WO2017159933A1 - Device and method for regenerating etching liquid and recovering copper - Google Patents

Device and method for regenerating etching liquid and recovering copper Download PDF

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Publication number
WO2017159933A1
WO2017159933A1 PCT/KR2016/008699 KR2016008699W WO2017159933A1 WO 2017159933 A1 WO2017159933 A1 WO 2017159933A1 KR 2016008699 W KR2016008699 W KR 2016008699W WO 2017159933 A1 WO2017159933 A1 WO 2017159933A1
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Prior art keywords
etching
copper
tank
etching solution
bath
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PCT/KR2016/008699
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French (fr)
Korean (ko)
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김영석
임성환
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레캅 주식회사
주식회사 코아켐테크날러지
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Priority to CN201680035666.8A priority Critical patent/CN107849717A/en
Publication of WO2017159933A1 publication Critical patent/WO2017159933A1/en

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    • 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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • C23F1/18—Acidic compositions for etching copper or alloys thereof
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
    • C25C3/34—Electrolytic production, recovery or refining of metals by electrolysis of melts of metals not provided for in groups C25C3/02 - C25C3/32
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/02—Electrodes; Connections thereof
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/06—Operating or servicing
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/59—Transmissivity

Definitions

  • the present invention relates to an etching solution regeneration and copper recovery apparatus and method, and more particularly, a regeneration tank and a regeneration tank for regenerating the waste etching solution generated in the etching bath when regenerating the waste etching solution aged as the etching proceeds in the etching bath.
  • a recovery tank for recovering the copper precipitated in the present invention and relates to an etching solution regeneration and copper recovery apparatus and method, which is possible to recover the waste etching solution and copper recovery through electrolytic copper plating.
  • Etching is used in the formation of circuits for electronic and precision parts such as PCB (Printed Circuit Board), Tape Automated Bonding (TAB), Ball Grid Array (BGA), Chip On Flexible Printed Circuit (COF), and lead frames. It is a process of removing copper and copper alloy, leaving only a circuit, optionally.
  • PCB Printed Circuit Board
  • TAB Tape Automated Bonding
  • BGA Ball Grid Array
  • COF Chip On Flexible Printed Circuit
  • lead frames It is a process of removing copper and copper alloy, leaving only a circuit, optionally.
  • the etching mechanism is performed by first etching the copper and the copper alloy to oxidize the surface of the copper oxide and the metal oxide, and dissolving the metal oxide.
  • the waste etching solution generated by the etching process is toxic, and in order to treat this, various methods such as chemical dilution, precipitation, and substitution of the waste etching solution are used.
  • Korean Patent Publication No. 10-1291554 (2013.08.08.) Discloses an etching solution regeneration and copper recovery apparatus and method using an Algibi color sensor.
  • the etching solution regeneration and copper recovery apparatus transfers the waste etching solution that is aging as the etching proceeds in the etching bath, and regenerates the waste etching solution in real time by electrolysis, thereby preventing generation of the waste etching solution, and toxic concentrated hydrochloric acid.
  • Patent Document 1 KR 10-1291554 B1 2013.08.08.
  • An object of the present invention is to eliminate the need for a regeneration tank for regenerating the waste etching solution generated in the etching bath and a recovery tank for recovering the copper precipitated in the regeneration bath when regenerating the waste etching solution aged as the etching proceeds in the etching bath,
  • the present invention provides an apparatus and method for etching solution recovery and copper recovery, which enables the recovery of waste etching solution and recovery of copper through copper plating.
  • the present invention provides the following means.
  • the present invention is an etching bath in which the etching process is performed; An etching liquid filling the etching bath and having an etching force; An optical sensor disposed in the etching bath to measure copper concentration; An electrolytic copper plating tank for regenerating the waste etching solution generated in the etching bath; A cathode electrode and an anode electrode disposed in the electrolytic copper plating bath; A rectifier connecting the cathode electrode and the anode electrode to apply a current; And a controller for controlling the etching bath and the rectifier; It provides an etching solution regeneration and copper recovery apparatus comprising a.
  • the etchant is hydrogen peroxide (H 2 O 2 ) and sulfuric acid (H 2 SO 4 ), sodium bisulfate (Na 2 S 2 O 8 ) and sulfuric acid (H 2 SO 4 ), potassium persulfate (K 2 S 2 O 8 ) And sulfuric acid (H 2 SO 4 ) and potassium hydrogen peroxide (KHSO 5 ) and sulfuric acid (H 2 SO 4 ) and any one selected from the group consisting of.
  • the area of the cathode electrode is less than twice the area of the anode electrode, and the optical sensor for detecting the copper concentration of the etching solution sends a signal to the controller when the copper concentration exceeds a predetermined level.
  • the present invention provides an etching solution regeneration and copper recovery method comprising a.
  • step 2 the voltage during electroplating is 2 ⁇ 6V, the current density is 3 ⁇ 16 (A / dm 2).
  • the etching bath is performed the etching process;
  • An etching liquid filling the etching bath and having an etching force;
  • An optical sensor disposed in the etching bath to measure copper concentration;
  • a controller for controlling the etching bath and the rectifier; It provides an etching solution regeneration and copper recovery apparatus comprising a.
  • the controller receives the copper concentration of the etching solution from the optical sensor, and when the copper concentration exceeds a predetermined level, the controller sends a signal to the rectifier to supply current from the rectifier to the anode and cathode electrodes.
  • Etching liquid regeneration and copper recovery apparatus and method by transferring the etched waste etching solution to the electrolytic copper plating bath as the etching proceeds in the etching bath, it is possible to prevent the generation of waste etching solution by regeneration by electroplating method. In addition, there is no need for a regeneration tank for regenerating the waste etching solution generated in the etching bath and a recovery tank for recovering the copper precipitated in the regeneration tank. There is this.
  • FIG. 1 is a schematic diagram of an etching solution regeneration and copper recovery apparatus according to an embodiment of the present invention.
  • FIG. 2 is a schematic view of an etching solution regeneration and copper recovery apparatus according to another embodiment of the present invention.
  • FIG. 1 is a schematic diagram of an etching solution regeneration and copper recovery apparatus according to an embodiment of the present invention.
  • An etching solution 20 filling the etching bath 10 and having an etching force
  • An optical sensor 30 disposed in the etching bath 10 to measure copper concentration
  • the etching bath 10 provides a space for performing an etching process on the metal layer formed on the insulating substrate.
  • the etching bath 10 is filled with an etching solution 20 having an etching force.
  • the etchant is hydrogen peroxide (H 2 O 2 ) and sulfuric acid (H 2 SO 4 ), sodium bisulfate (Na 2 S 2 O 8 ) and sulfuric acid (H 2 SO 4 ), potassium persulfate (K 2 S 2 O 8 ) And sulfuric acid (H 2 SO 4 ) and potassium hydrogen peroxide (KHSO 5 ) and sulfuric acid (H 2 SO 4 ) It is preferably included any one selected from the group consisting of.
  • the optical sensor 30 is a component for optimizing the copper recovery rate of the etching solution regeneration and copper recovery apparatus according to the present invention by measuring the copper concentration of the etching solution 20, as shown in Figure 1, the etching bath 10 ) Can be installed.
  • the electrolytic copper plating bath 40 is connected to the etching bath 10 to provide a waste etching solution 50 transferred from the etching bath 10.
  • the electrolytic copper plating bath 40 is provided with a cathode electrode 60 and a cathode electrode 70.
  • the waste etching solution 50 is regenerated and copper is recovered through electrolytic copper plating.
  • the anode electrode 70 preferably uses an insoluble electrode coated with a platinum group oxide including iridium on a titanium surface.
  • the material of the cathode electrode 60 is not particularly limited.
  • the area of the cathode electrode 60 is preferably not more than twice the area of the anode electrode 70, and preferably has a voltage of 2 to 6V during electroplating.
  • the cathode electrode 60 is preferably provided in the form of a plate or a mesh (Mesh).
