JP6748310B2 - Method of peeling adhered metal from metal plate - Google Patents
Method of peeling adhered metal from metal plate Download PDFInfo
- Publication number
- JP6748310B2 JP6748310B2 JP2019548121A JP2019548121A JP6748310B2 JP 6748310 B2 JP6748310 B2 JP 6748310B2 JP 2019548121 A JP2019548121 A JP 2019548121A JP 2019548121 A JP2019548121 A JP 2019548121A JP 6748310 B2 JP6748310 B2 JP 6748310B2
- Authority
- JP
- Japan
- Prior art keywords
- metal
- metal plate
- adhered
- peeling
- plate
- 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.)
- Active
Links
- 229910052751 metal Inorganic materials 0.000 title claims description 131
- 239000002184 metal Substances 0.000 title claims description 131
- 238000000034 method Methods 0.000 title claims description 24
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 30
- 238000005868 electrolysis reaction Methods 0.000 claims description 20
- 239000008151 electrolyte solution Substances 0.000 claims description 19
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 18
- 229910052737 gold Inorganic materials 0.000 claims description 18
- 239000010931 gold Substances 0.000 claims description 18
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 15
- 229910052759 nickel Inorganic materials 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 13
- 229910052804 chromium Inorganic materials 0.000 claims description 13
- 239000011651 chromium Substances 0.000 claims description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 12
- 229910017052 cobalt Inorganic materials 0.000 claims description 12
- 239000010941 cobalt Substances 0.000 claims description 12
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 12
- 229910052802 copper Inorganic materials 0.000 claims description 12
- 239000010949 copper Substances 0.000 claims description 12
- 229910052709 silver Inorganic materials 0.000 claims description 9
- 239000004332 silver Substances 0.000 claims description 9
- 229910001220 stainless steel Inorganic materials 0.000 claims description 9
- 239000010935 stainless steel Substances 0.000 claims description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 8
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 5
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 description 10
- 238000000151 deposition Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000003449 preventive effect Effects 0.000 description 4
- 239000000758 substrate Substances 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005363 electrowinning Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F5/00—Electrolytic stripping of metallic layers or coatings
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Electrolytic Production Of Metals (AREA)
- Physical Vapour Deposition (AREA)
- Chemical Vapour Deposition (AREA)
- Electroplating Methods And Accessories (AREA)
Description
本発明は、例えば、成膜装置で用いられる防着板のような金属板に、付着した金属を効率的に剥離する方法に関する。 TECHNICAL FIELD The present invention relates to a method for efficiently peeling a metal attached to a metal plate such as an adhesion-preventing plate used in a film forming apparatus.
ＰＶＤやＣＶＤの成膜装置では、成膜用基板以外にも、膜を構成する金属が付着することから、チャンバー内に防着板を設け、チャンバー内壁等に被膜が形成するのを防止している。しかし、防着板も使用し続けると、次第に付着した金属層の厚みが厚くなって、脱落するおそれがあることから、適当な時期に成膜装置から取り外して、付着した金属を剥離、洗浄した後、再利用することが行われている。 In a PVD or CVD film forming apparatus, since the metal forming the film adheres in addition to the film forming substrate, a deposition preventive plate is provided in the chamber to prevent the film from forming on the inner wall of the chamber. There is. However, if the deposition-prevention plate is also used continuously, the thickness of the adhered metal layer gradually becomes thicker and may fall off.Therefore, the adhered metal was removed from the film forming apparatus at an appropriate time, and the adhered metal was washed. After that, it is reused.
また、成膜用基板の上方に、金属板のマスクを配置して、必要な部分のみに金属膜を成膜して、電極パターンなどを形成することが行われている。このとき、マスク用金属板には膜と同一成分の金属が付着することから、その付着した金属の脱落による汚染を防止したり、マスキングとしての性能を維持するために、防着板と同様、適当な時期に成膜装置から取り外して、付着した金属を剥離等することが行われている。 Further, a mask of a metal plate is arranged above the film formation substrate, and a metal film is formed only on a necessary portion to form an electrode pattern or the like. At this time, since the metal having the same component as the film adheres to the mask metal plate, in order to prevent contamination due to the adhered metal falling off or to maintain the performance as masking, like the deposition-prevention plate, It is performed to remove the adhered metal from the film forming apparatus at an appropriate time.
