JPH02122084A - Method for controlling concentration of copper in hydrogen peroxide-sulfuric acid etching solution - Google Patents
Method for controlling concentration of copper in hydrogen peroxide-sulfuric acid etching solutionInfo
- Publication number
- JPH02122084A JPH02122084A JP27363888A JP27363888A JPH02122084A JP H02122084 A JPH02122084 A JP H02122084A JP 27363888 A JP27363888 A JP 27363888A JP 27363888 A JP27363888 A JP 27363888A JP H02122084 A JPH02122084 A JP H02122084A
- Authority
- JP
- Japan
- Prior art keywords
- etching
- copper
- soln
- etching solution
- sulfuric acid
- 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.)
- Pending
Links
- 238000005530 etching Methods 0.000 title claims abstract description 42
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 42
- 229910052802 copper Inorganic materials 0.000 title claims description 42
- 239000010949 copper Substances 0.000 title claims description 42
- 238000000034 method Methods 0.000 title claims description 10
- XEMZLVDIUVCKGL-UHFFFAOYSA-N hydrogen peroxide;sulfuric acid Chemical compound OO.OS(O)(=O)=O XEMZLVDIUVCKGL-UHFFFAOYSA-N 0.000 title 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 10
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 2
- 229910001431 copper ion Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 229910001220 stainless steel Inorganic materials 0.000 abstract 1
- 239000010935 stainless steel Substances 0.000 abstract 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 12
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 12
- 238000011084 recovery Methods 0.000 description 12
- 239000007788 liquid Substances 0.000 description 10
- 238000010586 diagram Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 1
- 239000003788 bath preparation Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/382—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
Landscapes
- ing And Chemical Polishing (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は印刷配線板の製造工程において銅表面の密着性
を向上させる為に銅表面を疎通するエツチング液の銅濃
度制御方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for controlling the copper concentration of an etching solution that passes through a copper surface in order to improve the adhesion of the copper surface in the manufacturing process of printed wiring boards.
従来、この種の銅濃度制御法は銅濃度がある規定値に達
したら浴を更新する使い捨て法、もしくは銅の液温によ
る溶解量の差を利用して硫酸銅として銅を回収する硫酸
銅回収装置による銅濃度制御が行われていた。Conventionally, this type of copper concentration control method has been a disposable method in which the bath is renewed when the copper concentration reaches a certain specified value, or a copper sulfate recovery method in which copper is recovered as copper sulfate by utilizing the difference in the amount of dissolved copper depending on the liquid temperature. Copper concentration was controlled by equipment.
溶解度差による銅回収システムの概念図を第２図に示す
。エツチング液槽ｌは、例えば５０℃と高温に保ち硫酸
銅回収タンク１４はチラー１２゜冷水タンク１３を用い
例えば２０℃の低温に保ち常にエツチング液槽ｌと硫酸
銅回収タンク１４間を循環させる。エツチング液槽１は
高温のため硫酸銅は溶解しやすく、硫酸銅回収槽１４は
低温のため二層間の液温差に相当する硫酸銅が結晶とし
て析出し沈澱する。硫酸銅回収タンク１４の底に沈澱し
た硫酸銅結晶はスクリューコンベア１５にて液切りしな
がらタンク外へ排出され回収される。Figure 2 shows a conceptual diagram of a copper recovery system based on solubility differences. The etching liquid tank 1 is kept at a high temperature of, for example, 50°C, and the copper sulfate recovery tank 14 is kept at a low temperature of 20°C, for example, using a chiller 12° cold water tank 13, and circulation is constantly made between the etching liquid tank 1 and the copper sulfate recovery tank 14. Since the etching liquid tank 1 has a high temperature, copper sulfate is easily dissolved, and the copper sulfate recovery tank 14 has a low temperature, so copper sulfate corresponding to the difference in liquid temperature between the two layers precipitates as crystals. The copper sulfate crystals deposited at the bottom of the copper sulfate recovery tank 14 are drained by a screw conveyor 15 and discharged out of the tank and recovered.
上述した従来の銅濃度制御法には以下のような欠点を有
していた。The conventional copper concentration control method described above had the following drawbacks.
（１）使い捨ての場合
ア、銅濃度がある規定量に達する度に建浴作業及び廃液
処理が生じる。(1) In the case of disposable use A. Every time the copper concentration reaches a certain specified amount, bath preparation work and waste liquid treatment are required.
イ、銅濃度が常に一定ではなく０から規定量の間で変化
するためエツチング速度が微妙に変化する。B. Since the copper concentration is not always constant but varies between 0 and a specified amount, the etching rate changes slightly.
（２）溶解度差によるリサイクルの場合ア、銅濃度を一
定に保つことは可能だが制御できる銅濃度がある程度限
定される。(2) In the case of recycling based on solubility difference a. It is possible to keep the copper concentration constant, but the controllable copper concentration is limited to some extent.
イ、溶解度差を利用するため、エツチング液の温度を高
温（約５０℃）にする必要がある。B. In order to take advantage of the solubility difference, it is necessary to raise the temperature of the etching solution to a high temperature (approximately 50°C).