  • the cathode electrode 60 is preferably configured to be easily replaced after the copper recovery.
  • the positive electrode 70 and the negative electrode 60 are connected to the rectifier 80.
  • the rectifier 80 supplies current to the anode electrode 70 and the cathode electrode 60.
  • the optical sensor 30 for detecting the copper concentration of the etching solution transmits a signal to the controller 90 when the copper concentration exceeds a predetermined level.
  • the control unit 90 receives the copper concentration of the etching solution 20 from the optical sensor 30, and when the copper concentration exceeds a predetermined level, sends a signal to the rectifier 80 to transmit the signal from the rectifier 80 to the anode electrode. A current is supplied to 70 and the cathode electrode 60.
  • the power applied to the anode electrode 70 and the cathode electrode 60 preferably supplies a DC power having a current density of 3 to 16 (A / dm 2) to each electrode. If the current density is less than 3 (A / dm 2), there is a problem that the copper electrodeposition rate is lowered, and when the current density exceeds 16 (A / dm 2), the phenomenon that the rectifier is down may occur.
  • An etching solution circulation line is installed in the etching bath 10 and the electrolytic copper plating bath 40, and the waste etching solution 50 generated in the etching bath 10 through the etching solution circulation line is the electrolytic copper plating bath 40. ), And the etching solution regenerated in the electrolytic copper plating tank 40 may be circulated to the etching bath 10.
  • step 2 If the copper concentration exceeds a predetermined level, applying power to the anode electrode 70 and the cathode electrode 60 (step 2); And
  • the etching solution 20 in the etching bath 10 is transferred to the electrolytic copper plating bath 40, and after electrolytic copper plating in the electrolytic copper plating bath 40, the circulation is transferred to the etching bath 10 again. This is done repeatedly.
  • step 1 the optical sensor 30 for detecting the copper concentration of the etching solution 20 sends a signal to the controller 90 when the copper concentration exceeds a predetermined level.
  • step 2 the control unit 90 receives the copper concentration of the etching solution 20 from the optical sensor 30, and when the copper concentration exceeds a predetermined level, it sends a signal to the rectifier 80 to rectifier 80 ) To supply current to the anode electrode 70 and the cathode electrode 60.
  • the power applied to the anode electrode 70 and the cathode electrode 60 may be provided by supplying DC power having a current density of 3 to 16 (A / dm 2) to each electrode.
  • the voltage is preferably 2-6V.
  • Copper ions are electrodeposited on the surface of the cathode electrode 60 by the application of power, and the concentration of copper ions in the waste etching solution 50 is lowered and regenerated.
  • the etching solution regenerated in the electrolytic copper plating tank 40 is circulated to the etching bath 10 by the driving of the etching solution circulation line and the pump.
  • Etching liquid regeneration and copper recovery apparatus and method according to the present invention by transferring the etched waste etching solution to the electrolytic copper plating bath as the etching proceeds in the etching bath, it is possible to prevent the generation of waste etching solution by regeneration by electroplating method. have.
  • FIG. 2 is a schematic view of an etching solution regeneration and copper recovery apparatus according to another embodiment of the present invention.
  • An etching solution 120 filling the etching bath 110 and having an etching force
  • An optical sensor 160 disposed in the etching bath 110 to measure copper concentration
  • the etching bath 110 provides a space for performing an etching process on the metal layer formed on the insulating substrate.
  • the etching bath 110 is filled with an etching solution 120 having an etching force.
  • the etching bath 110 performs not only an etching process but also a role of an electrolytic copper plating bath for recovering copper and regenerating waste etching solution, and thus, an electrolytic copper plating bath is not required.
  • the etchant is hydrogen peroxide (H 2 O 2 ) and sulfuric acid (H 2 SO 4 ), sodium bisulfate (Na 2 S 2 O 8 ) and sulfuric acid (H 2 SO 4 ), potassium persulfate (K 2 S 2 O 8 ) And sulfuric acid (H 2 SO 4 ) and potassium hydrogen peroxide (KHSO 5 ) and sulfuric acid (H 2 SO 4 ) It is preferably included any one selected from the group consisting of.
  • the anode electrode 130 is disposed in the etching bath 110, it is preferable to configure the anode electrode is dissolved so that the etching solution 120 does not dissolve when the power supply is connected, a platinum group oxide containing iridium is coated on the titanium surface It is preferable to use insoluble electrodes.
  • the cathode electrode 140 is disposed in the etching bath 110 to be spaced apart from the cathode electrode 130 by a predetermined distance, and the material is not particularly limited within a range that does not contaminate the etching liquid 120.
  • the area of the cathode electrode 140 is not more than twice the area of the anode electrode 130, and the voltage is preferably 2 to 6V when the power is connected. If the voltage is less than 2V, there is a problem that the copper recovery rate is lowered, and if the voltage is more than 6V, the rectifier is down may occur.
  • the cathode electrode 140 is preferably provided in the form of a plate or a mesh (Mesh).
  • the cathode electrode 140 is preferably configured to be easily replaced after the copper recovery.
  • the anode electrode 130 and the cathode electrode 140 are connected to the rectifier 150.
  • the rectifier 150 supplies current to the anode electrode 130 and the cathode electrode 140.
  • the optical sensor 160 is a component for optimizing the copper recovery rate of the etching solution regeneration and copper recovery apparatus according to the present invention by measuring the copper concentration of the etching solution 120, as shown in Figure 2, the etching bath 110 ) Can be installed.
  • the controller 170 receives the copper concentration of the etching solution 120 from the optical sensor 160, and when the copper concentration exceeds a predetermined level, sends a signal to the rectifier 150 to transmit the signal to the anode electrode from the rectifier 150.
  • the current is supplied to the 130 and the cathode electrode 140.
  • the power applied to the anode electrode 130 and the cathode electrode 140 preferably supplies a DC power having a current density of 3 to 16 (A / dm 2) to each electrode.
  • Copper is electrodeposited on the surface of the cathode electrode 140 by applying power, and thus, the waste etching solution is regenerated, and by replacing the cathode electrode 140, copper plated on the cathode electrode 140 is easily required without a recovery tank. There is an advantage that can be easily recovered.
  • Another embodiment of the present invention does not require a regeneration bath or an electrolytic copper plating bath, there is an advantage that the sulfuric acid-based etching solution regeneration and copper recovery directly in the etching solution in use.
  • An etching solution regeneration and a copper recovery device were manufactured as shown in FIG. 1.
  • the waste etching solution generated in the etching bath 10 was transferred to the electrolytic copper plating tank 40. Power was applied to the anode electrode 70 and the cathode electrode 60 so that copper ions were electrodeposited on the surface of the cathode electrode 60 in the waste etching solution so that the waste etching solution was regenerated.
  • the etching solution regenerated in the electrolytic copper plating tank 40 was circulated to the etching bath 10.
  • the etchant included hydrogen peroxide (H 2 O 2 ) and sulfuric acid (H 2 SO 4 ).
  • the power source applied to the anode electrode 70 and the cathode electrode 60 located in the electrolytic copper plating tank 40 supplied a DC power source having a current density of 6 (A / dm 2) to each electrode.
  • the electrolytic copper plating time was 5 minutes.
  • Example 1 except that the etching solution contained sodium peroxide (Na 2 S 2 O 8 ) and sulfuric acid (H 2 SO 4 ) instead of hydrogen peroxide (H 2 O 2 ) and sulfuric acid (H 2 SO 4 ), the remainder was the same. It was made.
  • Example 1 except that the etchant included potassium peroxide (K 2 S 2 O 8 ) and sulfuric acid (H 2 SO 4 ) instead of hydrogen peroxide (H 2 O 2 ) and sulfuric acid (H 2 SO 4 ), The same was done.
  • K 2 S 2 O 8 potassium peroxide
  • H 2 SO 4 sulfuric acid
  • Example 1 the etching solution was the same except that hydrogen peroxide (H 2 O 2 ) and sulfuric acid (H 2 SO 4 ) instead of potassium hydrogen peroxide (KHSO 5 ) and sulfuric acid (H 2 SO 4 ).