上記成膜装置内の金属板としては通常、耐食性が高いステンレスが用いられている。また、付着する金属としては、膜の用途に応じて、その種類は決定されるが、主として銅、アルミニウム、金、銀、ニッケル、クロム、コバルトが用いられている。例えば、金電極を形成する場合、密着性向上のためにニッケルやクロムの下地膜を成膜した後、金を成膜することが行われている。 As the metal plate in the film forming apparatus, stainless steel having high corrosion resistance is usually used. Further, as the metal to be attached, the type thereof is determined depending on the use of the film, but copper, aluminum, gold, silver, nickel, chromium, cobalt are mainly used. For example, when forming a gold electrode, a gold or gold film is formed after forming a nickel or chromium base film to improve adhesion.
上記のような成膜工程を繰り返し行うと、金属板の上には、次第に金とニッケル又はクロムが交互に積層されることになる。通常、このような金属板から付着金属を剥離する場合、金属板を溶液に浸漬して、付着金属を溶解することが行われる。例えば、金とニッケルの溶解はシアン化アルカリ溶液で行い、一方、クロムの溶解はセリウム化酸性溶液で行い、これら二つの溶解操作を交互に繰り返す処理が行われる。 When the film forming process as described above is repeated, gold and nickel or chromium are gradually stacked alternately on the metal plate. Usually, when peeling the adhered metal from such a metal plate, the metal plate is immersed in a solution to dissolve the adhered metal. For example, the dissolution of gold and nickel is performed with an alkali cyanide solution, while the dissolution of chromium is performed with a cerium acid solution, and a process of alternately repeating these two dissolution operations is performed.
しかし、この方法は、二種類の溶液に交互に浸漬させる作業が必要であり、入れ替え作業に時間が掛かるという問題があった。特に、マスクの場合は、金属層の数が多く、交互浸漬によって溶解処理していくと、全ての金属層を剥離するために多くの処理日数を要していた。さらに、防着板の場合は、膜厚が厚いことから、浸漬処理で完全に溶解しないことがあり、物理的に手作業で剥離するという作業が必要であった。 However, this method has a problem that it requires a work of alternately immersing it in two kinds of solutions, and the replacement work takes time. In particular, in the case of a mask, the number of metal layers was large, and when the dissolution treatment was performed by alternate dipping, many treatment days were required to peel off all the metal layers. Further, in the case of the adhesion-preventing plate, since the film thickness is large, it may not be completely dissolved by the dipping treatment, and a work of physically peeling it is necessary.
これに対し、複数の金属層が積層した金属板から該金属層を剥離する他の方法として、シアン化系アルカリ溶液内において、金属板を陽極として、通電と無通電を交互に繰り返すパルス電解を行うことで、積層された金属層を順次剥離する方法が提案されている（特許文献１）。しかし、このようなパルス通電を行う場合、対象金属層により適切な通電／無通電時間を設定する必要があり、条件設定が複雑であるという問題があった。 On the other hand, as another method of peeling the metal layer from a metal plate having a plurality of metal layers laminated, pulse electrolysis in which an electric current and a non-electric current are alternately repeated in a cyanide-based alkaline solution using the metal plate as an anode. A method of sequentially peeling the stacked metal layers by performing the method has been proposed (Patent Document 1). However, when such pulse energization is performed, it is necessary to set an appropriate energization/non-energization time depending on the target metal layer, and there is a problem that the condition setting is complicated.
