JP2012052205A - Method of removing tin or tin alloy layer on surface of copper or copper alloy material - Google Patents

Method of removing tin or tin alloy layer on surface of copper or copper alloy material Download PDF

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JP2012052205A
JP2012052205A JP2010197281A JP2010197281A JP2012052205A JP 2012052205 A JP2012052205 A JP 2012052205A JP 2010197281 A JP2010197281 A JP 2010197281A JP 2010197281 A JP2010197281 A JP 2010197281A JP 2012052205 A JP2012052205 A JP 2012052205A
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tin
copper
alloy layer
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stripping solution
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Masayuki Iwata
雅之 岩田
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Dowa Metaltech Co Ltd
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PROBLEM TO BE SOLVED: To provide a method of removing tin or a tin alloy layer on a surface of copper or a copper alloy material, wherein the tin or the tin alloy plating layer can be removed easily at low cost from the copper or copper alloy material, on surfaces of which the tin or the tin alloy plating layer is formed, even with small amount of removing liquid.SOLUTION: The tin or the tin alloy layer on the surface of the copper or the copper alloy material is dissolved in the removing liquid by applying a shower of the removing liquid for removing the tin or the tin alloy layer to the copper or the copper alloy material 10 each having the tin or the tin alloy layer on the surface thereof, thereby removing the tin or the tin alloy layer from the surface of the copper or the copper ally material.

Description

本発明は、銅または銅合金材の表面の錫または錫合金層の剥離方法に関し、特に、表面に錫または錫合金めっき層が形成された銅または銅合金材から錫または錫合金めっき層を剥離する方法に関する。   The present invention relates to a method for peeling a tin or tin alloy layer on the surface of a copper or copper alloy material, and in particular, a tin or tin alloy plating layer is peeled from a copper or copper alloy material having a tin or tin alloy plating layer formed on the surface. On how to do.

純銅、黄銅、リン青銅の他、Ｆｅ、Ｎｉ、Ｓｉ、Ｓｎ、Ｐ、Ｍｇ、Ｚｒ、Ｃｒ、Ｔｉ、Ａｌ、Ａｇなどの一種以上の元素を数百質量ｐｐｍ〜３０質量％の範囲で含有するＣｕ系材料（銅または銅合金材）は、インゴットから圧延や焼鈍などの工程を経て、板厚０．１〜４．０ｍｍの条材や線材として仕上られた後、車載用、民生機器用、産業機器用などの端子、バスバー、ばねなどの通電部品の材料として広く使用されている。このような材料として使用される銅または銅合金材の表面には、一般に、通電時の接触信頼性や耐食性を確保するために、比較的安価な錫（Ｓｎ）が０．５〜５．０μｍの厚さでめっきされている。   In addition to pure copper, brass, phosphor bronze, one or more elements such as Fe, Ni, Si, Sn, P, Mg, Zr, Cr, Ti, Al, and Ag are contained in the range of several hundred mass ppm to 30 mass%. Cu-based materials (copper or copper alloy materials) are processed from ingots to rolling and annealing, and finished as strips and wires with a plate thickness of 0.1 to 4.0 mm. It is widely used as a material for current-carrying parts such as terminals for industrial equipment, bus bars and springs. On the surface of copper or copper alloy material used as such a material, in general, relatively inexpensive tin (Sn) is 0.5 to 5.0 μm in order to ensure contact reliability and corrosion resistance during energization. Plated with a thickness of.

Ｓｎめっきが施された銅または銅合金材から通電部品を製造するために、一般に、Ｓｎめっきが施された銅または銅合金材のスリット加工やプレス加工などが行われており、その加工の際にスクラップが発生する。このスクラップを銅または銅合金材の原料として再利用するためにそのまま溶解すると、Ｓｎめっき分だけＳｎ成分が多くなる。そのため、このスクラップを銅または銅合金材の原料として再利用することができるように、Ｓｎめっきを剥離して除去する必要がある。   In order to manufacture a current-carrying part from Sn-plated copper or copper alloy material, generally, slitting or pressing of Sn-plated copper or copper alloy material is performed. Scrap is generated. If this scrap is melted as it is to be reused as a raw material for copper or a copper alloy material, the Sn component increases by the amount of Sn plating. Therefore, it is necessary to peel and remove the Sn plating so that this scrap can be reused as a raw material for copper or a copper alloy material.