  • Example 1 The etching solution in Example 1 was the same except that the copper chloride (CuCl 2 ⁇ 2H 2 O) and hydrochloric acid (HCl) instead of hydrogen peroxide (H 2 O 2 ) and sulfuric acid (H 2 SO 4 ).
  • CuCl 2 ⁇ 2H 2 O copper chloride
  • HCl hydrochloric acid
  • the electrolytic copper plating was repeated four times in the electrolytic copper plating tanks 40 of Examples 1 to 4 and Comparative Example 1, respectively, and the amounts of copper remaining in the waste etching solution were measured and shown in Table 1 below.
  • or Example 4 are very excellent in copper recovery compared with the comparative example 1.
  • optical sensor 40 electrolytic copper plating bath
  • etching bath 120 etching solution

Abstract

The present invention relates to a device for regenerating an etching liquid and recovering copper, the device being technically characterized by comprising: an etching tank in which an etching process is performed; an etching liquid that fills the etching tank and has an etching capability; an optical sensor arranged in the etching tank to measure coper concentration; an electrolytic copper plating tank for regenerating a waste etching liquid generated in the etching tank; negative and positive electrodes arranged in the electrolytic copper plating tank; a rectifier that connects the negative and positive electrodes and applies a current; and a controller for controlling the etching tank and the rectifier. The present invention has the following advantages: the waste etching liquid that ages as etching proceeds in the etching tank is transferred to the electrolytic copper plating tank and is regenerated in an electroplating type, thereby preventing generation of the waste etching liquid; there is no need to provide either a regenerating tank for regenerating the waste etching liquid generated in the etching tank or a recovering tank for recovering copper precipitated in the regenerating tank; and it is possible to recover copper and to regenerate the waste etching liquid using a simple method through electrolytic copper plating.

Description

에칭액 재생 및 구리 회수 장치 및 방법Etching solution regeneration and copper recovery apparatus and method
본 발명은 에칭액 재생 및 구리 회수 장치 및 방법에 관한 것으로, 더욱 상세하게는 에칭조에서 에칭이 진행됨에 따라 노화되는 폐 에칭액을 재생시, 에칭조에서 생성된 폐 에칭액을 재생시키기 위한 재생조와 재생조에서 석출된 구리를 회수하기 위한 회수조가 필요 없으며, 전해구리도금을 통해 폐 에칭액의 재생 및 구리의 회수가 가능한, 에칭액 재생 및 구리 회수 장치 및 방법에 관한 것이다.The present invention relates to an etching solution regeneration and copper recovery apparatus and method, and more particularly, a regeneration tank and a regeneration tank for regenerating the waste etching solution generated in the etching bath when regenerating the waste etching solution aged as the etching proceeds in the etching bath. There is no need for a recovery tank for recovering the copper precipitated in the present invention, and relates to an etching solution regeneration and copper recovery apparatus and method, which is possible to recover the waste etching solution and copper recovery through electrolytic copper plating.
에칭은 PCB(Printed Circuit Board), TAB(Tape Automated Bonding), BGA(Ball Grid Array), COF(Chip On Flexible Printed Circuit), 리드 프레임(Lead frame)등의 전자부품 및 정밀부품의 회로 형성에 있어서, 선택적으로 회로만을 남겨두고 구리 및 구리합금을 제거하는 공정이다.Etching is used in the formation of circuits for electronic and precision parts such as PCB (Printed Circuit Board), Tape Automated Bonding (TAB), Ball Grid Array (BGA), Chip On Flexible Printed Circuit (COF), and lead frames. It is a process of removing copper and copper alloy, leaving only a circuit, optionally.
일반적으로, 에칭 메카니즘은 먼저 에칭액이 구리 및 구리합금의 표면을 산화시켜 금속산화물이 되고, 이러한 금속산화물을 용해시키는 과정을 반복하여 이루어지게 된다.In general, the etching mechanism is performed by first etching the copper and the copper alloy to oxidize the surface of the copper oxide and the metal oxide, and dissolving the metal oxide.
이러한 에칭 공정에 의해 발생되는 폐 에칭액은 유독성을 가지며, 이를 처리하기 위하여 폐 에칭액의 화학적인 희석, 침전, 치환 등의 여러 가지 방법을 사용하고 있는 실정이다.The waste etching solution generated by the etching process is toxic, and in order to treat this, various methods such as chemical dilution, precipitation, and substitution of the waste etching solution are used.
그러나, 폐 에칭액을 처리하기 위하여, 다량의 중화제 및 산화 환원제의 사용하는 것은 2차 오염물을 생성시키는 원인이 되고 있으며, 화학적 처리 방법에 의해 생성되는 슬러지를 다시 처리해야 한다는 문제점이 있었다.However, in order to treat the waste etching solution, the use of a large amount of neutralizing agent and redox agent causes the generation of secondary contaminants, and there is a problem that the sludge produced by the chemical treatment method needs to be treated again.
상기 문제점을 해결하기 위해, 대한민국등록특허공보 제10-1291554호(2013.08.08.)에는 알지비 컬러센서를 이용한 에칭액 재생 및 구리 회수 장치 및 방법이 개시되어 있다.In order to solve the problem, Korean Patent Publication No. 10-1291554 (2013.08.08.) Discloses an etching solution regeneration and copper recovery apparatus and method using an Algibi color sensor.
상기 에칭액 재생 및 구리 회수 장치는 에칭조에서 에칭이 진행됨에 따라 노화되는 폐 에칭액을 재생조로 이송시키고, 이를 전기분해 방식으로 실시간 재생시킴으로써, 폐 에칭액이 발생되는 것을 방지할 수 있고, 유독한 농염산의 음극실액과 섞인 구리를 자동으로 분리 회수한 후, 압착 방식으로 염산액을 짜내어 구리를 덩어리 형태로 회수하여 작업자를 유독한 환경으로부터 보호할 수 있는 장점이 있지만, 염산 기반의 에칭액 재생에 적용되는 것으로 황산 기반의 에칭액 재생에는 적합하지 않으며, 에칭조에서 생성된 폐 에칭액을 재생시키기 위한 재생조와 재생조에서 석출된 구리를 회수하기 위한 회수조가 별도로 구비되어야 하는 단점이 있다.The etching solution regeneration and copper recovery apparatus transfers the waste etching solution that is aging as the etching proceeds in the etching bath, and regenerates the waste etching solution in real time by electrolysis, thereby preventing generation of the waste etching solution, and toxic concentrated hydrochloric acid. Automatically separate and recover the copper mixed with the cathode chamber solution, and then squeeze the hydrochloric acid solution by compression method to recover the copper in the form of lumps to protect the operator from the toxic environment, but it is applied to the recovery of hydrochloric acid-based etching solution It is not suitable for sulfuric acid-based etching solution regeneration, there is a disadvantage that a recovery tank for recovering the waste etching solution generated in the etching tank and a recovery tank for recovering the copper precipitated in the regeneration tank must be provided separately.
[선행기술문헌][Preceding technical literature]
[특허문헌][Patent Documents]
(특허문헌 1) KR 10-1291554 B1 2013.08.08. (Patent Document 1) KR 10-1291554 B1 2013.08.08.
본 발명의 목적은 에칭조에서 에칭이 진행됨에 따라 노화되는 폐 에칭액을 재생시, 에칭조에서 생성된 폐 에칭액을 재생시키기 위한 재생조와 재생조에서 석출된 구리를 회수하기 위한 회수조가 필요 없으며, 전해구리도금을 통해 폐 에칭액의 재생 및 구리의 회수가 가능한, 에칭액 재생 및 구리 회수 장치 및 방법을 제공하는 것이다.An object of the present invention is to eliminate the need for a regeneration tank for regenerating the waste etching solution generated in the etching bath and a recovery tank for recovering the copper precipitated in the regeneration bath when regenerating the waste etching solution aged as the etching proceeds in the etching bath, The present invention provides an apparatus and method for etching solution recovery and copper recovery, which enables the recovery of waste etching solution and recovery of copper through copper plating.