本発明は、上記従来技術の問題点に鑑みてなされたものであって、平坦な直流電圧を用いた電解装置において、金属板に付着した一種以上の金属を同時期に溶解することができ、付着金属の剥離時間を短縮することを目的とする。 The present invention has been made in view of the above problems of the prior art, in the electrolysis device using a flat DC voltage, it is possible to dissolve one or more metals attached to the metal plate at the same time, The purpose is to shorten the peeling time of the adhered metal.
本発明者は、上記課題を解決するために鋭意研究を行った結果、平坦な直流電圧を用いた電解装置においても、陽極電位を適切に調整することにより、付着金属を効率よく剥離することができるという知見を見出した。
この知見に基づき、以下の発明を提供する。The present inventor, as a result of earnest research to solve the above problems, even in an electrolysis device using a flat DC voltage, by appropriately adjusting the anode potential, it is possible to efficiently peel off the adhered metal. I found that I can do it.
Based on this finding, the following inventions are provided.
１）平坦な直流電圧を用いた電解装置によって金属板に付着した金属を剥離する方法であって、金属が付着した金属板を電解液に浸漬した後、該金属板を陽極として、陽極電位を０．１〜３．０Ｖ（Ａｇ／ＡｇＣｌ参照電極）の条件で電解することにより、該付着金属を金属板から剥離することを特徴とする金属板から付着金属を剥離する方法。
２）付着金属が、銅、アルミニウム、金、銀、ニッケル、クロム、コバルトの中から選択されるいずれか一種以上の金属であることを特徴とする上記１）記載の金属板から付着金属を剥離する方法。
３）付着金属が、銅、アルミニウム、金、銀、ニッケル、クロム、コバルトの場合、電解液としてシアン化アルカリ溶液を用い、付着金属が、銅、ニッケル、コバルトの場合、電解液として硫酸塩溶液を用いる、ことを特徴とする上記１）又は２）記載の金属板から付着金属を剥離する方法。
４）電圧値を０．５Ｖ〜３０Ｖ、電流値を０．０５Ａ／ｄｍ２〜１Ａ／ｄｍ２とすることを特徴とする上記１）〜３）のいずれか一に記載の金属板から付着金属を剥離する方法。
５）電解液温度を２０℃〜６０℃とすることを特徴とする上記１）〜４）のいずれか一に記載の金属板から付着金属を剥離する方法。1) A method of peeling a metal adhered to a metal plate by an electrolysis apparatus using a flat DC voltage, wherein the metal plate adhered to the metal is immersed in an electrolytic solution, and then the metal plate is used as an anode to adjust an anode potential. A method for peeling a deposited metal from a metal plate, characterized by peeling the deposited metal from the metal plate by electrolyzing under a condition of 0.1 to 3.0 V (Ag/AgCl reference electrode).
2) The adhered metal is any one or more kinds of metals selected from copper, aluminum, gold, silver, nickel, chromium, and cobalt, and the adhered metal is peeled off from the metal plate described in 1) above. how to.
3) When the adhered metal is copper, aluminum, gold, silver, nickel, chromium, or cobalt, an alkali cyanide solution is used as the electrolytic solution, and when the adhered metal is copper, nickel, or cobalt, a sulfate solution is used as the electrolytic solution. The method of peeling the adhered metal from the metal plate according to the above 1) or 2), characterized by using.
4) A metal attached from the metal plate described in any one of 1) to 3) above, which has a voltage value of 0.5 V to 30 V and a current value of 0.05 A/dm 2 to 1 A/dm 2. How to peel off.
5) The method for peeling the adhered metal from the metal plate according to any one of 1) to 4) above, wherein the temperature of the electrolytic solution is set to 20°C to 60°C.