従来、Ｓｎめっきが施された銅または銅合金材からＳｎめっきを剥離する方法として、Ｃｕイオンを含有する硫酸または硝酸の水溶液中にＳｎめっきが施された銅または銅合金材を浸漬する方法が提案されている（例えば、特許文献１参照）。また、Ｓｎを溶解する方法として、水酸化アルカリ水溶液中に金属錫または錫合金を投入し、反応促進剤として過酸化水素水を滴下しながら錫酸塩水溶液を得る方法が提案されている（例えば、特許文献２参照）。   Conventionally, as a method of peeling Sn plating from copper or copper alloy material subjected to Sn plating, there is a method of immersing copper or copper alloy material subjected to Sn plating in an aqueous solution of sulfuric acid or nitric acid containing Cu ions. It has been proposed (see, for example, Patent Document 1). Further, as a method for dissolving Sn, there has been proposed a method in which metal tin or a tin alloy is introduced into an alkali hydroxide aqueous solution and a stannate aqueous solution is obtained while dropping hydrogen peroxide as a reaction accelerator (for example, , See Patent Document 2).

また、本出願人により、被めっき物をバレル内のめっき液に浸漬してバレルを回転させながらめっきをする所謂バレルめっき法と同様に、Ｓｎめっきを施した銅または銅合金材をバレル内の薬液に浸漬してバレルを回転させながらＳｎめっきを剥離する方法が提案されている（特願２００９−２８４３０２）。この方法では、プレス加工による油などが付着したリードフレームのプレス屑などのスクラップからＳｎめっきを剥離する場合でも、所謂バレルめっき法において被めっき物同士が接触している表面にめっき液を接触させるように、プレス加工による油などによってスクラップ同士がくっついている表面に薬液を接触されるために、スクラップを入れたバレルを回転させることによってスクラップ同士がくっついていた表面を露出させて、スクラップの表面に薬液を万遍なく接触させるようにしている。   Further, the present applicant, like the so-called barrel plating method in which the object to be plated is immersed in a plating solution in the barrel and plating is performed while rotating the barrel, the Sn-plated copper or copper alloy material is placed in the barrel. A method has been proposed in which Sn plating is peeled off while being immersed in a chemical solution and rotating a barrel (Japanese Patent Application No. 2009-284302). In this method, even when Sn plating is peeled off from scraps such as pressed scraps of lead frames to which oil or the like is adhered by pressing, the plating solution is brought into contact with the surface where the objects to be plated are in contact with each other in the so-called barrel plating method. The surface of the scrap is exposed by rotating the barrel containing the scrap so that the surface of the scrap is stuck by rotating the barrel containing the scrap so that the scrap is stuck to the surface by the press working oil The liquid is in contact with the liquid evenly.

特開昭５８−８７２７５公報（第２頁）JP 58-87275 A (page 2) 特開２０００−２２６２１４号公報（段落番号０００９）JP 2000-226214 A (paragraph number 0009)

しかし、特許文献１の方法では、Ｃｕイオンを含有する硫酸または硝酸の水溶液（剥離液）中にＳｎめっきが施された銅または銅合金材（被処理物）を浸漬するため、被処理物のかさ容積と比べて非常に大きい体積の剥離液が必要になるので、大掛かりな槽が必要になり、コストが高くなる。また、Ｓｎめっきが施された銅または銅合金材からＳｎめっきを剥離する場合に特許文献２の方法を利用しても、過酸化水素水を滴下した水酸化アルカリ水溶液（剥離液）中にＳｎめっきが施された銅または銅合金材（被処理物）を浸漬するため、被処理物のかさ容積と比べて非常に大きい体積の剥離液が必要になるので、大掛かりな槽が必要になり、コストが高くなる。同様に、Ｓｎめっきを施した銅または銅合金材をバレル内の薬液に浸漬してバレルを回転させながらＳｎめっきを剥離する方法でも、被処理物のかさ容積と比べて非常に大きい体積の剥離液が必要になるので、大掛かりな槽が必要になり、コストが高くなる。   However, in the method of Patent Document 1, since the copper or copper alloy material (processed object) subjected to Sn plating is immersed in an aqueous solution (stripping solution) of sulfuric acid or nitric acid containing Cu ions, Since a stripping solution having a very large volume as compared with the bulk volume is required, a large tank is required and the cost is increased. Further, even when the method of Patent Document 2 is used to remove Sn plating from copper or a copper alloy material on which Sn plating has been applied, Sn in an aqueous alkali hydroxide solution (peeling solution) into which hydrogen peroxide solution has been dropped is used. In order to immerse the plated copper or copper alloy material (object to be treated), a very large volume of stripping solution is required compared to the bulk volume of the object to be treated, so a large tank is required. Cost increases. Similarly, even if the Sn plating is peeled off while rotating the barrel by immersing the Sn-plated copper or copper alloy material in the chemical solution in the barrel, the peeling is very large compared to the bulk volume of the workpiece. Since liquid is required, a large tank is required and the cost is increased.