상기 목적을 달성하기 위하여 본 발명은 다음과 같은 수단을 제공한다.In order to achieve the above object, the present invention provides the following means.
본 발명은 에칭공정이 수행되는 에칭조; 상기 에칭조를 채우며, 에칭력을 갖는 에칭액; 상기 에칭조에 배치되어 구리 농도를 측정하는 광센서; 상기 에칭조에서 생성된 폐 에칭액을 재생시키기 위한 전해구리도금조; 상기 전해구리도금조에 배치된 음극전극 및 양극전극; 상기 음극전극과 양극전극을 연결하여 전류를 인가하는 정류기; 및 상기 에칭조와 정류기를 제어하기 위한 제어부; 를 포함하는 에칭액 재생 및 구리 회수 장치를 제공한다.The present invention is an etching bath in which the etching process is performed; An etching liquid filling the etching bath and having an etching force; An optical sensor disposed in the etching bath to measure copper concentration; An electrolytic copper plating tank for regenerating the waste etching solution generated in the etching bath; A cathode electrode and an anode electrode disposed in the electrolytic copper plating bath; A rectifier connecting the cathode electrode and the anode electrode to apply a current; And a controller for controlling the etching bath and the rectifier; It provides an etching solution regeneration and copper recovery apparatus comprising a.
상기 에칭액은 과산화수소(H2O2)와 황산(H2SO4), 과산화이중황산나트륨(Na2S2O8)과 황산(H2SO4), 과산화이중황산칼륨(K2S2O8)과 황산(H2SO4) 및 과산화황산수소칼륨(KHSO5)과 황산(H2SO4)으로 구성된 군으로부터 선택된 어느 하나를 포함한다.The etchant is hydrogen peroxide (H 2 O 2 ) and sulfuric acid (H 2 SO 4 ), sodium bisulfate (Na 2 S 2 O 8 ) and sulfuric acid (H 2 SO 4 ), potassium persulfate (K 2 S 2 O 8 ) And sulfuric acid (H 2 SO 4 ) and potassium hydrogen peroxide (KHSO 5 ) and sulfuric acid (H 2 SO 4 ) and any one selected from the group consisting of.
상기 음극전극의 면적은 상기 양극전극의 면적의 2배 이하이며, 에칭액의 구리 농도를 감지하는 광센서는 구리 농도가 일정 수준을 초과할 경우 제어부에 신호를 송출한다.The area of the cathode electrode is less than twice the area of the anode electrode, and the optical sensor for detecting the copper concentration of the etching solution sends a signal to the controller when the copper concentration exceeds a predetermined level.
또한, 본 발명은, 에칭액의 구리 농도를 감지하는 단계(단계 1); 구리 농도가 일정 수준을 초과하면 양극전극 및 음극전극에 전원을 인가하는 단계(단계 2); 및 상기 구리 이온이 표면에 전착된 음극전극을 교체하는 단계(단계 3); 를 포함하는 에칭액 재생 및 구리 회수 방법을 제공한다.In addition, the present invention, the step of detecting the copper concentration of the etching solution (step 1); If the copper concentration exceeds a predetermined level, applying power to the positive electrode and the negative electrode (step 2); And replacing the cathode electrode in which the copper ions are electrodeposited on the surface (step 3). It provides an etching solution regeneration and copper recovery method comprising a.
상기 단계 2에서, 전기도금시 전압이 2~6V이며, 전류밀도는 3~16(A/d㎡) 이다.In step 2, the voltage during electroplating is 2 ~ 6V, the current density is 3 ~ 16 (A / dm 2).
또한, 본 발명은, 에칭공정이 수행되는 에칭조; 상기 에칭조를 채우며, 에칭력을 갖는 에칭액; 상기 에칭조에 배치된 양극전극 및 음극전극; 상기 양극전극과 음극전극을 연결하여 전류를 인가하는 정류기; 상기 에칭조에 배치되어 구리 농도를 측정하는 광센서; 및 상기 에칭조와 정류기를 제어하기 위한 제어부; 를 포함하는 에칭액 재생 및 구리 회수 장치를 제공한다.In addition, the present invention, the etching bath is performed the etching process; An etching liquid filling the etching bath and having an etching force; An anode electrode and a cathode electrode disposed in the etching bath; A rectifier connecting the positive electrode and the negative electrode to apply a current; An optical sensor disposed in the etching bath to measure copper concentration; And a controller for controlling the etching bath and the rectifier; It provides an etching solution regeneration and copper recovery apparatus comprising a.
상기 제어부는 상기 광센서로부터 상기 에칭액의 구리 농도를 전달받으며, 구리 농도가 일정 수준을 초과하면 정류기에 신호를 송출하여 상기 정류기로부터 상기 양극전극과 음극전극에 전류를 공급하도록 한다.The controller receives the copper concentration of the etching solution from the optical sensor, and when the copper concentration exceeds a predetermined level, the controller sends a signal to the rectifier to supply current from the rectifier to the anode and cathode electrodes.
본 발명에 따른 에칭액 재생 및 구리 회수 장치 및 방법은, 에칭조에서 에칭이 진행됨에 따라 노화되는 폐 에칭액을 전해구리도금조로 이송시키고, 전기도금 방식으로 재생시킴으로써, 폐 에칭액이 발생되는 것을 방지할 수 있으며, 에칭조에서 생성된 폐 에칭액을 재생시키기 위한 재생조와 재생조에서 석출된 구리를 회수하기 위한 회수조가 필요 없으며, 전해구리도금을 통해 간단한 방법으로 구리를 회수하고 폐 에칭액을 재생시킬 수 있는 장점이 있다.Etching liquid regeneration and copper recovery apparatus and method according to the present invention, by transferring the etched waste etching solution to the electrolytic copper plating bath as the etching proceeds in the etching bath, it is possible to prevent the generation of waste etching solution by regeneration by electroplating method. In addition, there is no need for a regeneration tank for regenerating the waste etching solution generated in the etching bath and a recovery tank for recovering the copper precipitated in the regeneration tank. There is this.
도 1은 본 발명의 일실시예에 따른 에칭액 재생 및 구리 회수 장치의 개략도이다.1 is a schematic diagram of an etching solution regeneration and copper recovery apparatus according to an embodiment of the present invention.
도 2는 본 발명의 다른 실시예에 따른 에칭액 재생 및 구리 회수 장치의 개략도이다.2 is a schematic view of an etching solution regeneration and copper recovery apparatus according to another embodiment of the present invention.
이하, 본 발명을 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail.
도 1은 본 발명의 일실시예에 따른 에칭액 재생 및 구리 회수 장치의 개략도이다.1 is a schematic diagram of an etching solution regeneration and copper recovery apparatus according to an embodiment of the present invention.
도 1을 참조하면, 본 발명에 따른 에칭액 재생 및 구리 회수 장치는, Referring to Figure 1, the etching solution regeneration and copper recovery apparatus according to the present invention,
에칭공정이 수행되는 에칭조(10); An etching bath 10 in which an etching process is performed;
상기 에칭조(10)를 채우며, 에칭력을 갖는 에칭액(20); An etching solution 20 filling the etching bath 10 and having an etching force;
상기 에칭조(10)에 배치되어 구리 농도를 측정하는 광센서(30); An optical sensor 30 disposed in the etching bath 10 to measure copper concentration;
상기 에칭조(10)에서 생성된 폐 에칭액(50)을 재생시키기 위한 전해구리도금조(40);An electrolytic copper plating tank 40 for regenerating the waste etching solution 50 generated in the etching bath 10;
상기 전해구리도금조(40)에 배치된 음극전극(60) 및 양극전극(70);A cathode electrode 60 and an anode electrode 70 disposed in the electrolytic copper plating tank 40;
상기 음극전극(60)과 양극전극(70)을 연결하여 전류를 인가하는 정류기(80); 및A rectifier 80 connecting the cathode electrode 60 and the anode electrode 70 to apply a current; And
상기 에칭조(10)와 정류기(80)를 제어하기 위한 제어부(90); A control unit 90 for controlling the etching bath 10 and the rectifier 80;
를 포함한다.It includes.