本発明は、平坦な直流電流を用いた電解装置においても、その陽極電圧を適切に調整することによって、一種以上の付着金属を、同時期に溶解することができるので、付着する金属の種類に応じて、溶液の種類や、電解条件（通電／無通電）を変更する必要がなく、付着金属の剥離に伴う時間を短縮することができるという優れた効果を有する。本方法は、付着金属が均一に付着（積層）していない場合においても、有効である。 The present invention, even in an electrolysis device using a flat DC current, by appropriately adjusting the anode voltage, it is possible to dissolve one or more kinds of adhered metal at the same time. Accordingly, there is no need to change the type of solution or the electrolysis conditions (energization/non-energization), and the excellent effect of being able to shorten the time associated with peeling of the adhered metal can be obtained. This method is effective even when the adhered metal is not uniformly adhered (laminated).
本発明は、平坦な直流電圧を用いた電解法によって、金属板から付着金属を剥離する方法である。ここで平坦な直流電圧とは、電圧波形がパルス波形ではなく、平坦な波形であることを意味する。本発明は、平坦な直流電圧を用いた電解装置においても、陽極電位を適切に調整することにより、金属板から一種以上の付着金属を同時期に剥離することを可能とすることができ、ひいては、剥離の処理時間と処理工程を短縮することができるというものである。 The present invention is a method of peeling adhered metal from a metal plate by an electrolysis method using a flat DC voltage. Here, the flat DC voltage means that the voltage waveform is not a pulse waveform but a flat waveform. The present invention, even in an electrolysis apparatus using a flat DC voltage, by appropriately adjusting the anode potential, it is possible to peel one or more kinds of adhered metal from the metal plate at the same time. It is possible to shorten the peeling processing time and the processing steps.
金属板は、防着板やマスク等に使用されるものであって、通常、ステンレスのような表面が酸化膜に覆われている材料が用いられる。ステンレス以外にも、表面に酸化膜が形成されたアルミニウム板などが用いられる場合がある。このような金属板は、防着材やマスク等として一定期間使用し続けると、その表面には成膜に伴う金属が付着、積層する。そして、金属の付着量が多くなると、次第に付着した金属が脱落して、基板を汚染等することになる。したがって、金属板は、定期的に付着した金属を剥離、洗浄する必要がある。 The metal plate is used for a deposition preventive plate, a mask or the like, and a material such as stainless steel whose surface is covered with an oxide film is usually used. In addition to stainless steel, an aluminum plate having an oxide film formed on its surface may be used. When such a metal plate is continuously used as a deposition preventive material, a mask, or the like for a certain period of time, the metal accompanying the film formation adheres to the surface and is laminated. Then, when the amount of adhered metal increases, the adhered metal gradually falls off, and the substrate is contaminated. Therefore, it is necessary for the metal plate to regularly remove and wash the adhered metal.
付着する金属の種類は、成膜する膜の種類（用途）によって異なる。例えば、半導体配線用膜を成膜する場合には、配線材としての銅やアルミニウム、コバルトなどが付着することになる。また、水晶振動子等における電極用膜を成膜する場合には、電極としての金や銀と、下地層としてのニッケルやクロムとが、交互に積層されることになる。なお、本発明は、金属板に銅、アルミニウム、金、銀、ニッケル、クロム、コバルトのいずれいか一種以上の金属が付着している場合に対して、有効であり、どのような用途（過程）で付着された金属であるかについては、特に問わない。 The type of metal that adheres depends on the type (use) of the film to be formed. For example, when a film for semiconductor wiring is formed, copper, aluminum, cobalt, or the like as a wiring material is attached. Further, when forming an electrode film for a crystal oscillator or the like, gold or silver as an electrode and nickel or chromium as a base layer are alternately laminated. The present invention is effective for the case where any one or more metals such as copper, aluminum, gold, silver, nickel, chromium, and cobalt are attached to the metal plate, and what use (process) It does not matter whether or not the metal is adhered by the method.
本発明の剥離方法について具体的に説明する。
まず、図１に示すように、金属が付着する金属板を、電解槽の電解液中に浸漬する。電解液には、付着金属と安定な溶存形態を形成する成分を含み、且つ、金属板の金属酸化膜が不溶性である液種を選択する。例えば、付着金属が銅、アルミニウム、金、銀、ニッケル、クロム、コバルトであり、金属板がステンレスの場合には、電解液として、シアン化ナトリウム溶液を使用することができる。また、付着金属が銅、ニッケル、コバルトであり、金属板がアルミニウム（表面には酸化膜が形成されている）の場合には硫酸アンモニウム溶液を用いることができる。The peeling method of the present invention will be specifically described.