したがって、本発明は、このような従来の問題点に鑑み、剥離液の量が少なくても、表面に錫または錫合金めっき層が形成された銅または銅合金材から錫または錫合金めっき層を簡単且つ安価に剥離することができる、銅または銅合金材の表面の錫または錫合金層の剥離方法を提供することを目的とする。   Therefore, in view of such conventional problems, the present invention provides a tin or tin alloy plating layer from a copper or copper alloy material having a tin or tin alloy plating layer formed on the surface, even if the amount of the stripping solution is small. It is an object of the present invention to provide a method for peeling a tin or tin alloy layer on the surface of a copper or copper alloy material that can be easily and inexpensively peeled off.

本発明者らは、上記課題を解決するために鋭意研究した結果、表面に錫または錫合金層を有する銅または銅合金材に、錫または錫合金層を剥離する剥離液のシャワーをかけることにより、銅または銅合金材の表面の錫または錫合金層を剥離液に溶解させて、銅または銅合金材の表面から錫または錫合金層を剥離すれば、剥離液の量が少なくても、表面に錫または錫合金めっき層が形成された銅または銅合金材から錫または錫合金めっき層を簡単且つ安価に剥離することができることを見出し、本発明を完成するに至った。   As a result of diligent research to solve the above problems, the present inventors have applied a shower of a stripping solution for stripping the tin or tin alloy layer to a copper or copper alloy material having a tin or tin alloy layer on the surface. If the tin or tin alloy layer on the surface of the copper or copper alloy material is dissolved in the stripping solution and the tin or tin alloy layer is stripped from the surface of the copper or copper alloy material, The present inventors have found that a tin or tin alloy plating layer can be easily and inexpensively peeled off from a copper or copper alloy material on which a tin or tin alloy plating layer is formed.

すなわち、本発明による銅または銅合金材の表面の錫または錫合金層の剥離方法は、表面に錫または錫合金層を有する銅または銅合金材に、錫または錫合金層を剥離する剥離液のシャワーをかけることにより、銅または銅合金材の表面の錫または錫合金層を剥離液に溶解させて、銅または銅合金材の表面から錫または錫合金層を剥離することを特徴とする。この銅または銅合金材の表面の錫または錫合金層の剥離方法において、剥離液が過酸化水素水を添加したアルカリ水溶液からなるのが好ましい。   That is, the method for stripping a tin or tin alloy layer on the surface of a copper or copper alloy material according to the present invention comprises a stripping solution for stripping a tin or tin alloy layer on a copper or copper alloy material having a tin or tin alloy layer on the surface. By applying a shower, the tin or tin alloy layer on the surface of the copper or copper alloy material is dissolved in a stripping solution, and the tin or tin alloy layer is stripped from the surface of the copper or copper alloy material. In this method for stripping the tin or tin alloy layer on the surface of copper or copper alloy material, the stripping solution is preferably composed of an alkaline aqueous solution to which hydrogen peroxide water is added.

また、上記の銅または銅合金材の表面の錫または錫合金層の剥離方法において、表面に錫または錫合金層を有する銅または銅合金材に剥離液のシャワーをかけた後に、錫または錫合金層が溶解した剥離液を回収して、銅または銅合金材に回収した剥離液のシャワーを繰り返しかけるのが好ましい。この場合、銅または銅合金材に回収した剥離液のシャワーをかける前に、回収した剥離液に過酸化水素水を添加するのが好ましい。また、表面に錫または錫合金層を有する銅または銅合金材を破砕した状態で容器に入れ、その容器の上方から剥離液のシャワーをかけるとともに、錫または錫合金層が溶解した剥離液を容器の底部から回収するのが好ましい。   Further, in the above method for stripping a tin or tin alloy layer on the surface of copper or copper alloy material, after the copper or copper alloy material having a tin or tin alloy layer on the surface is showered with a stripping solution, tin or tin alloy It is preferable that the stripping solution in which the layer is dissolved is collected, and showering of the stripping solution collected on the copper or copper alloy material is repeated. In this case, it is preferable to add hydrogen peroxide to the recovered stripping solution before showering the recovered stripping solution on the copper or copper alloy material. Also, copper or copper alloy material having a tin or tin alloy layer on the surface is put into a container in a crushed state, and a stripping solution is showered from above the container, and the stripping solution in which the tin or tin alloy layer is dissolved is placed in the container. It is preferable to recover from the bottom.

また、上記の銅または銅合金材の表面の錫または錫合金層の剥離方法において、底面部と上面部を有し且つ底面部付近と上面部付近にそれぞれ投入口および取出口が設けられた略円筒形の容器を傾斜して配置し、表面に錫または錫合金層を有する銅または銅合金材を破砕した状態の被処理物を容器の投入口から投入し、底面部と上面部の略中心を結ぶ中心線のまわりに容器を回転させて、被処理物を容器の内面に沿って上方に移動させる間に、上面部付近から被処理物に剥離液のシャワーをかけた後、被処理物を取出口から取り出してもよい。   Further, in the above-described method for peeling off the tin or tin alloy layer on the surface of copper or copper alloy material, it is substantially the case that has a bottom surface portion and a top surface portion, and that an inlet and an outlet are provided near the bottom surface portion and the top surface portion, respectively. A cylindrical container is placed in an inclined manner, and the object to be processed in which copper or a copper alloy material having a tin or tin alloy layer on the surface is crushed is introduced from the container inlet, and the center of the bottom surface and the top surface is approximately centered. Rotate the container around the center line connecting the two and move the object to be processed upward along the inner surface of the container. You may take out from an outlet.

