alloy scrap surface from which the silver plating was peeled was analyzed by EPMA, there was no contamination due to residual sulfur (S) or the like. The copper or copper alloy scrap from which the silver plating was peeled was used for melting and casting as a part of the raw material for producing the copper alloy, and when the hot-rolled copper alloy sheet was visually examined, no cracks were produced.
On the other hand, 45 g of silver was obtained in the bag 5 surrounding the cathode 4, and when analyzed by IPC, the Cu content was 100 ppm or less, and no other metal elements were detected.
以上のように、本発明の方法によると、銀めっきが施された銅又は銅合金屑から銀めっきを短時間にて効率的に剥離し、剥離後にエッチング処理する必要はなく、銀めっきが剥離された銅又は銅合金屑を溶解鋳造等の原料としてそのままリサイクル可能であることがわかる。また、電解剥離液から銀粒子を効果的に分離採取することができ、有価物としてリサイクル可能であることが確認された。
なお、本発明は上記実施形態に限定されるものではなく、本発明の趣旨を逸脱しない範囲において種々の変更を加えることは可能である。
As described above, according to the method of the present invention, the silver plating is efficiently peeled off from the copper-plated copper or copper alloy scrap in a short time, and it is not necessary to perform an etching process after peeling, and the silver plating is peeled off. It can be seen that the processed copper or copper alloy scrap can be recycled as it is as a raw material for melting and casting. Moreover, it was confirmed that silver particles can be effectively separated and collected from the electrolytic stripping solution and can be recycled as valuable resources.
In addition, this invention is not limited to the said embodiment, A various change is possible in the range which does not deviate from the meaning of this invention.
１ 銀めっき剥離装置
２ 電解槽
３ ドラム籠
４ カソード
５ ポテンシオスタット
６ 袋
７ 攪拌機
８ 参照電極
Ｅ 電解剥離液
Ｃ 銅又は銅合金屑
DESCRIPTION OF SYMBOLS 1 Silver plating peeling apparatus 2 Electrolysis tank 3 Drum tank 4 Cathode 5 Potentiostat 6 Bag 7 Stirrer 8 Reference electrode E Electrolytic peeling liquid C Copper or copper alloy waste
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| JP2010009111A JP2011149037A (en) | 2010-01-19 | 2010-01-19 | Method for recycling scrap of copper or copper alloy plated with silver |
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| JP2010009111A JP2011149037A (en) | 2010-01-19 | 2010-01-19 | Method for recycling scrap of copper or copper alloy plated with silver |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPWO2019073819A1 (en) * | 2017-10-12 | 2020-09-03 | 松田産業株式会社 | How to peel off adhered metal from metal plate |
| JP2021046567A (en) * | 2019-09-17 | 2021-03-25 | アサヒプリテック株式会社 | Electrolytic device, and peeling method |
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| JPWO2019073819A1 (en) * | 2017-10-12 | 2020-09-03 | 松田産業株式会社 | How to peel off adhered metal from metal plate |
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