상기 에칭조(10)는 절연기판 상에 형성된 금속층에 대하여 에칭 공정을 행하기 위한 공간을 제공한다. 상기 에칭조(10)에는 에칭력을 갖는 에칭액(20)으로 채워진다.The etching bath 10 provides a space for performing an etching process on the metal layer formed on the insulating substrate. The etching bath 10 is filled with an etching solution 20 having an etching force.
상기 에칭액은 과산화수소(H2O2)와 황산(H2SO4), 과산화이중황산나트륨(Na2S2O8)과 황산(H2SO4), 과산화이중황산칼륨(K2S2O8)과 황산(H2SO4) 및 과산화황산수소칼륨(KHSO5)과 황산(H2SO4)으로 구성된 군으로부터 선택된 어느 하나를 포함하는 것이 바람직하다.The etchant is hydrogen peroxide (H 2 O 2 ) and sulfuric acid (H 2 SO 4 ), sodium bisulfate (Na 2 S 2 O 8 ) and sulfuric acid (H 2 SO 4 ), potassium persulfate (K 2 S 2 O 8 ) And sulfuric acid (H 2 SO 4 ) and potassium hydrogen peroxide (KHSO 5 ) and sulfuric acid (H 2 SO 4 ) It is preferably included any one selected from the group consisting of.
상기 광센서(30)는 상기 에칭액(20)의 구리 농도를 측정하여 본 발명에 따른 에칭액 재생 및 구리 회수 장치의 구리 회수율을 최적화시키기 위한 구성요소로써, 도 1에서와 같이, 상기 에칭조(10)에 설치될 수 있다.The optical sensor 30 is a component for optimizing the copper recovery rate of the etching solution regeneration and copper recovery apparatus according to the present invention by measuring the copper concentration of the etching solution 20, as shown in Figure 1, the etching bath 10 ) Can be installed.
상기 전해구리도금조(40)는 에칭조(10)와 배관 연결되어 에칭조(10)로부터 이송된 폐 에칭액(50)을 수용하도록 마련된다.The electrolytic copper plating bath 40 is connected to the etching bath 10 to provide a waste etching solution 50 transferred from the etching bath 10.
상기 전해구리도금조(40)에는 음극전극(60) 및 양극전극(70)이 설치된다.The electrolytic copper plating bath 40 is provided with a cathode electrode 60 and a cathode electrode 70.
상기 전해구리도금조(40)에서는 전해구리도금을 통해 폐 에칭액(50)의 재생 및 구리의 회수가 이루어진다. In the electrolytic copper plating tank 40, the waste etching solution 50 is regenerated and copper is recovered through electrolytic copper plating.
상기 양극전극(70)은 티타늄 표면에 이리듐을 포함한 백금족 산화물이 코팅된 불용성 전극을 사용하는 것이 바람직하다.The anode electrode 70 preferably uses an insoluble electrode coated with a platinum group oxide including iridium on a titanium surface.
상기 음극전극(60)의 재질은 특별히 한정되지 아니한다.The material of the cathode electrode 60 is not particularly limited.
상기 음극전극(60)의 면적은 상기 양극전극(70)의 면적의 2배 이하인 것이 바람직하며, 전기도금시 전압이 2~6V 인 것이 바람직하다.The area of the cathode electrode 60 is preferably not more than twice the area of the anode electrode 70, and preferably has a voltage of 2 to 6V during electroplating.
상기 음극전극(60)의 면적이 상기 양극전극(70)의 면적의 2배 초과이면 전압이 상승하여 정류기가 Down되는 현상이 발생할 수 있다. 상기 전기도금시 전압이 2V 미만이면 구리 회수율이 저하되는 문제가 있고, 6V 초과이면 정류기가 Down되는 현상이 발생할 수 있다. When the area of the cathode electrode 60 is greater than twice the area of the cathode electrode 70, a voltage may increase to cause the rectifier to go down. When the voltage is less than 2V during the electroplating, there is a problem that the copper recovery rate is lowered.
상기 음극전극(60)은 플레이트 형태 또는 메쉬(Mesh) 형태로 마련되는 것이 바람직하다.The cathode electrode 60 is preferably provided in the form of a plate or a mesh (Mesh).
상기 음극전극(60)은 구리 회수 후, 쉽게 교체할 수 있도록 구성하는 것이 바람직하다.The cathode electrode 60 is preferably configured to be easily replaced after the copper recovery.
상기 양극전극(70)과 음극전극(60)은 상기 정류기(80)로 연결된다. 상기 정류기(80)는 상기 양극전극(70)과 음극전극(60)에 전류를 공급한다.The positive electrode 70 and the negative electrode 60 are connected to the rectifier 80. The rectifier 80 supplies current to the anode electrode 70 and the cathode electrode 60.
에칭액의 구리 농도를 감지하는 광센서(30)는 구리 농도가 일정 수준을 초과할 경우 제어부(90)에 신호를 송출한다. The optical sensor 30 for detecting the copper concentration of the etching solution transmits a signal to the controller 90 when the copper concentration exceeds a predetermined level.
상기 제어부(90)는 상기 광센서(30)로부터 상기 에칭액(20)의 구리 농도를 전달받으며, 구리 농도가 일정 수준을 초과하면 정류기(80)에 신호를 송출하여 정류기(80)로부터 상기 양극전극(70)과 음극전극(60)에 전류를 공급하도록 한다. The control unit 90 receives the copper concentration of the etching solution 20 from the optical sensor 30, and when the copper concentration exceeds a predetermined level, sends a signal to the rectifier 80 to transmit the signal from the rectifier 80 to the anode electrode. A current is supplied to 70 and the cathode electrode 60.
상기 양극전극(70)과 음극전극(60)에 인가되는 전원은, 전류밀도 3~16(A/d㎡)의 직류 전원을 각 전극에 공급하는 것이 바람직하다. 상기 전류밀도가 3(A/d㎡) 미만이면 구리 전착율이 저하되는 문제가 있고, 16(A/d㎡) 초과이면 정류기가 Down되는 현상이 발생할 수 있다. The power applied to the anode electrode 70 and the cathode electrode 60 preferably supplies a DC power having a current density of 3 to 16 (A / dm 2) to each electrode. If the current density is less than 3 (A / dm 2), there is a problem that the copper electrodeposition rate is lowered, and when the current density exceeds 16 (A / dm 2), the phenomenon that the rectifier is down may occur.
전원 인가로 인해 폐 에칭액(50) 속에 구리 이온이 음극전극(60)의 표면에 전착되며, 폐 에칭액(50)은 재생 처리된다.By applying power, copper ions are electrodeposited on the surface of the cathode electrode 60 in the waste etching solution 50, and the waste etching solution 50 is regenerated.
상기 에칭조(10)와 전해구리도금조(40)에는 에칭액순환라인이 설치되며, 상기 에칭액순환라인을 통해 상기 에칭조(10)에서 생성된 폐 에칭액(50)이 상기 전해구리도금조(40)로 이송되며, 상기 전해구리도금조(40)에서 재생된 에칭액이 상기 에칭조(10)로 순환되도록 마련될 수 있다.An etching solution circulation line is installed in the etching bath 10 and the electrolytic copper plating bath 40, and the waste etching solution 50 generated in the etching bath 10 through the etching solution circulation line is the electrolytic copper plating bath 40. ), And the etching solution regenerated in the electrolytic copper plating tank 40 may be circulated to the etching bath 10.
이하, 본 발명에 따른 에칭액 재생 및 구리 회수 방법을 상세히 설명한다.Hereinafter, the etching solution regeneration and copper recovery method according to the present invention will be described in detail.
본 발명에 따른 에칭액 재생 및 구리 회수 방법은,Etching solution regeneration and copper recovery method according to the present invention,
에칭액(20)의 구리 농도를 감지하는 단계(단계 1);Sensing the copper concentration of the etching solution 20 (step 1);
구리 농도가 일정 수준을 초과하면 양극전극(70) 및 음극전극(60)에 전원을 인가하는 단계(단계 2); 및If the copper concentration exceeds a predetermined level, applying power to the anode electrode 70 and the cathode electrode 60 (step 2); And
상기 구리 이온이 표면에 전착된 음극전극(60)을 교체하는 단계(단계 3);Replacing the cathode electrode 60 in which the copper ions are electrodeposited on the surface (step 3);
를 포함한다.It includes.
본 발명은 에칭조(10)에 있는 에칭액(20)이 전해구리도금조(40)로 이송되고, 전해구리도금조(40)에서 전해구리도금을 실시한 후에 다시 에칭조(10)로 이송되는 순환이 반복적으로 수행된다. In the present invention, the etching solution 20 in the etching bath 10 is transferred to the electrolytic copper plating bath 40, and after electrolytic copper plating in the electrolytic copper plating bath 40, the circulation is transferred to the etching bath 10 again. This is done repeatedly.
상기 단계 1에서, 에칭액(20)의 구리 농도를 감지하는 광센서(30)는 구리 농도가 일정 수준을 초과할 경우 제어부(90)에 신호를 송출한다. In step 1, the optical sensor 30 for detecting the copper concentration of the etching solution 20 sends a signal to the controller 90 when the copper concentration exceeds a predetermined level.
상기 단계 2에서, 상기 제어부(90)는 상기 광센서(30)로부터 상기 에칭액(20)의 구리 농도를 전달받으며, 구리 농도가 일정 수준을 초과하면 정류기(80)에 신호를 송출하여 정류기(80)로부터 상기 양극전극(70)과 음극전극(60)에 전류를 공급하도록 한다. In step 2, the control unit 90 receives the copper concentration of the etching solution 20 from the optical sensor 30, and when the copper concentration exceeds a predetermined level, it sends a signal to the rectifier 80 to rectifier 80 ) To supply current to the anode electrode 70 and the cathode electrode 60.
상기 양극전극(70) 및 음극전극(60)에 인가되는 전원은, 전류밀도 3~16(A/d㎡)의 직류 전원을 각 전극에 공급하는 단계로 마련될 수 있다. 전기도금시 전압이 2~6V인 것이 바람직하다. The power applied to the anode electrode 70 and the cathode electrode 60 may be provided by supplying DC power having a current density of 3 to 16 (A / dm 2) to each electrode. When electroplating, the voltage is preferably 2-6V.
상기 전류밀도가 3(A/d㎡) 미만이면 구리 전착율이 저하되는 문제가 있고, 16(A/d㎡) 초과이면 정류기가 Down되는 현상이 발생할 수 있다. If the current density is less than 3 (A / dm 2), there is a problem that the copper electrodeposition rate is lowered, and when the current density exceeds 16 (A / dm 2), the phenomenon that the rectifier is down may occur.
상기 전압이 2V 미만이면 구리 회수율이 저하되는 문제가 있고, 6V 초과이면 정류기가 Down되는 현상이 발생할 수 있다. If the voltage is less than 2V, there is a problem that the copper recovery rate is lowered, and if the voltage is more than 6V, the rectifier is down may occur.
전원 인가로 인해 폐 에칭액(50) 속에 구리 이온이 음극전극(60)의 표면에 전착되며, 폐 에칭액(50) 속의 구리 이온 농도가 낮아져서 재생된다. Copper ions are electrodeposited on the surface of the cathode electrode 60 by the application of power, and the concentration of copper ions in the waste etching solution 50 is lowered and regenerated.
*상기 전해구리도금조(40)에서 재생된 에칭액이 에칭액순환라인 및 펌프의 구동에 의해 에칭조(10)로 순환된다. * The etching solution regenerated in the electrolytic copper plating tank 40 is circulated to the etching bath 10 by the driving of the etching solution circulation line and the pump.
상기 단계 3에서 상기 음극전극(60)를 교체하므로써 회수조가 필요없이 음극전극(60)에 도금된 구리를 용이하게 회수할 수 있는 장점이 있다.By replacing the cathode electrode 60 in step 3, there is an advantage in that the copper plated on the cathode electrode 60 can be easily recovered without requiring a recovery tank.
전술한 과정이 반복됨으로써, 에칭 공정의 진행과 동시에 구리를 간단한 방법으로 회수시킬 수 있으며, 폐 에칭액 또한 재생시켜 반복적으로 사용이 가능하게 된다.By repeating the above-described process, it is possible to recover copper by a simple method at the same time as the etching process proceeds, and the waste etching solution can also be recycled and used repeatedly.
본 발명에 따른 에칭액 재생 및 구리 회수 장치 및 방법은, 에칭조에서 에칭이 진행됨에 따라 노화되는 폐 에칭액을 전해구리도금조로 이송시키고, 전기도금 방식으로 재생시킴으로써, 폐 에칭액이 발생되는 것을 방지할 수 있다.Etching liquid regeneration and copper recovery apparatus and method according to the present invention, by transferring the etched waste etching solution to the electrolytic copper plating bath as the etching proceeds in the etching bath, it is possible to prevent the generation of waste etching solution by regeneration by electroplating method. have.
또한, 에칭조에서 생성된 폐 에칭액을 재생시키기 위한 재생조와 재생조에서 석출된 구리를 회수하기 위한 회수조가 필요 없으며, 전해구리도금을 통해 간단한 방법으로 구리를 회수하고 폐 에칭액을 재생시킬 수 있다.In addition, there is no need for a regeneration tank for regenerating the waste etching solution generated in the etching bath and a recovery tank for recovering the copper precipitated in the regeneration tank.
다음은, 도 2를 참조하여 본 발명의 다른 실시예에 따른 에칭액 재생 및 구리 회수 장치에 대해 설명한다.Next, an etching solution regeneration and copper recovery device according to another embodiment of the present invention will be described with reference to FIG. 2.
도 2는 본 발명의 다른 실시예에 따른 에칭액 재생 및 구리 회수 장치의 개략도이다.2 is a schematic view of an etching solution regeneration and copper recovery apparatus according to another embodiment of the present invention.
도 2를 참조하면, 본 발명에 따른 에칭액 재생 및 구리 회수 장치는, 2, the etching solution regeneration and copper recovery apparatus according to the present invention,
에칭공정이 수행되는 에칭조(110); An etching bath 110 in which an etching process is performed;
상기 에칭조(110)를 채우며, 에칭력을 갖는 에칭액(120); An etching solution 120 filling the etching bath 110 and having an etching force;
상기 에칭조(110)에 배치된 양극전극(130) 및 음극전극(140);An anode electrode 130 and a cathode electrode 140 disposed in the etching bath 110;
상기 양극전극(130)과 음극전극(140)을 연결하여 전류를 인가하는 정류기(150);A rectifier 150 connecting the positive electrode 130 and the negative electrode 140 to apply a current;
상기 에칭조(110)에 배치되어 구리 농도를 측정하는 광센서(160); 및An optical sensor 160 disposed in the etching bath 110 to measure copper concentration; And
상기 에칭조(110)와 정류기(150)를 제어하기 위한 제어부(170); A controller 170 for controlling the etching bath 110 and the rectifier 150;
를 포함한다.It includes.
상기 에칭조(110)는 절연기판 상에 형성된 금속층에 대하여 에칭 공정을 행하기 위한 공간을 제공한다. 상기 에칭조(110)에는 에칭력을 갖는 에칭액(120)으로 채워진다.The etching bath 110 provides a space for performing an etching process on the metal layer formed on the insulating substrate. The etching bath 110 is filled with an etching solution 120 having an etching force.
상기 에칭조(110)는 에칭 공정뿐만 아니라, 구리 회수 및 폐 에칭액을 재생시키는 전해구리도금조의 역할까지 수행하므로, 별도로 전해구리도금조가 필요없는 것이 특징이다.The etching bath 110 performs not only an etching process but also a role of an electrolytic copper plating bath for recovering copper and regenerating waste etching solution, and thus, an electrolytic copper plating bath is not required.
상기 에칭액은 과산화수소(H2O2)와 황산(H2SO4), 과산화이중황산나트륨(Na2S2O8)과 황산(H2SO4), 과산화이중황산칼륨(K2S2O8)과 황산(H2SO4) 및 과산화황산수소칼륨(KHSO5)과 황산(H2SO4)으로 구성된 군으로부터 선택된 어느 하나를 포함하는 것이 바람직하다.The etchant is hydrogen peroxide (H 2 O 2 ) and sulfuric acid (H 2 SO 4 ), sodium bisulfate (Na 2 S 2 O 8 ) and sulfuric acid (H 2 SO 4 ), potassium persulfate (K 2 S 2 O 8 ) And sulfuric acid (H 2 SO 4 ) and potassium hydrogen peroxide (KHSO 5 ) and sulfuric acid (H 2 SO 4 ) It is preferably included any one selected from the group consisting of.
상기 양극전극(130)은 상기 에칭조(110)에 배치되며, 전원연결 시 양극전극이 용해되어 상기 에칭액(120)을 용해시키지 않도록 구성하는 것이 바람직하며, 티타늄 표면에 이리듐을 포함한 백금족 산화물이 코팅된 불용성 전극을 사용하는 것이 바람직하다.The anode electrode 130 is disposed in the etching bath 110, it is preferable to configure the anode electrode is dissolved so that the etching solution 120 does not dissolve when the power supply is connected, a platinum group oxide containing iridium is coated on the titanium surface It is preferable to use insoluble electrodes.
상기 음극전극(140)은 상기 양극전극(130)과 일정 거리 이격되어 상기 에칭조(110)에 배치되며, 상기 에칭액(120)을 오염시키지 않는 범위 내에서 재질이 특별히 한정되지 아니한다.The cathode electrode 140 is disposed in the etching bath 110 to be spaced apart from the cathode electrode 130 by a predetermined distance, and the material is not particularly limited within a range that does not contaminate the etching liquid 120.
상기 음극전극(140)의 면적은 상기 양극전극(130)의 면적의 2배 이하인 것이 바람직하며, 전원 연결시 전압이 2~6V 인 것이 바람직하다. 상기 전압이 2V 미만이면 구리 회수율이 저하되는 문제가 있고, 6V 초과이면 정류기가 Down되는 현상이 발생할 수 있다. It is preferable that the area of the cathode electrode 140 is not more than twice the area of the anode electrode 130, and the voltage is preferably 2 to 6V when the power is connected. If the voltage is less than 2V, there is a problem that the copper recovery rate is lowered, and if the voltage is more than 6V, the rectifier is down may occur.
상기 음극전극(140)은 플레이트 형태 또는 메쉬(Mesh) 형태로 마련되는 것이 바람직하다.The cathode electrode 140 is preferably provided in the form of a plate or a mesh (Mesh).
상기 음극전극(140)은 구리 회수 후, 쉽게 교체할 수 있도록 구성하는 것이 바람직하다.The cathode electrode 140 is preferably configured to be easily replaced after the copper recovery.
상기 양극전극(130)과 음극전극(140)은 상기 정류기(150)로 연결된다. 상기 정류기(150)는 상기 양극전극(130)과 음극전극(140)에 전류를 공급한다.The anode electrode 130 and the cathode electrode 140 are connected to the rectifier 150. The rectifier 150 supplies current to the anode electrode 130 and the cathode electrode 140.
상기 광센서(160)는 상기 에칭액(120)의 구리 농도를 측정하여 본 발명에 따른 에칭액 재생 및 구리 회수 장치의 구리 회수율을 최적화시키기 위한 구성요소로써, 도 2에서와 같이, 상기 에칭조(110)에 설치될 수 있다.The optical sensor 160 is a component for optimizing the copper recovery rate of the etching solution regeneration and copper recovery apparatus according to the present invention by measuring the copper concentration of the etching solution 120, as shown in Figure 2, the etching bath 110 ) Can be installed.
상기 제어부(170)는 상기 광센서(160)로부터 상기 에칭액(120)의 구리 농도를 전달받으며, 구리 농도가 일정 수준을 초과하면 정류기(150)에 신호를 송출하여 정류기(150)로부터 상기 양극전극(130)과 음극전극(140)에 전류를 공급하도록 한다. The controller 170 receives the copper concentration of the etching solution 120 from the optical sensor 160, and when the copper concentration exceeds a predetermined level, sends a signal to the rectifier 150 to transmit the signal to the anode electrode from the rectifier 150. The current is supplied to the 130 and the cathode electrode 140.
상기 양극전극(130)과 음극전극(140)에 인가되는 전원은, 전류밀도 3~16(A/d㎡)의 직류 전원을 각 전극에 공급하는 것이 바람직하다.The power applied to the anode electrode 130 and the cathode electrode 140 preferably supplies a DC power having a current density of 3 to 16 (A / dm 2) to each electrode.
전원 인가로 인해 상기 음극전극(140) 표면에 구리가 전착되고, 이에 따라 폐 에칭액은 재생 처리되며, 상기 음극전극(140)를 교체하므로써 회수조가 필요없이 음극전극(140)에 도금된 구리를 용이하게 회수할 수 있는 장점이 있다.Copper is electrodeposited on the surface of the cathode electrode 140 by applying power, and thus, the waste etching solution is regenerated, and by replacing the cathode electrode 140, copper plated on the cathode electrode 140 is easily required without a recovery tank. There is an advantage that can be easily recovered.
본 발명의 다른 실시예는 재생조 또는 전해구리도금조가 필요 없으며, 사용 중인 에칭액 내에서 곧바로 황산 기반의 에칭액 재생 및 구리 회수가 가능한 장점이 있다.Another embodiment of the present invention does not require a regeneration bath or an electrolytic copper plating bath, there is an advantage that the sulfuric acid-based etching solution regeneration and copper recovery directly in the etching solution in use.
이하, 실시 예를 통하여 본 발명의 구성 및 효과를 더욱 상세히 설명하고자 한다. 이들 실시 예는 오로지 본 발명을 예시하기 위한 것일 뿐 본 발명의 범위가 이들 실시 예에 의해 제한되는 것은 아니다. Hereinafter, the configuration and effects of the present invention through the embodiments will be described in more detail. These examples are only for illustrating the present invention, but the scope of the present invention is not limited by these examples.
[실시예 1]Example 1
도 1과 같이 에칭액 재생 및 구리 회수 장치를 제조하였다. 에칭조(10)에서 생성된 폐 에칭액을 전해구리도금조(40)로 이송시켰다. 양극전극(70) 및 음극전극(60)에 전원을 인가하여 폐 에칭액 속에 구리 이온이 음극전극(60)의 표면에 전착되며, 폐 에칭액이 재생되도록 하였다. 상기 전해구리도금조(40)에서 재생된 에칭액이 에칭조(10)로 순환되도록 하였다. 상기 에칭액은 과산화수소(H2O2)와 황산(H2SO4)을 포함하도록 하였다. 전해구리도금조(40)에 위치한 양극전극(70)과 음극전극(60)에 인가되는 전원은, 전류밀도 6(A/d㎡)의 직류 전원을 각 전극에 공급하였다. 전해구리도금 시간은 5분으로 하였다. An etching solution regeneration and a copper recovery device were manufactured as shown in FIG. 1. The waste etching solution generated in the etching bath 10 was transferred to the electrolytic copper plating tank 40. Power was applied to the anode electrode 70 and the cathode electrode 60 so that copper ions were electrodeposited on the surface of the cathode electrode 60 in the waste etching solution so that the waste etching solution was regenerated. The etching solution regenerated in the electrolytic copper plating tank 40 was circulated to the etching bath 10. The etchant included hydrogen peroxide (H 2 O 2 ) and sulfuric acid (H 2 SO 4 ). The power source applied to the anode electrode 70 and the cathode electrode 60 located in the electrolytic copper plating tank 40 supplied a DC power source having a current density of 6 (A / dm 2) to each electrode. The electrolytic copper plating time was 5 minutes.