First, as shown in FIG. 1, a metal plate to which a metal is attached is immersed in an electrolytic solution in an electrolytic cell. For the electrolytic solution, a liquid type containing a component that forms a stable dissolved form with the adhered metal and in which the metal oxide film of the metal plate is insoluble is selected. For example, when the adhered metal is copper, aluminum, gold, silver, nickel, chromium, cobalt and the metal plate is stainless steel, a sodium cyanide solution can be used as the electrolytic solution. Further, when the adhered metals are copper, nickel and cobalt and the metal plate is aluminum (an oxide film is formed on the surface), an ammonium sulfate solution can be used.
図１では、金属板を金属製（例えば、ステンレス）カゴに設置して、そのカゴ本体を電解液に浸漬させている。このようにすることで、陽極とした金属板の陽極電位を厳密に調整することができると共に、複数の金属板を同時に処理することができるので作業効率が高めることができる。このように、陽極として金属板の場合だけでなく、金属製のカゴを用いることも有効である。また、陰極には、ステンレスなど、本発明の電解条件において不溶性である材質のものを使用する。 In FIG. 1, the metal plate is placed in a metal (for example, stainless steel) basket, and the basket body is immersed in the electrolytic solution. By doing so, the anode potential of the metal plate used as the anode can be strictly adjusted, and a plurality of metal plates can be processed at the same time, so that work efficiency can be improved. Thus, it is effective not only to use a metal plate as the anode, but also to use a metal basket. The cathode is made of a material that is insoluble under the electrolytic conditions of the present invention, such as stainless steel.
次に、整流器を用いて電解を行う。電解中は、陽極電位が０．１Ｖ〜３．０Ｖ（参照電極：Ａｇ／ＡｇＣｌ）となるように調整することが、重要である。上記の電位範囲においては、付着金属（銅、アルミニウム、金、銀、ニッケル、クロム、コバルト）が、電極反応により効率的に酸化されて、剥離することが可能となる。一方、０．１Ｖ未満であると、電流値が小さいために剥離速度が遅く、３．０Ｖ超であると、水の電気分解が優勢となり、付着金属の剥離が進まない。したがって、陽極電位はこの範囲とする。 Next, electrolysis is performed using a rectifier. During electrolysis, it is important to adjust the anode potential to be 0.1 V to 3.0 V (reference electrode: Ag/AgCl). In the above potential range, the adhered metal (copper, aluminum, gold, silver, nickel, chromium, cobalt) is efficiently oxidized by the electrode reaction and can be peeled off. On the other hand, when it is less than 0.1 V, the peeling speed is slow because the current value is small, and when it is more than 3.0 V, electrolysis of water becomes dominant and the peeling of the adhered metal does not proceed. Therefore, the anode potential is within this range.
本発明において電解条件は、電圧値を０．５Ｖ〜３０Ｖとし、電流値を０．０５Ａ／ｄｍ２〜１Ａ／ｄｍ２とすることが好ましい。また、電解液の温度は２０℃〜６０℃とすることが好ましい。電解液の温度が２０℃未満であると、電力消費量が増加し、一方、６０℃を超えると、電解液が揮発することがあるためである。
そして、電流値が１ｍＡ／ｄｍ２未満となった時点で、付着金属がほぼ無くなったと判断して、電解を停止する。In the present invention, the electrolysis conditions are preferably a voltage value of 0.5 V to 30 V and a current value of 0.05 A/dm 2 to 1 A/dm 2 . The temperature of the electrolytic solution is preferably 20°C to 60°C. This is because if the temperature of the electrolytic solution is lower than 20°C, the power consumption increases, while if it exceeds 60°C, the electrolytic solution may volatilize.