つ１回収装置が大掛りであり、また構造上硫酸銅が目詰
りしやすく、維持・管理工数がかかる。The recovery equipment is large-scale, and due to its structure, copper sulfate tends to clog easily, requiring many man-hours for maintenance and management.
本発明の目的はかかる従来欠点を除去したエツチング液
における銅濃度制御法を提供することにある。An object of the present invention is to provide a method for controlling the copper concentration in an etching solution that eliminates such conventional drawbacks.
本発明によればエツチング液においてエツチング液専用
電解槽２を設け常時液を循環させ該電解槽にて不活性電
極９を用い電解することによりエツチング液中の銅イオ
ンを金属銅１１として析出・回収しエツチング液中の濃
度を常に一定に保つ銅濃度制御法が得られる。According to the present invention, an electrolytic bath 2 dedicated to the etching solution is provided for the etching solution, and the solution is constantly circulated, and electrolysis is carried out using an inert electrode 9 in the electrolytic bath, thereby depositing and recovering copper ions in the etching solution as metallic copper 11. A method for controlling the copper concentration can be obtained that keeps the concentration in the etching solution constant.
次に、本発明の一実施例について図面を参照して説明す
る。第１図は本発明の一実施例である電解による銅回収
装置システムの概念図である。まずエツチング液層１の
ドレンからエツチング液の液面より高い位置に設置した
電解槽２ヘボンブにてエツチング液を移送する。電解槽
２にはオーバーフロー機構も設け、オーバーフローした
エツチング液は落差にてエツチング液層ｌへ戻るように
配管する。また、エツチング液の補充液である過酸化水
素水、硫酸、添加剤のそれぞれの補充ボア フト整流器
７の制御用パソコン６ヘコントローラー８から信号を送
れるように配線する。Next, an embodiment of the present invention will be described with reference to the drawings. FIG. 1 is a conceptual diagram of a copper recovery system using electrolysis, which is an embodiment of the present invention. First, the etching solution is transferred from the drain of the etching solution layer 1 to the electrolytic cell 2 installed at a higher position than the level of the etching solution. The electrolytic cell 2 is also provided with an overflow mechanism, and piping is provided so that the overflowing etching liquid returns to the etching liquid layer l via a head. In addition, wiring is provided so that signals can be sent from the controller 8 to the personal computer 6 for controlling the replenishment boreft rectifier 7 for each of the replenishing solutions of hydrogen peroxide, sulfuric acid, and additives for the etching solution.
電解槽ではアノード９に例えば白金電極等の不活性電極
を用いカノード１０には銅析出用のサス板等を用いて電
解することによりカソード上に金属銅１１が析出する。In the electrolytic cell, an inert electrode such as a platinum electrode is used as the anode 9 and a suspension plate for depositing copper is used as the cathode 10 to conduct electrolysis, thereby depositing metal copper 11 on the cathode.
電解時の電流密度は被エツチング面積より銅エツチング
量を計算し、それと同量の銅回収を行うように設定して
おく。その後、エツチング液組成コントローラー８によ
る銅濃度変化をパソコン６で処理し、常に一定の銅濃度
を維持するように電流密度を変化させる。The current density during electrolysis is set so that the amount of copper etched is calculated from the area to be etched, and the same amount of copper is recovered. Thereafter, changes in the copper concentration caused by the etching solution composition controller 8 are processed by the personal computer 6, and the current density is changed so as to always maintain a constant copper concentration.
以上説明したように本発明により次の効果がある。 As explained above, the present invention has the following effects.
（１） 消費された分の過酸化水素水を補充すること
によりエツチング液の寿命が半永久的であり、液交換が
不要であり廃液処理も不要である。(1) The life of the etching solution is semi-permanent by replenishing the amount of hydrogen peroxide that has been consumed, and there is no need to replace the solution or treat waste solution.
（２）銅濃度を一定に保てるために、銅濃度の影響によ
るエツチング速度の変化がない。(2) Since the copper concentration can be kept constant, there is no change in the etching rate due to the influence of the copper concentration.
（３）エツチングされた銅は金属銅１１として回収され
るため売却可である。(3) The etched copper is recovered as metal copper 11 and can be sold.
（４）電解による銅濃度制御のため、電流密度等を変更
することにより容易に銅濃度を変えて管理できる。(4) Since the copper concentration is controlled by electrolysis, the copper concentration can be easily changed and managed by changing the current density, etc.
（５）電解による銅濃度制御のためエツチング液の液温
を銅回収システムのために変更する必要はなく、エツチ
ング量に対する最適値が設定できる。(5) Since the copper concentration is controlled by electrolysis, there is no need to change the temperature of the etching solution for the copper recovery system, and the optimum value for the etching amount can be set.
（６）本発明による電解槽２はエツチング液槽１に対し
１７１０以下でも十分その効果を発揮できるため狭い面
積でシステムが組める。(6) The electrolytic cell 2 according to the present invention can sufficiently exhibit its effect even if the electrolytic cell 2 has an etching temperature of 1,710 or less compared to the etching liquid tank 1, so that a system can be constructed in a small area.