また、上記の銅または銅合金材の表面の錫または錫合金層の剥離方法において、表面に錫または錫合金層を有する銅または銅合金材にシャワーをかけるために用意する剥離液の体積が、表面に錫または錫合金層を有する銅または銅合金材のかさ体積より小さいのが好ましい。   Further, in the method for peeling off the tin or tin alloy layer on the surface of the copper or copper alloy material, the volume of the peeling solution prepared for showering the copper or copper alloy material having a tin or tin alloy layer on the surface, It is preferably smaller than the bulk volume of a copper or copper alloy material having a tin or tin alloy layer on the surface.

本発明によれば、剥離液の量が少なくても、表面に錫または錫合金めっき層が形成された銅または銅合金材から錫または錫合金めっき層を簡単且つ安価に剥離することができる。   According to the present invention, even if the amount of the stripping solution is small, the tin or tin alloy plating layer can be easily and inexpensively peeled from the copper or copper alloy material having the tin or tin alloy plating layer formed on the surface.

本発明による銅または銅合金材の表面の錫または錫合金層の剥離方法の実施の形態に使用する装置の例を概略的に示す図である。It is a figure which shows roughly the example of the apparatus used for embodiment of the peeling method of the tin or tin alloy layer of the surface of the copper or copper alloy material by this invention. 本発明による銅または銅合金材の表面の錫または錫合金層の剥離方法の実施の形態に使用する装置の他の例を概略的に示す図である。It is a figure which shows schematically the other example of the apparatus used for embodiment of the peeling method of the tin or tin alloy layer of the surface of the copper or copper alloy material by this invention.

本発明による銅または銅合金材の表面の錫または錫合金層の剥離方法の実施の形態では、表面に錫または錫合金層を有する銅または銅合金材（被処理物）に、錫または錫合金層を剥離する剥離液のシャワーをかけることにより、銅または銅合金材の表面の錫または錫合金層を剥離液に溶解させて、銅または銅合金材の表面から錫または錫合金層を剥離する。   In the embodiment of the peeling method of the tin or tin alloy layer on the surface of the copper or copper alloy material according to the present invention, the copper or copper alloy material (object to be treated) having the tin or tin alloy layer on the surface is tin or tin alloy. The tin or tin alloy layer on the surface of the copper or copper alloy material is dissolved in the stripping solution by showering with a stripping solution that peels the layer, and the tin or tin alloy layer is peeled off from the surface of the copper or copper alloy material. .

錫または錫合金層を剥離する剥離液としては、水酸化ナトリウム水溶液や水酸化カリウム水溶液などのアルカリ水溶液に過酸化水素水を添加した剥離液を使用するのが好ましい。表面に錫または錫合金層を有する銅または銅合金材にシャワーをかける際の剥離液の温度は、好ましくは６０〜１０５℃、さらに好ましくは７０〜１００℃である。剥離液の温度が６０℃より低いと錫または錫合金層を剥離する速度が遅く、一方、１０５℃を超えると過酸化水素水の添加時に突沸が起こる可能性があるからであり、安全上１００℃以下にするのが好ましい。   As the stripping solution for stripping the tin or tin alloy layer, it is preferable to use a stripping solution obtained by adding hydrogen peroxide to an aqueous alkali solution such as an aqueous sodium hydroxide solution or an aqueous potassium hydroxide solution. The temperature of the stripping solution when showering copper or a copper alloy material having a tin or tin alloy layer on the surface is preferably 60 to 105 ° C, more preferably 70 to 100 ° C. This is because if the temperature of the stripping solution is lower than 60 ° C., the rate of stripping the tin or tin alloy layer is slow, while if it exceeds 105 ° C., bumping may occur when hydrogen peroxide water is added. It is preferable to set the temperature at or below.

アルカリ水溶液中のアルカリ濃度は、好ましくは５〜２０質量％であり、さらに好ましくは７〜１４質量％である。   The alkali concentration in the aqueous alkali solution is preferably 5 to 20% by mass, more preferably 7 to 14% by mass.