Then, when the current value becomes less than 1 mA/dm 2 , it is determined that the adhered metal has almost disappeared, and the electrolysis is stopped.
電解終了後は、電解槽から金属板あるいは金属板が設置された金属製かごを取り出し、金属板を洗浄する。洗浄には、純水を用いることができるが特に制限はない。洗浄後、金属板は、再度、防着板あるいはマスク等として、再利用することができる。一方、電解液中に溶解した各種金属は電解採取することによって、有価金属として、分離、回収することができる。なお、金については、電解中に陰極に電着するので、電着金属として、回収することができる。 After the electrolysis is completed, the metal plate or the metal cage in which the metal plate is installed is taken out from the electrolytic cell and the metal plate is washed. Pure water can be used for cleaning, but there is no particular limitation. After washing, the metal plate can be reused again as an adhesion-preventing plate or a mask. On the other hand, various metals dissolved in the electrolytic solution can be separated and recovered as valuable metals by electrowinning. Since gold is electrodeposited on the cathode during electrolysis, it can be recovered as an electrodeposited metal.
以上より、複雑な電解工程を行うことなく、一般的な電解装置を用いて、金属板から付着金属を剥離することができるので、処理時間及び処理工程を大幅に短縮することができる。また、本発明の方法は、付着金属が交互に積層された場合だけでなく、同一面内に複数の付着金属が存在するような場合であっても、同時期に付着金属を剥離することができる。 As described above, the adhering metal can be peeled off from the metal plate by using a general electrolysis apparatus without performing a complicated electrolyzing process, so that the processing time and the processing step can be significantly shortened. Further, the method of the present invention is not limited to the case where the adhered metals are alternately laminated, but the adhered metals can be peeled off at the same time even when there are a plurality of adhered metals in the same plane. it can.
ステンレス（ＳＵＳ３０４）製の金属板に、金層とクロム層とを積層させて、金属が付着した金属板のサンプルを作製した。金層の膜厚は０．１μｍとし、クロム層の膜厚は０．０１μｍ、全体の膜厚は５μｍとした。次に、このサンプルをシアン化ナトリウム溶液の電解液に浸漬して、各サンプルに対して、それぞれの陽極電位を０．０５Ｖ〜５．０Ｖ（参照電極：Ａｇ／ＡｇＣｌ）に設定して、電解処理を行った。そして、電流値が１ｍＡ／ｄｍ２未満になった時点で、付着金属が剥離したものとして、その剥離に要した時間を計測した。なお、電解液温度を２０℃に設定した。A gold layer and a chrome layer were laminated on a metal plate made of stainless steel (SUS304) to prepare a sample of the metal plate to which the metal was attached. The thickness of the gold layer was 0.1 μm, the thickness of the chromium layer was 0.01 μm, and the total thickness was 5 μm. Next, this sample was immersed in an electrolytic solution of a sodium cyanide solution, and the anode potential of each sample was set to 0.05 V to 5.0 V (reference electrode: Ag/AgCl) to perform electrolysis. Processed. Then, when the current value became less than 1 mA/dm 2 , it was determined that the adhered metal had peeled off, and the time required for the peeling was measured. The electrolyte temperature was set to 20°C.
下記の表１に示される通り、陽極電位を０．１Ｖ〜３．０Ｖの範囲では、剥離時間がいずれも１００分以内と剥離時間の短縮が確認された。一方、陽極電位が０．０５Ｖ、あるいは、３．５Ｖ以上の場合には、剥離時間が２００分超と長くなっていた。なお、従来技術に基づき、シアン化アルカリ溶液とセリウム化酸性溶液に交互に浸漬し、それぞれ金層とクロム層を交互に溶かした場合の剥離時間は１３０分であり、この従来技術の方法と比べて、剥離時間の大幅な短縮が確認できる。 As shown in Table 1 below, when the anode potential was in the range of 0.1 V to 3.0 V, it was confirmed that the peeling time was within 100 minutes and the peeling time was shortened. On the other hand, when the anode potential was 0.05 V or 3.5 V or higher, the peeling time was longer than 200 minutes. It should be noted that, based on the conventional technique, the peeling time was 130 minutes when the gold layer and the chrome layer were alternately immersed in an alkaline cyanide solution and a cerium acid solution, respectively, and compared with this conventional method. Therefore, it can be confirmed that the peeling time is significantly shortened.