（７）銅濃度を低濃度で管理することにより硫酸銅の結
晶が目詰りすることもなく維持・管理が容易である。(7) By controlling the copper concentration at a low concentration, copper sulfate crystals do not become clogged and maintenance and management are easy.
（８）電解反応によって硫酸が発生するため、理論的に
は硫酸の補充を０にすることができる。(8) Since sulfuric acid is generated by the electrolytic reaction, it is theoretically possible to reduce the amount of sulfuric acid replenishment to zero.
第１図は本発明の電解による銅回収装置システムの概念
図、第２図は従来技術の溶解度差による銅回収装置シス
テムの概念図である。
１・・・・・・エツチング液槽、２・・・・・・電解槽
、３・・・・・・過酸化水素水タンク、４・・・・・・
硫酸タンク、５・・・・・・添加剤タンク、６・・・・
・・パーソナルコンピュータ、７・・・・・・整流器、
８・・・・・・コントローラー ９・・・・・・アノー
ド、１０・・・・・・カソード、１１・・・・・・析出
銅（金属銅）、１２・・・・・・チラー １３・旧・・
冷水タンク、１４・・・・・・硫酸銅回収タンク、１５
・・・・・・スクリューコンベア。FIG. 1 is a conceptual diagram of a copper recovery system using electrolysis according to the present invention, and FIG. 2 is a conceptual diagram of a conventional copper recovery system using solubility differences. 1... Etching liquid tank, 2... Electrolytic tank, 3... Hydrogen peroxide tank, 4...
Sulfuric acid tank, 5... Additive tank, 6...
...Personal computer, 7... Rectifier,
8...Controller 9...Anode, 10...Cathode, 11...Deposited copper (metallic copper), 12...Chiller 13. Old...
Cold water tank, 14... Copper sulfate recovery tank, 15
・・・・・・Screw conveyor.
Claims (1)
液と略す。）においてエッチング液専用電解槽２（以下
電解槽と略す。）を設け常時液を循環させ該電解槽２に
て不活性電極９を用い電解することによりエッチング液
中の銅イオンを金属銅１１として析出、回収しエッチン
グ液中の銅濃度を常に一定に保つことを特徴とする銅濃
度制御法。An electrolytic tank 2 (hereinafter referred to as the electrolytic tank) dedicated to the etching solution is prepared using a hydrogen peroxide/sulfuric acid based copper etching solution (hereinafter referred to as the "etching solution"), and the solution is constantly circulated to form an inert electrode 9 in the electrolytic tank 2. A method for controlling copper concentration, characterized in that copper ions in an etching solution are precipitated and recovered as metallic copper 11 by electrolysis using a method of electrolysis, and the copper concentration in the etching solution is always kept constant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27363888A JPH02122084A (en) | 1988-10-28 | 1988-10-28 | Method for controlling concentration of copper in hydrogen peroxide-sulfuric acid etching solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27363888A JPH02122084A (en) | 1988-10-28 | 1988-10-28 | Method for controlling concentration of copper in hydrogen peroxide-sulfuric acid etching solution |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02122084A true JPH02122084A (en) | 1990-05-09 |
Family
ID=17530482
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27363888A Pending JPH02122084A (en) | 1988-10-28 | 1988-10-28 | Method for controlling concentration of copper in hydrogen peroxide-sulfuric acid etching solution |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02122084A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20030006809A (en) * | 2001-07-16 | 2003-01-23 | (주)오알켐 | Composite in order to recycle etchant which can continuously operate and supply, and the supply method |
| KR100416989B1 (en) * | 2001-07-16 | 2004-02-05 | (주)오알켐 | Computerized automatic etchant dosing system |
| WO2011050488A2 (en) * | 2009-10-27 | 2011-05-05 | Juan Horacio Gonzalez Reyes | System for the electro-production of copper |
| CN102510669A (en) * | 2011-11-09 | 2012-06-20 | 金悦通电子（翁源）有限公司 | Method for chemically cleaning copper surface of substrate |
| CN109023375A (en) * | 2018-08-30 | 2018-12-18 | 深圳市华星光电技术有限公司 | Etch fluid circulation and Etaching device |
-
1988
- 1988-10-28 JP JP27363888A patent/JPH02122084A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20030006809A (en) * | 2001-07-16 | 2003-01-23 | (주)오알켐 | Composite in order to recycle etchant which can continuously operate and supply, and the supply method |
| KR100416989B1 (en) * | 2001-07-16 | 2004-02-05 | (주)오알켐 | Computerized automatic etchant dosing system |
| WO2011050488A2 (en) * | 2009-10-27 | 2011-05-05 | Juan Horacio Gonzalez Reyes | System for the electro-production of copper |
| WO2011050488A3 (en) * | 2009-10-27 | 2011-07-07 | Juan Horacio Gonzalez Reyes | System for the electro-production of copper |
| CN102510669A (en) * | 2011-11-09 | 2012-06-20 | 金悦通电子（翁源）有限公司 | Method for chemically cleaning copper surface of substrate |
| CN109023375A (en) * | 2018-08-30 | 2018-12-18 | 深圳市华星光电技术有限公司 | Etch fluid circulation and Etaching device |
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