また、アルカリ水溶液に添加する過酸化水素水中のＨ２Ｏ２の濃度は、好ましくは３〜５０質量％、さらに好ましくは３〜３５質量％である。Ｈ２Ｏ２の濃度が３質量％より低いと、必要なモル数のＨ２Ｏ２を満たすための過酸化水素水の量が多くなり、アルカリ水溶液のアルカリ濃度が非常に薄くなってしまう。そのため、錫または錫合金層を連続的に剥離する場合、薄くなった剥離液を抜き取って廃棄し、アルカリを補充する必要があり、コスト的に不利になる。一方、Ｈ２Ｏ２の濃度が５０質量％を超えると、局所的な反応が起こりやすく、Ｈ２Ｏ２を必要以上に消費してしまうため、コスト的に不利になる。 Further, the concentration of the H 2 O 2 hydrogen peroxide water is added to the alkaline aqueous solution is preferably 3 to 50 wt%, more preferably 3 to 35 mass%. If the concentration of H 2 O 2 is lower than 3% by mass, the amount of hydrogen peroxide solution for satisfying the required number of moles of H 2 O 2 increases, and the alkali concentration of the aqueous alkali solution becomes very thin. For this reason, when the tin or tin alloy layer is continuously peeled, it is necessary to extract and discard the thinned stripping solution and replenish the alkali, which is disadvantageous in terms of cost. On the other hand, when the concentration of H 2 O 2 exceeds 50% by mass, a local reaction is likely to occur, and H 2 O 2 is consumed more than necessary, which is disadvantageous in terms of cost.

また、過酸化水素水は、アルカリ水溶液１Ｌに対してＨ２Ｏ２が好ましくは０．０２〜１．０ｇ／分、さらに好ましくは０．０２〜０．５ｇ／分になる添加速度でアルカリ水溶液に連続的に添加する。 Further, the aqueous hydrogen peroxide solution is an alkaline aqueous solution at an addition rate such that H 2 O 2 is preferably 0.02 to 1.0 g / min, more preferably 0.02 to 0.5 g / min with respect to 1 L of the alkaline aqueous solution. Added continuously.

本実施の形態の銅または銅合金材の表面の錫または錫合金層の剥離方法において、表面に錫または錫合金層を有する銅または銅合金材に剥離液のシャワーをかけた後に、錫または錫合金層が溶解した剥離液を回収して、銅または銅合金材に回収した剥離液のシャワーを繰り返しかけるのが好ましい。この場合、銅または銅合金材に回収した剥離液のシャワーをかける前に、回収した剥離液に過酸化水素水を添加するのが好ましい。また、表面に錫または錫合金層を有する銅または銅合金材を破砕した状態で容器に入れ、その容器の上方から剥離液のシャワーをかけるとともに、錫または錫合金層が溶解した剥離液を容器の底部から回収するのが好ましい。   In the peeling method of the tin or tin alloy layer on the surface of the copper or copper alloy material of the present embodiment, after the copper or copper alloy material having the tin or tin alloy layer on the surface is showered with the stripping solution, the tin or tin It is preferable that the stripping solution in which the alloy layer is dissolved is collected and repeated showering of the stripping solution collected on the copper or copper alloy material is repeated. In this case, it is preferable to add hydrogen peroxide to the recovered stripping solution before showering the recovered stripping solution on the copper or copper alloy material. Also, copper or copper alloy material having a tin or tin alloy layer on the surface is put into a container in a crushed state, and a stripping solution is showered from above the container, and the stripping solution in which the tin or tin alloy layer is dissolved is placed in the container. It is preferable to recover from the bottom.

例えば、図１に示すように、表面に錫または錫合金層を有する銅または銅合金材を破砕したスクラップ（被処理物）１０をかご（かご状容器）１２に入れ、このかご１２を容器１４内に設置した後、容器１４の上方に配置されたノズル１６から（過酸化水素水がアルカリ水溶液に添加された）剥離液のシャワーを被処理物１０に連続的にかける。また、かご１２から容器１４の底部に溜まった剥離液（錫または錫合金層が溶解した剥離液）を回収して、ホース１８を介してポンプ２０によりノズル１６に供給して、そのシャワーを被処理物１０に繰り返しかける。また、ホース１８の途中（ポンプ２０とノズル１６の間）に接続された過酸化水素水供給管２２から過酸化水素水を剥離液に添加する。   For example, as shown in FIG. 1, a scrap (processed object) 10 obtained by crushing copper or a copper alloy material having a tin or tin alloy layer on the surface thereof is put in a car (cage-like container) 12, and the car 12 is put in a container 14. After being installed inside, a shower of stripping solution (with hydrogen peroxide added to the alkaline aqueous solution) is continuously applied to the object to be processed 10 from the nozzle 16 disposed above the container 14. Further, the stripping solution (the stripping solution in which the tin or tin alloy layer is dissolved) collected at the bottom of the container 14 is collected from the cage 12 and supplied to the nozzle 16 by the pump 20 through the hose 18 to cover the shower. Repeat the treatment 10. Further, hydrogen peroxide solution is added to the stripping solution from a hydrogen peroxide solution supply pipe 22 connected in the middle of the hose 18 (between the pump 20 and the nozzle 16).

このように、Ｓｎめっきが施された銅または銅合金材のスクラップのような被処理物１０が容器１４内に山積みに収容されていても、被処理物１０を移動させることなく、容器１４の上方に配置されたノズル１６から剥離液のシャワーを被処理物１０に連続的にかけることによって、Ｓｎめっきのような錫または錫合金層を剥離することができる。すなわち、被処理物１０が静止した状態でも、剥離液の浸透力によって錫または錫合金層を剥離することができる。また、被処理物１０の形状、重なり方、量などによって１回のシャワーで全ての錫または錫合金層を剥離することができなくても、剥離液のシャワーを被処理物１０に繰り返しかければ、錫または錫合金層を確実に剥離することができる。また、錫または錫合金層の剥離に要する時間は、被処理物１０を剥離液に浸漬する方法と比べて、同程度または短くなる。さらに、錫または錫合金層を剥離するために被処理物１０を移動させる必要がないので、容器１４を移動させる駆動装置などが必要な方法と比べて、コストの低減や省スペース化が可能になる。   In this way, even if the objects 10 to be processed such as Sn-plated copper or copper alloy scrap are piled up in the container 14, the objects 10 can be moved without moving the objects 10 to be processed. The tin or tin alloy layer such as Sn plating can be peeled off by continuously applying a stripping solution shower from the nozzle 16 disposed above the workpiece 10. That is, even when the workpiece 10 is stationary, the tin or tin alloy layer can be peeled off by the penetration force of the stripping solution. Moreover, even if not all the tin or tin alloy layers can be peeled off by a single shower depending on the shape, overlapping method, amount, etc. of the object to be treated 10, if the stripping liquid shower is repeated on the object to be treated 10. In addition, the tin or tin alloy layer can be reliably peeled off. In addition, the time required for peeling off the tin or tin alloy layer is approximately the same or shorter than the method of immersing the workpiece 10 in the peeling solution. Furthermore, since it is not necessary to move the workpiece 10 in order to peel off the tin or tin alloy layer, it is possible to reduce costs and save space as compared with a method that requires a driving device for moving the container 14 or the like. Become.

また、本実施の形態の銅または銅合金材の表面の錫または錫合金層の剥離方法において、底面部と上面部を有し且つ底面部付近と上面部付近にそれぞれ投入口および取出口が設けられた略円筒形の容器を傾斜して配置し、表面に錫または錫合金層を有する銅または銅合金材を破砕した状態の被処理物を容器の投入口から（連続的または断続的に）投入し、底面部と上面部の略中心を結ぶ中心線のまわりに容器を回転させて、被処理物を容器の内面に沿って上方に移動させる間に、上面部付近から被処理物に剥離液のシャワーをかけた後、被処理物を取出口から（連続的または断続的に）取り出してもよい。   Further, in the peeling method of the tin or tin alloy layer on the surface of the copper or copper alloy material of the present embodiment, it has a bottom surface portion and an upper surface portion, and an inlet and an outlet are provided near the bottom surface portion and the upper surface portion, respectively. An approximately cylindrical container placed in a slant is placed, and the object to be processed in a state in which the copper or copper alloy material having the tin or tin alloy layer on the surface is crushed from the container inlet (continuously or intermittently) While the container is rotated around the center line connecting the approximate center of the bottom surface and the top surface, the object to be processed moves upward along the inner surface of the container. After the liquid shower is applied, the object to be processed may be taken out from the outlet (continuously or intermittently).

例えば、図２に示すように、ロータリーキルンと同様の形状の底面部と上面部を有する略円筒形の中空の容器１００を傾斜して配置し、表面に錫または錫合金層を有する銅または銅合金材を破砕した（図示しない）被処理物を、容器１００の底面部付近に設けられた投入口１０２から投入し、容器１００をその回転軸（底面部と上面部の略中心を結ぶ中心線）のまわりに（図中矢印の方向に）回転させて、被処理物を容器１００の内面に沿って上方に移動させる間に、上面部付近に設けた（図示しない）ノズルから被処理物に剥離液のシャワーをかけた後、容器１００の上面部付近に設けられた取出口１０４から取り出す。   For example, as shown in FIG. 2, copper or a copper alloy having a substantially cylindrical hollow container 100 having a bottom surface and a top surface having the same shape as that of a rotary kiln is inclined and has a tin or tin alloy layer on the surface. An object to be processed (not shown) whose material has been crushed is charged from an inlet 102 provided near the bottom surface of the container 100, and the container 100 is rotated (a center line connecting the approximate center of the bottom surface and the top surface). Is rotated around (in the direction of the arrow in the figure), and the object to be processed is moved upward along the inner surface of the container 100, and the object to be processed is peeled off from a nozzle (not shown) provided near the upper surface. After the liquid is showered, the liquid is taken out from an outlet 104 provided near the upper surface of the container 100.

なお、本実施の形態の銅または銅合金材の表面の錫または錫合金層の剥離方法において、剥離液のシャワーの体積は被処理物のかさ体積より小さくてもよい。   Note that in the peeling method of the tin or tin alloy layer on the surface of the copper or copper alloy material of the present embodiment, the volume of the shower of the peeling solution may be smaller than the bulk volume of the object to be processed.

以下、本発明による銅または銅合金材の表面の錫または錫合金層の剥離方法の実施例について詳細に説明する。   Hereinafter, the Example of the peeling method of the tin or tin alloy layer of the surface of the copper or copper alloy material by this invention is described in detail.

［実施例１］
図１と同様の装置を使用して、１２質量％のＮａＯＨ溶液５００ｍＬに３５質量％の過酸化水素水１２．５ｍＬを３０分間で添加した８０℃の剥離液のシャワー（ＮａＯＨ溶液１Ｌに対するＨ２Ｏ２の添加速度０．２９２ｇ／分）を、厚さ１．２μｍのＳｎめっきが施された銅スクラップ１０００ｇ（かさ容積約１０００ｃｃ、かさ密度約１ｇ／ｃｍ３）に３０分間かけて、銅スクラップからＳｎめっきを剥離したところ、Ｓｎめっきの厚さが０．００〜０．０４μｍになり、少ない剥離液でＳｎめっきを十分に剥離することができることがわかった。 [Example 1]
Using a device similar to FIG. 1, a shower of stripping solution at 80 ° C. in which 12.5 mL of 35% hydrogen peroxide solution was added to 500 mL of 12% NaOH solution over 30 minutes (H 2 with respect to 1 L of NaOH solution) the O addition rate 0.292 g / min of 2), over a period of 30 minutes to a thickness 1.2μm of Sn plating applied copper scrap 1000 g (bulk volume of about 1000 cc, a bulk density of about 1 g / cm 3), copper scrap When the Sn plating was peeled off, the thickness of the Sn plating became 0.00 to 0.04 μm, and it was found that the Sn plating could be sufficiently peeled with a small amount of stripping solution.

［実施例２］
図１と同様の装置を使用して、１０質量％のＮａＯＨ溶液５００ｍＬに３５質量％の過酸化水素水８ｍＬを３０分間で添加した８５℃の剥離液のシャワー（ＮａＯＨ溶液１Ｌに対するＨ２Ｏ２の添加速度０．１８７ｇ／分）を、厚さ１．０μｍのＳｎめっきが施された銅スクラップ１０００ｇ（かさ容積約８００ｃｃ、かさ密度約１．２５ｇ／ｃｍ３）に３０分間かけて、銅スクラップからＳｎめっきを剥離したところ、Ｓｎめっきの厚さが０．００〜０．０４μｍになり、少ない剥離液でＳｎめっきを十分に剥離することができることがわかった。 [Example 2]
Using a device similar to FIG. 1, a 85 ° C. stripper shower (H 2 O 2 with respect to 1 L of NaOH solution) obtained by adding 8 mL of 35% hydrogen peroxide solution to 500 mL of 10% NaOH solution over 30 minutes. Is added to 1000 g of copper scrap with a thickness of 1.0 μm (bulk volume of about 800 cc, bulk density of about 1.25 g / cm 3 ) over 30 minutes. When the Sn plating was peeled off, the thickness of the Sn plating became 0.00 to 0.04 μm, and it was found that the Sn plating could be sufficiently peeled with a small amount of stripping solution.

１０ 被処理物
１２ かご
１４ 容器
１６ ノズル
１８ ホース
２０ ポンプ
２２ 過酸化水素水供給管
１００ 容器
１０２ 投入口
１０４ 取出口
DESCRIPTION OF SYMBOLS 10 To-be-processed object 12 Basket 14 Container 16 Nozzle 18 Hose 20 Pump 22 Hydrogen peroxide water supply pipe 100 Container 102 Input port 104 Outlet

Claims (7)

表面に錫または錫合金層を有する銅または銅合金材に、錫または錫合金層を剥離する剥離液のシャワーをかけることにより、銅または銅合金材の表面の錫または錫合金層を剥離液に溶解させて、銅または銅合金材の表面から錫または錫合金層を剥離することを特徴とする、銅または銅合金材の表面の錫または錫合金層の剥離方法。 A copper or copper alloy material having a tin or tin alloy layer on the surface is showered with a stripping solution for stripping the tin or tin alloy layer, thereby making the tin or tin alloy layer on the surface of the copper or copper alloy material a stripping solution. A method for peeling a tin or tin alloy layer on a surface of a copper or copper alloy material, comprising melting and peeling a tin or tin alloy layer from the surface of a copper or copper alloy material. 前記剥離液が過酸化水素水を添加したアルカリ水溶液からなることを特徴とする、請求項１に記載の銅または銅合金材の表面の錫または錫合金層の剥離方法。 The method for stripping a tin or tin alloy layer on the surface of a copper or copper alloy material according to claim 1, wherein the stripper comprises an alkaline aqueous solution to which hydrogen peroxide is added. 前記表面に錫または錫合金層を有する銅または銅合金材に前記剥離液のシャワーをかけた後に、前記錫または錫合金層が溶解した剥離液を回収して、前記銅または銅合金材に回収した剥離液のシャワーを繰り返しかけることを特徴とする、請求項１または２に記載の銅または銅合金材の表面の錫または錫合金層の剥離方法。 The copper or copper alloy material having a tin or tin alloy layer on the surface is showered with the stripping solution, and then the stripping solution in which the tin or tin alloy layer is dissolved is recovered and recovered into the copper or copper alloy material. 3. The method for peeling a tin or tin alloy layer on a surface of a copper or copper alloy material according to claim 1 or 2, wherein a shower of the peeled liquid is repeatedly applied. 前記銅または銅合金材に前記回収した剥離液のシャワーをかける前に、前記回収した剥離液に過酸化水素水を添加することを特徴とする、請求項３に記載の銅または銅合金材の表面の錫または錫合金層の剥離方法。 The copper or copper alloy material according to claim 3, wherein a hydrogen peroxide solution is added to the recovered stripping solution before the copper or copper alloy material is showered with the recovered stripping solution. A method for peeling a surface tin or tin alloy layer. 前記表面に錫または錫合金層を有する銅または銅合金材を破砕した状態で容器に入れ、その容器の上方から前記剥離液のシャワーをかけるとともに、前記錫または錫合金層が溶解した剥離液を容器の底部から回収することを特徴とする、請求項３または４に記載の銅または銅合金材の表面の錫または錫合金層の剥離方法。 Put copper or copper alloy material having a tin or tin alloy layer on the surface in a crushed state, shower the stripping solution from above the container, and remove the stripping solution in which the tin or tin alloy layer is dissolved. The method for stripping a tin or tin alloy layer on the surface of a copper or copper alloy material according to claim 3 or 4, wherein the method recovers from the bottom of the container. 底面部と上面部を有し且つ底面部付近と上面部付近にそれぞれ投入口および取出口が設けられた略円筒形の容器を傾斜して配置し、前記表面に錫または錫合金層を有する銅または銅合金材を破砕した状態の被処理物を容器の投入口から投入し、底面部と上面部の略中心を結ぶ中心線のまわりに容器を回転させて、被処理物を容器の内面に沿って上方に移動させる間に、上面部付近から被処理物に前記剥離液のシャワーをかけた後、被処理物を取出口から取出すことを特徴とする、請求項１または２に記載の銅または銅合金材の表面の錫または錫合金層の剥離方法。 Copper having a bottom portion and a top portion, and a substantially cylindrical container having an inlet and an outlet provided near the bottom portion and the top portion, respectively, and having a tin or tin alloy layer on the surface Alternatively, the object to be processed in a state in which the copper alloy material is crushed is charged from the container inlet, and the container is rotated around the center line connecting the approximate center of the bottom surface part and the top surface part, and the object to be processed is placed on the inner surface of the container. 3. The copper according to claim 1, wherein the workpiece is taken out from the outlet after the stripper is showered on the workpiece from near the upper surface while being moved upward along the copper plate. Or the peeling method of the tin or tin alloy layer of the surface of a copper alloy material. 前記表面に錫または錫合金層を有する銅または銅合金材にシャワーをかけるために用意する剥離液の体積が、前記表面に錫または錫合金層を有する銅または銅合金材のかさ体積より小さいことを特徴とする、請求項１乃至６のいずれかに記載の銅または銅合金材の表面の錫または錫合金層の剥離方法。 The volume of the stripping solution prepared for showering the copper or copper alloy material having a tin or tin alloy layer on the surface is smaller than the bulk volume of the copper or copper alloy material having a tin or tin alloy layer on the surface. The peeling method of the tin or tin alloy layer of the surface of the copper or copper alloy material in any one of Claim 1 thru | or 6 characterized by these.
JP2010197281A 2010-09-03 2010-09-03 Method of removing tin or tin alloy layer on surface of copper or copper alloy material Pending JP2012052205A (en)

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KR102618832B1 (en) 2022-11-25 2023-12-29 주식회사 호진플라텍 Copper-tin alloy layer forming method

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