本発明によれば、付着する金属の種類に応じて、電解条件等を変更する必要がなく、付着金属の剥離に伴う処理時間や処理工程を大幅に短縮することができる。さらに、本発明は、付着金属を剥離した金属板を防着板やマスクとして、再利用することができ、また、電解液中に溶出させた各種金属を有価物として回収することができる。さらに、金属回収後の電解液を廃液にすることなく再利用することができる。本発明は、成膜装置の防着板やマスク、メッキ治具など、金属が付着した金属板の再生方法として有用である。 According to the present invention, it is not necessary to change the electrolysis conditions and the like according to the type of the metal to be attached, and it is possible to greatly reduce the processing time and the processing step involved in the removal of the attached metal. Further, according to the present invention, the metal plate from which the adhered metal has been peeled off can be reused as an adhesion-preventing plate or a mask, and various metals eluted in the electrolytic solution can be recovered as valuables. Furthermore, the electrolytic solution after recovering the metal can be reused without being discarded. INDUSTRIAL APPLICABILITY The present invention is useful as a method for regenerating a metal plate to which a metal is attached, such as a deposition preventive plate of a film forming apparatus, a mask, a plating jig, and the like.
Claims (2)
When the adhered metal is any two or more selected from copper, aluminum, gold, silver, nickel, chromium, and cobalt, and the metal plate is stainless steel, the alkali cyanide solution is used as the electrolytic solution to adhere the metal. 2. The metal according to claim 1, wherein the metal is any two or more selected from copper, nickel and cobalt, and when the metal plate is aluminum, a sulfate solution is used as an electrolytic solution. A method of peeling adhered metal from a plate.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017198109 | 2017-10-12 | ||
| JP2017198109 | 2017-10-12 | ||
| PCT/JP2018/036234 WO2019073819A1 (en) | 2017-10-12 | 2018-09-28 | Method for removing adhered metals from metal plate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP6748310B2 true JP6748310B2 (en) | 2020-08-26 |
| JPWO2019073819A1 JPWO2019073819A1 (en) | 2020-09-03 |
Family
ID=66100619
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2019548121A Active JP6748310B2 (en) | 2017-10-12 | 2018-09-28 | Method of peeling adhered metal from metal plate |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP6748310B2 (en) |
| MY (1) | MY180984A (en) |
| TW (1) | TWI725345B (en) |
| WO (1) | WO2019073819A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7330831B2 (en) * | 2019-09-17 | 2023-08-22 | アサヒプリテック株式会社 | Electrolytic device and stripping method |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54145322A (en) * | 1978-05-04 | 1979-11-13 | Furukawa Seimitsu Kinzoku Koug | Electrolytic recover of silver from silver attached iron composite material |
| JPH02104699A (en) * | 1988-10-11 | 1990-04-17 | C Uyemura & Co Ltd | Electrolytic peeling agent for silver and electrolytically peeling method |
| US6428683B1 (en) * | 2000-12-15 | 2002-08-06 | United Technologies Corporation | Feedback controlled airfoil stripping system with integrated water management and acid recycling system |
| US7033466B2 (en) * | 2002-09-27 | 2006-04-25 | United Technologies Corporation | Electrochemical stripping using single loop control |
| US20080202552A1 (en) * | 2006-12-07 | 2008-08-28 | Lawrence Bernard Kool | Method for selectively removing coatings from metal substrates |
| JP2011149037A (en) * | 2010-01-19 | 2011-08-04 | Mitsubishi Shindoh Co Ltd | Method for recycling scrap of copper or copper alloy plated with silver |
| TWI426157B (en) * | 2011-05-18 | 2014-02-11 | Uwin Nanotech Co Ltd | The stripping gold components and the method of stripping gold |
| CN104419975A (en) * | 2013-09-05 | 2015-03-18 | 通用电气公司 | System and method for controlling electrochemical stripping process |