[실시예 2]Example 2
실시예 1에서 에칭액을 과산화수소(H2O2)와 황산(H2SO4) 대신 과산화이중황산나트륨(Na2S2O8)과 황산(H2SO4)을 포함한 것을 제외하고, 나머지는 동일하게 하였다. In Example 1, except that the etching solution contained sodium peroxide (Na 2 S 2 O 8 ) and sulfuric acid (H 2 SO 4 ) instead of hydrogen peroxide (H 2 O 2 ) and sulfuric acid (H 2 SO 4 ), the remainder was the same. It was made.
[실시예 3]Example 3
실시예 1에서 에칭액을 과산화수소(H2O2)와 황산(H2SO4) 대신 과산화이중황산칼륨(K2S2O8)과 황산(H2SO4)을 포함한 것을 제외하고, 나머지는 동일하게 하였다. In Example 1, except that the etchant included potassium peroxide (K 2 S 2 O 8 ) and sulfuric acid (H 2 SO 4 ) instead of hydrogen peroxide (H 2 O 2 ) and sulfuric acid (H 2 SO 4 ), The same was done.
[실시예 4]Example 4
실시예 1에서 에칭액을 과산화수소(H2O2)와 황산(H2SO4) 대신 과산화황산수소칼륨(KHSO5)과 황산(H2SO4)을 포함한 것을 제외하고, 나머지는 동일하게 하였다. In Example 1, the etching solution was the same except that hydrogen peroxide (H 2 O 2 ) and sulfuric acid (H 2 SO 4 ) instead of potassium hydrogen peroxide (KHSO 5 ) and sulfuric acid (H 2 SO 4 ).
[비교예 1]Comparative Example 1
실시예 1에서 에칭액을 과산화수소(H2O2)와 황산(H2SO4) 대신 염화제이구리(CuCl2·2H2O)와 염산(HCl)을 포함한 것을 제외하고, 나머지는 동일하게 하였다. The etching solution in Example 1 was the same except that the copper chloride (CuCl 2 · 2H 2 O) and hydrochloric acid (HCl) instead of hydrogen peroxide (H 2 O 2 ) and sulfuric acid (H 2 SO 4 ).
[실험예 1]Experimental Example 1
실시예 1 내지 실시예 4 및 비교예 1의 전해구리도금조(40)에서 전해구리도금을 각각 4회 반복 실시하였으며, 폐 에칭액에 남아 있는 구리의 양을 측정하여 표 1에 나타내었다.The electrolytic copper plating was repeated four times in the electrolytic copper plating tanks 40 of Examples 1 to 4 and Comparative Example 1, respectively, and the amounts of copper remaining in the waste etching solution were measured and shown in Table 1 below.
폐 에칭액에 있는 Cu농도(g/ℓ)Cu concentration in waste etching solution (g / ℓ) 남아있는 Cu농도 (g/ℓ)Remaining Cu Concentration (g / ℓ)
1One 22 33 44
실시예 1Example 1 34.934.9 3.23.2 3.13.1 2.32.3 1.91.9
실시예 2Example 2 33.933.9 2.92.9 2.22.2 1.91.9 1.31.3
실시예 3Example 3 35.935.9 3.63.6 3.23.2 2.62.6 2.22.2
실시예 4Example 4 34.634.6 3.83.8 3.53.5 2.92.9 2.32.3
비교예 1Comparative Example 1 36.636.6 25.525.5 18.718.7 10.510.5 9.79.7
표 1에 의하면, 실시예 1 내지 실시예 4는 비교예 1에 비하여 구리 회수율이 매우 우수한 것을 확인할 수 있다.According to Table 1, it can confirm that Example 1 thru | or Example 4 are very excellent in copper recovery compared with the comparative example 1.
[부호의 설명][Description of the code]
10 : 에칭조 20 : 에칭액 10: etching bath 20: etching solution
30 : 광센서 40 : 전해구리도금조30: optical sensor 40: electrolytic copper plating bath
50 : 폐 에칭액 60 : 음극전극50: waste etching solution 60: cathode electrode
70 : 양극전극 80 : 정류기70 anode electrode 80 rectifier
90 : 제어부90: control unit
110 : 에칭조 120 : 에칭액110: etching bath 120: etching solution
130 : 양극전극 140 : 음극전극130: anode electrode 140: cathode electrode
150 : 정류기 160 : 광센서150: rectifier 160: optical sensor
170 : 제어부170: control unit

Claims (2)

  1. 에칭공정이 수행되는 에칭조; An etching bath in which an etching process is performed;
    상기 에칭조를 채우며, 에칭력을 갖는 에칭액; An etching liquid filling the etching bath and having an etching force;
    상기 에칭조에 배치되어 구리 농도를 측정하는 광센서; An optical sensor disposed in the etching bath to measure copper concentration;
    상기 에칭조에서 생성된 폐 에칭액을 재생시키기 위한 전해구리도금조;An electrolytic copper plating tank for regenerating the waste etching solution generated in the etching bath;
    상기 전해구리도금조에 배치된 음극전극 및 양극전극;A cathode electrode and an anode electrode disposed in the electrolytic copper plating bath;
    상기 음극전극과 양극전극을 연결하여 전류를 인가하는 정류기; 및A rectifier connecting the cathode electrode and the anode electrode to apply a current; And
    상기 에칭조와 정류기를 제어하기 위한 제어부; A control unit for controlling the etching bath and the rectifier;
    를 포함하되.Including but not limited to.
    상기 양극전극은 티타늄 표면에 이리듐을 포함한 백금족 산화물이 코팅된 불용성 전극을 사용하며,The anode electrode uses an insoluble electrode coated with a platinum group oxide including iridium on the titanium surface,
    에칭액의 구리 농도를 감지하는 광센서는 구리 농도가 일정 수준을 초과할 경우 제어부에 신호를 송출하는,The optical sensor for detecting the copper concentration of the etchant sends a signal to the controller when the copper concentration exceeds a certain level,
    에칭액 재생 및 구리 회수 장치.Etching solution regeneration and copper recovery device.
  2. 제 1항에 있어서,The method of claim 1,
    상기 에칭액은 과산화수소(H2O2)와 황산(H2SO4), 과산화이중황산나트륨(Na2S2O8)과 황산(H2SO4), 과산화이중황산칼륨(K2S2O8)과 황산(H2SO4) 및 과산화황산수소칼륨(KHSO4)과 황산(H2SO4)으로 구성된 군으로부터 선택된 어느 하나를 포함하는,The etchant is hydrogen peroxide (H 2 O 2 ) and sulfuric acid (H 2 SO 4 ), sodium bisulfate (Na 2 S 2 O 8 ) and sulfuric acid (H 2 SO 4 ), potassium persulfate (K 2 S 2 O 8 ) And any one selected from the group consisting of sulfuric acid (H 2 SO 4 ) and potassium hydrogen peroxide (KHSO 4 ) and sulfuric acid (H 2 SO 4 ),
    에칭액 재생 및 구리 회수 장치.Etching solution regeneration and copper recovery device.
PCT/KR2016/008699 2016-03-14 2016-08-08 Device and method for regenerating etching liquid and recovering copper WO2017159933A1 (en)

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JPH10140386A (en) * 1996-11-11 1998-05-26 Chuo Seisakusho Ltd Copper electrodeposition vessel for alkaline etchant regenerating device
JP2000119891A (en) * 1998-10-07 2000-04-25 Zenken:Kk Treating and recovering device for aqueous solution containing copper, sulfuric acid and nitric acid
JP2005187865A (en) * 2003-12-25 2005-07-14 Nittetsu Mining Co Ltd Method and apparatus for recovering copper from copper etching waste solution by electrolysis
KR101291554B1 (en) * 2012-03-23 2013-08-08 (주)화백엔지니어링 Device and method for regeneration of etchant and copper recovery using rgb color sensor
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