-
2018
- 2018-09-28 WO PCT/JP2018/036234 patent/WO2019073819A1/en active Application Filing
- 2018-09-28 JP JP2019548121A patent/JP6748310B2/en active Active
- 2018-09-28 MY MYPI2020001781A patent/MY180984A/en unknown
- 2018-10-04 TW TW107135033A patent/TWI725345B/en active
Also Published As
| Publication number | Publication date |
|---|---|
| WO2019073819A1 (en) | 2019-04-18 |
| TW201923167A (en) | 2019-06-16 |
| MY180984A (en) | 2020-12-15 |
| JPWO2019073819A1 (en) | 2020-09-03 |
| TWI725345B (en) | 2021-04-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10138567B2 (en) | Apparatus and method for ionic liquid electroplating | |
| US9758893B2 (en) | Electroplating methods for semiconductor substrates | |
| JP4076751B2 (en) | Electro-copper plating method, phosphor-containing copper anode for electrolytic copper plating, and semiconductor wafer plated with these and having less particle adhesion | |
| JP6748310B2 (en) | Method of peeling adhered metal from metal plate | |
| US2457060A (en) | Method for bonding a nickel electrodeposit to a nickel surface | |
| KR20130018655A (en) | High-purity copper anode for copper electroplating, method for producing same, and copper electroplating method | |
| JP2011162850A (en) | Plating pretreatment method for aluminum alloy | |
| JP2007254866A (en) | Plating pretreatment method for aluminum or aluminum alloy raw material | |
| JP4949994B2 (en) | Method for peeling a metal plate from a metal plate having a plurality of metal layers | |
| JP5505213B2 (en) | Electrical nickel plating equipment for steel strip | |
| US2966448A (en) | Methods of electroplating aluminum and alloys thereof | |
| JP2008095203A (en) | Electrolytic copper plating method | |
| JPWO2004074545A1 (en) | Component for film forming apparatus and cleaning method thereof | |
| CN109267115A (en) | A kind of copper components nickel plating process | |
| CN110144609A (en) | A kind of electroplating processing method of repeatedly heavy zinc | |
| JPH0885894A (en) | Electrode | |
| US11965265B1 (en) | Hybrid electro-processing of a metal workpiece | |
| JP7334095B2 (en) | Tin electrowinning method | |
| JP5234844B2 (en) | Electro-copper plating method, phosphor-containing copper anode for electrolytic copper plating, and semiconductor wafer plated with these and having less particle adhesion | |
| JP3406403B2 (en) | Electrode for strong acid water | |
| JP2011149037A (en) | Method for recycling scrap of copper or copper alloy plated with silver | |
| US720326A (en) | Process of preparing storage-battery plates. | |
| JP2003171788A (en) | Equipment for fractional recovery of metallic base material from object to be plated and method for fractional recovery of the same | |
| JP4147079B2 (en) | Method for removing Ag from chloride bath | |
| TW201038766A (en) | Method of electroless gold plating over miniature circuits on substrate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A529 | Written submission of copy of amendment under article 34 pct |
Free format text: JAPANESE INTERMEDIATE CODE: A5211 Effective date: 20200303 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20200311 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20200311 |
|
| A871 | Explanation of circumstances concerning accelerated examination |
Free format text: JAPANESE INTERMEDIATE CODE: A871 Effective date: 20200311 |
|
| A975 | Report on accelerated examination |
Free format text: JAPANESE INTERMEDIATE CODE: A971005 Effective date: 20200623 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20200804 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20200806 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6748310 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |