JP3193152B2 - Metal etching method - Google Patents
Metal etching methodInfo
- Publication number
- JP3193152B2 JP3193152B2 JP26472092A JP26472092A JP3193152B2 JP 3193152 B2 JP3193152 B2 JP 3193152B2 JP 26472092 A JP26472092 A JP 26472092A JP 26472092 A JP26472092 A JP 26472092A JP 3193152 B2 JP3193152 B2 JP 3193152B2
- Authority
- JP
- Japan
- Prior art keywords
- etching
- solution
- hydrogen chloride
- supply
- oxidation
- 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.)
- Expired - Lifetime
Links
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
- 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
- C23F1/08—Apparatus, e.g. for photomechanical printing surfaces
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Weting (AREA)
- ing And Chemical Polishing (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は金属のエッチング方法に
関し、更に詳しくは塩化第二鉄水溶液を使用する銅、
鉄、ニッケルなどの金属及びこれらの合金の連続エッチ
ング方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for etching metal, and more particularly, to copper using an aqueous ferric chloride solution.
The present invention relates to a method for continuously etching metals such as iron and nickel and alloys thereof.
【０００２】[0002]
【従来の技術】塩化第二鉄水溶液による銅のエッチング
はエッチングが進行するに従って次式の反応によりエッ
チング液中の銅イオン及び第一鉄イオンが増大し、それ
に伴ってエッチング速度が低下する。 Ｆｅ+++＋Ｃｕ0→Ｆｅ++＋Ｃｕ+ Ｆｅ+++＋Ｃｕ+→Ｆｅ++＋Ｃｕ++ 2. Description of the Related Art In the etching of copper with an aqueous ferric chloride solution, as the etching progresses, copper ions and ferrous ions in the etching solution increase by the following reaction, and the etching rate decreases accordingly. Fe +++ + Cu 0 → Fe ++ + Cu + Fe +++ + Cu + → Fe ++ + Cu ++
【０００３】この問題を解決するため従来の塩化第二鉄
水溶液による銅の連続的エッチングにおいては、エッチ
ングの有効距離を長くし実用的なライン速度を確保する
方法が採られていた。しかしながら、この方法において
は設備費が高くなること、薬液を多量に必要とするなど
の欠点があった。これらの欠点は銅以外の金属のエッチ
ングについても同様である。In order to solve this problem, in the conventional continuous etching of copper with an aqueous solution of ferric chloride, a method has been adopted in which the effective distance of etching is increased to ensure a practical line speed. However, this method has disadvantages such as an increase in equipment cost and a large amount of a chemical solution. These drawbacks apply to the etching of metals other than copper.
【０００４】このような欠点を解決する方法として、塩
素酸塩と塩化水素をエッチング液に供給し、エッチング
により生成した塩化第一鉄を塩化第二鉄に戻し、エッチ
ング性能を回復する方法が特開昭64−87788号公報、特
開平２−14968号公報に示されており、更に、塩化水素
の低濃度管理が提案されている。As a method of solving such a drawback, a method of supplying chlorate and hydrogen chloride to an etching solution, returning ferrous chloride generated by etching to ferric chloride, and restoring etching performance is a feature. It is disclosed in Japanese Unexamined Patent Publication (Kokai) No. 64-87788 and Japanese Unexamined Patent Publication (Kokai) No. 2-14968, and furthermore, low concentration control of hydrogen chloride has been proposed.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、上記の
方法では今日におけるプリント配線板回路の微細化、リ
ードフレームの多ピン化は急速に進み対応が困難となっ
ている。すなわち、従来のエッチング方法においては、
エッチング作業中に発生するエッチング液組成制御の外
乱因子に対処する充分な方法はなく、緻密な液制御は不
可能であった。However, in the above-mentioned method, the miniaturization of the printed wiring board circuit and the increase in the number of pins of the lead frame are rapidly progressing today, and it is difficult to cope with the problem. That is, in the conventional etching method,
There is no sufficient method to cope with a disturbance factor in controlling the composition of the etching solution generated during the etching operation, and precise control of the solution is impossible.
【０００６】従って、本発明の目的は、エッチング液組
成制御に対する外乱因子を取り除くための手段を備えて
なる制御装置を使用する金属のエッチング方法を提供す
ることにある。Accordingly, it is an object of the present invention to provide a method for etching metal using a control device having means for removing a disturbance factor for controlling the composition of an etching solution.
【０００７】[0007]
【課題を解決するための手段】本発明者らはエッチング
作業中に発生するエッチング液制御に対する外乱因子を
追求し、この外乱因子を取り除くいくつかの手段を見出
し、エッチング液の組成を緻密に制御することができ、
それによって微細パターンのエッチングが可能な金属の
エッチング方法を完成するに至った。Means for Solving the Problems The present inventors have pursued a disturbance factor with respect to the control of an etching solution generated during an etching operation, found some means for removing the disturbance factor, and precisely controlled the composition of the etching solution. Can be
As a result, a metal etching method capable of etching a fine pattern has been completed.
【０００８】即ち、本発明は、塩素酸ナトリウム、塩素
酸カリウム及び塩素酸カルシウムからなる群から選択さ
れる塩素酸塩１モルに対し、塩化水素６〜９モル、塩化
第二鉄２．５〜３０モルの割合で塩素酸塩水溶液、塩化
水素水溶液、塩化第二鉄水溶液を供給するにあたり、酸
化還元電位・塩化水素濃度・比重及び温度検出部におい
て、エッチング液の酸化還元電位を検知し、この検知結
果に基づき上記水溶液をエッチング液へ供給して予め設
定された酸化還元電位を連続的に維持し、比重を検知
し、この検知結果に基づき水をエッチング液へ供給して
予め設定された比重を連続的に維持することからなる塩
化第二鉄水溶液を用いる金属のエッチング方法におい
て、制御装置が所定温度以下では新液及び／または水の
供給を禁止する手段を備えてなることを特徴とする金属
のエッチング方法であり、本発明方法によれば、これま
での塩化第二鉄水溶液を使用する金属のエッチングに関
する不具合を一挙に解決する。また、本発明方法では、
酸化還元電位・塩化水素濃度・比重及び温度検出部にお
いて、塩化水素含量を検知し、この検知結果に基づき塩
化水素を含む水溶液をエッチング液へ供給して予め設定
された塩化水素濃度を連続的に維持することもできる。 That is, the present invention relates to 6 to 9 moles of hydrogen chloride and 2.5 to 2.5 moles of ferric chloride to 1 mole of a chlorate selected from the group consisting of sodium chlorate, potassium chlorate and calcium chlorate. When supplying the chlorate aqueous solution, the hydrogen chloride aqueous solution, and the ferric chloride aqueous solution at a ratio of 30 mol, the acid
Oxidation / reduction potential, hydrogen chloride concentration, specific gravity and temperature
Te detects the redox potential of the etchant, the detection result the aqueous solution based on the maintaining redox potential set in advance is supplied to the etching liquid is continuously detects the specific gravity, the result of the detection In a metal etching method using an aqueous solution of ferric chloride, which comprises continuously supplying water to an etching solution and maintaining a predetermined specific gravity based on the water, the control device controls a new solution and / or water at a predetermined temperature or lower. A method for etching a metal, comprising a means for inhibiting the supply of the metal. According to the method of the present invention, the problems associated with the etching of a metal using an aqueous ferric chloride solution can be solved at once. In the method of the present invention,
Redox potential, hydrogen chloride concentration, specific gravity and temperature detection
To detect the content of hydrogen chloride,
Supply an aqueous solution containing hydrogen fluoride to the etchant and set it in advance
The determined hydrogen chloride concentration can be continuously maintained.
【０００９】本発明方法の第一の特長は、所定温度以下
では新液及び／または水の供給を自動的に禁止すること
により、不必要な新液及び／または水の供給を避け、エ
ッチング液の組成変化を防ぐことにある。すなわち、酸
化還元電位、塩化水素濃度に拘わる電位は温度により変
化する。このため、所定の温度以下で制御装置を稼働さ
せると酸化還元電位、塩化水素濃度に拘わる電位が本来
の値より低い値となり、余分な新液供給が行われ、エッ
チング液組成、エッチング性能も変化するが、本発明で
は制御装置に所定温度以下では新液及び／または水の供
給を禁止する手段を組み込み、温度変化による不必要な
エッチング液組成変化を防止するものである。The first feature of the method of the present invention is that the supply of a new solution and / or water is automatically prohibited at a temperature lower than a predetermined temperature, so that unnecessary supply of a new solution and / or water is avoided and an etching solution is unnecessary. In order to prevent the composition change. That is, the oxidation-reduction potential and the potential related to the hydrogen chloride concentration change with temperature. Therefore, when the control device is operated at a predetermined temperature or lower, the oxidation-reduction potential and the potential related to the hydrogen chloride concentration become lower than the original values, an extra supply of a new solution is performed, and the etching solution composition and etching performance also change. However, in the present invention, means for inhibiting the supply of a new solution and / or water below a predetermined temperature is incorporated in the control device to prevent unnecessary change in the composition of the etching solution due to a change in temperature.
【００１０】また、比重も温度により変化するため、上
記と同様に所定温度以下では水の供給を禁止する手段が
必要である。Further, since the specific gravity also changes depending on the temperature, it is necessary to provide a means for inhibiting the supply of water at a temperature lower than the predetermined temperature as described above.
【００１１】本発明方法の第二の特長は、新液の供給を
所定時間行った後、所定時間供給を休止することにより
新液の過剰供給を防止することにある。すなわち、新液
供給の後に短時間で槽内のエッチング液の組成を均一に
する工夫は種々行われているが限界がある。これは本来
必要である新液の供給が行われても、検出される値は制
御設定値より低く、供給が継続されることを意味する。A second feature of the method of the present invention resides in that the supply of the new liquid is stopped for a predetermined time after the supply of the new liquid for a predetermined time, thereby preventing the excessive supply of the new liquid. That is, various attempts have been made to make the composition of the etching solution in the tank uniform in a short time after the supply of the new solution, but there is a limit. This means that even if the supply of a new liquid that is originally required is performed, the detected value is lower than the control set value, and the supply is continued.
【００１２】本発明方法では、所定時間新液を供給した
後で検出される値が設定値以下であっても所定時間供給
を休止し、この後の値が設定値以下であればこの操作を
自動的に繰り返す手段を制御装置に組み込むことにより
上記問題を解決した。In the method of the present invention, the supply is stopped for a predetermined time even if the value detected after supplying the new liquid for a predetermined time is equal to or less than a set value. The above problem was solved by incorporating a means for automatically repeating in the control device.
【００１３】本発明方法の第三の特長は、エッチング温
度を変更するに際して、酸化還元電位、塩酸濃度に拘わ
る電位を自動的に変更することにある。A third feature of the method of the present invention resides in that, when the etching temperature is changed, the oxidation-reduction potential and the potential relating to the concentration of hydrochloric acid are automatically changed.
【００１４】エッチング対象の金属、求められるエッチ
ング表面平滑度、生産性の見合いでエッチング温度の変
更が行われる。一方、前記したように同一組成のエッチ
ング液でも温度により酸化還元電位、塩化水素濃度に拘
わる電位が変化する。例えば、温度を上げると酸化還元
電位の検出値は高くなり、エッチングを行うことで次第
に下がり、制御設定値でコントロールされることになる
が、この間液組成は逐次変化することになり、正確なエ
ッチングを行うことが困難になる。エッチング温度を下
げた場合もエッチング液組成が変化する。The etching temperature is changed in consideration of the metal to be etched, the required etching surface smoothness, and the productivity. On the other hand, as described above, even with an etching solution having the same composition, the oxidation-reduction potential and the potential related to the hydrogen chloride concentration change depending on the temperature. For example, when the temperature is increased, the detection value of the oxidation-reduction potential is increased, and the detected value is gradually decreased by performing the etching, and is controlled by the control set value. Will be difficult to do. Even when the etching temperature is lowered, the composition of the etching solution changes.
【００１５】本発明方法では、温度変化に対する酸化還
元電位、塩化水素濃度に拘わる指数の変化を測定し、予
めこの値を制御装置に記憶させておき、温度制御設定値
の変更に対応して自動的に酸化還元電位、塩化水素濃度
に拘わる電位の制御設定値を変更させるものである。In the method of the present invention, the change in the index relating to the oxidation-reduction potential and the hydrogen chloride concentration with respect to the temperature change is measured, and this value is stored in the control device in advance, and the automatic control is performed in response to the change in the temperature control set value. Specifically, the control set value of the potential related to the oxidation-reduction potential and the concentration of hydrogen chloride is changed.
【００１６】比重についても同様に制御設定値を自動変
更することが好ましいが、エッチング温度の変更は通常
５〜１０℃であり、この温度変化に対応する比重の変化
幅は小さいため変更しなくても良い。Similarly, it is preferable to automatically change the control set value for the specific gravity. However, the change in the etching temperature is usually 5 to 10 ° C., and the change in the specific gravity corresponding to this temperature change is small. Is also good.
【００１７】本発明方法の第四の特長は、スプレーポン
プ及びエッチング液循環ポンプを設置したエッチング装
置を使用し、酸化還元電位・塩化水素濃度・比重及び温
度検出部へのエッチング液の送液を上記ポンプのいずれ
かを使用して行う際して、上記検出部へのエッチング液
の送液を行わない方のポンプが停止した場合には新液の
供給を自動的に禁止することにある。The fourth feature of the method of the present invention is that an etching apparatus equipped with a spray pump and an etchant circulation pump is used to perform etching on a redox potential / hydrogen chloride concentration / specific gravity and temperature detection unit. the liquid feed of the liquid on the occasion performed using one of the pumps, the etching liquid to the detection unit
In the case where the pump that does not send the liquid stops, the supply of the new liquid is automatically prohibited.
【００１８】上記２台のポンプのうち酸化還元電位・塩
化水素濃度・比重及び温度検出部への液送りポンプが停
止した場合には制御装置がこれを検知し、新液供給を自
動的に停止する方法は一般に行われている。When the liquid feed pump to the redox potential / hydrogen chloride concentration / specific gravity and temperature detecting section of the two pumps is stopped, the control device detects this and automatically stops the supply of the new liquid. The way to do it is generally done.
【００１９】本発明方法では、他方のポンプが停止した
場合にも新液供給を禁止するものであるが、これは１台
でもポンプが停止すると液の撹拌が弱くなり、槽内のエ
ッチング液組成の均一性が失われ、多くの場合は新液の
過剰供給が行われることを防止するものである。In the method of the present invention, the supply of a new solution is prohibited even when the other pump is stopped. However, when one pump is stopped, the stirring of the solution becomes weak, and the composition of the etching solution in the tank is reduced. Is lost, and in many cases, oversupply of fresh liquid is prevented.
【００２０】本発明における酸化還元電位の検知は通常
のＯＲＰ電極を使用して行えば良く、塩化水素濃度の検
知はガラス電極の発生電位を測定すれば良い。In the present invention, the detection of the oxidation-reduction potential may be performed using a normal ORP electrode, and the detection of the hydrogen chloride concentration may be performed by measuring the generated potential of the glass electrode.
【００２１】酸化還元電位の検知結果で、供給する塩素
酸塩と塩化水素の供給比率は塩素酸塩１モル当たり、６
〜９モルとするのが良いが、更に好ましくは６〜７モル
とするのが良い。塩化水素濃度検知結果により行われる
塩化水素含有水溶液の供給は、エッチング液中の塩化第
一鉄が空気酸化により塩化第二鉄になる際に消費される
塩化水素の補給のために行うものであり、制御設定値を
選択することでエッチング液中の塩化水素濃度を３％以
下とすることが好ましい。According to the detection result of the oxidation-reduction potential, the supply ratio of chlorate and hydrogen chloride to be supplied is 6 per mole of chlorate.
The amount is preferably from 9 to 9 mol, and more preferably from 6 to 7 mol. The supply of the hydrogen chloride-containing aqueous solution based on the hydrogen chloride concentration detection result is performed to replenish hydrogen chloride consumed when ferrous chloride in the etching solution becomes ferric chloride by air oxidation. It is preferable that the concentration of hydrogen chloride in the etching solution be 3% or less by selecting a control setting value.
【００２２】通常、レジストとしてドライフィルムを使
用し、プリント配線板銅箔のエッチングを行う場合に
は、塩化水素濃度を１％前後とし、ニッケル合金、ニッ
ケル、クロム合金を対象とした場合には０.２％以下と
すると好結果が得られる。Normally, when a dry film is used as a resist and a copper foil of a printed wiring board is etched, the concentration of hydrogen chloride is set to about 1%, and when a nickel alloy, nickel or chromium alloy is used, 0 is used. Good results are obtained when the content is less than .2%.
【００２３】塩化第二鉄水溶液の供給はエッチングによ
り増加するエッチング液中の銅、ニッケルなどの金属濃
度を一定に調節するために行うものであり、対象金属、
要求されるエッチング性能により適宜供給量を変えれば
良く、例えば鉄または鉄の含量の高い鉄系合金の場合は
少なくし、Ｃｒ含量が上がるとエッチング性能が低下す
るステンレス材が対象となる場合は多く供給すると良
い。実用上は塩素酸塩１モルに対し、２.５〜３０モル
とするのが好ましい。The supply of the aqueous ferric chloride solution is carried out in order to keep the concentration of metals such as copper and nickel in the etching solution increased by etching constant.
The supply amount may be appropriately changed depending on the required etching performance.For example, iron or an iron-based alloy having a high iron content is reduced, and if the Cr content is increased, the stainless steel material whose etching performance is reduced is often used. Good to supply. Practically, it is preferably 2.5 to 30 mol per 1 mol of the chlorate.
【００２４】本発明方法で使用する塩素酸塩は水溶液で
供給されるが、その濃度は例えば塩素酸ナトリウムの場
合は３５〜４０％とするのが良い。The chlorate used in the method of the present invention is supplied as an aqueous solution, and its concentration is preferably 35 to 40% for sodium chlorate, for example.
【００２５】塩化水素は３０〜３５％溶液として供給
し、塩化第二鉄は４０〜５０°Ｂｅの水溶液として供給
するのが好ましい。Hydrogen chloride is preferably supplied as a 30-35% solution, and ferric chloride is preferably supplied as an aqueous solution at 40-50 ° Be.
【００２６】予め塩化水素と塩化第二鉄の水溶液を前記
の割合で混合して供給することは、設備の保全、取り扱
い上からみて好ましい。Mixing and supplying the aqueous solution of hydrogen chloride and ferric chloride in the above ratio in advance is preferable from the viewpoint of maintenance and handling of the equipment.
【００２７】また、塩化水素濃度検知による塩化水素水
溶液の供給は金属溶解量を一定に保つために、前記した
割合で塩化第二鉄水溶液と同時に供給するのが良く、塩
化第二鉄との混合物として供給するのがより好ましい。The supply of the aqueous solution of hydrogen chloride by detecting the concentration of hydrogen chloride is preferably carried out simultaneously with the aqueous solution of ferric chloride in the above-mentioned ratio in order to keep the amount of dissolved metal constant. More preferably, it is supplied as.
【００２８】更に、特開平２−149684号公報に記載され
ているアンモニウム塩、アミン、アミン塩例えば塩化ア
ンモニウム、臭化アンモニウム、エチレンジアミン、モ
ノエタノールアミンを添加すると良い。これらの使用量
はエッチング液全量に対し、窒素換算量で０.０２〜３
％とするのが良く、好ましくは０.０５〜２％とするの
が良い。Further, ammonium salts, amines and amine salts described in JP-A-2-149684, for example, ammonium chloride, ammonium bromide, ethylenediamine and monoethanolamine may be added. The amount of these used is 0.02 to 3 in terms of nitrogen based on the total amount of the etching solution.
%, Preferably 0.05 to 2%.
【００２９】エッチング液比重の制御設定値は１.１〜
１.６、好ましくは１.３〜１.５とするのが良い。The control set value of the specific gravity of the etching solution is 1.1 to 1.1.
It is good to be 1.6, preferably 1.3-1.5.
【００３０】エッチング温度は通常行われているように
３０〜７０℃とするのが良く、硬質塩化ビニル製のエッ
チング槽を使用した場合は３０〜５０℃が良い。The etching temperature is preferably in the range of 30 to 70 ° C. as usual, and is preferably 30 to 50 ° C. when a hard vinyl chloride etching tank is used.
【００３１】本発明は浸漬法、スプレー法のいずれでも
実施できるが、スプレー法の場合は圧力を０.５〜５ｋ
ｇ／ｃｍ2とすると良い。The present invention can be carried out by any of the immersion method and the spray method. In the case of the spray method, the pressure is 0.5 to 5 k.
g / cm 2 .
【００３２】次に、本発明方法を実施するに適したエッ
チング装置の１実施態様を図１に従って説明する。図１
中、エッチング槽（１）のエッチング液をエッチング液
送り配管（１２）を通し、エッチング液送り、スプレー
ポンプ（６）により酸化還元電位・塩化水素濃度・比重
及び温度検出部（２）へ送液する。更に、オーバーフロ
ーしたエッチング液をエッチング液戻り配管（１３）に
よりエッチング槽（１）に戻すことによりエッチング液
を循環させる。また、エッチング液送り、スプレーポン
プ（６）と酸化還元電位・塩化水素濃度・比重及び温度
検出部（２）の間において分岐したスプレー用液送り配
管（１４）によりエッチング液をエッチング槽（１）に
スプレー方式で供給させる。更に、エッチング液循環ポ
ンプ（１０）から液循環用配管を介してエッチング液を
循環させる。このエッチング液の循環は常時行われる。Next, one embodiment of an etching apparatus suitable for carrying out the method of the present invention will be described with reference to FIG. FIG.
In the middle, the etchant in the etching tank (1) is passed through the etchant feed pipe (12), the etchant is sent, and the oxidation-reduction potential / hydrogen chloride concentration / specific gravity is applied by the spray pump (6).
And the liquid is sent to the temperature detector (2). Further, the etching solution is circulated by returning the overflowing etching solution to the etching tank (1) through the etching solution return pipe (13). The feed etchant, etching bath etching solution by the liquid feed piping branched spray (14) between the spray pump (6) and the oxidation-reduction potential, hydrogen chloride concentrations, specific gravity and temperature detector (2) (1) To be supplied by a spray method. Further, the etchant is circulated from the etchant circulation pump (10) via a liquid circulation pipe. The circulation of the etching solution is always performed.
【００３３】酸化還元電位・塩化水素濃度・比重及び温
度検出部（２）において、酸化還元電位の測定結果が設
定値以下となったら、制御装置（２０）からの信号を酸
化還元電位に拘わる制御信号配線（Ａ）を介して塩化第
二鉄水溶液送りポンプ（７）に送り、該ポンプを稼働さ
せ、塩化第二鉄水溶液貯槽（３）から塩化第二鉄水溶液
を塩化第二鉄水溶液供給配管（１７）を通してエッチン
グ槽（１）に供給する。同様に、塩化水素水溶液送りポ
ンプ（８）を稼働させ、塩化水素水溶液を塩化水素水溶
液貯槽（４）から塩化水素水溶液供給配管（１８）を通
しエッチング槽（１）へ供給する。更に、塩素酸塩水溶
液送りポンプ（９）を稼働させ、塩素酸塩水溶液を塩素
酸塩水溶液貯槽（５）から塩素酸塩水溶液供給配管（１
６）を通しエッチング槽（１）へ供給する。酸化還元電
位の測定値が設定値以上となったら、酸化還元電位に拘
わる制御信号配線（Ａ）を使用し、各ポンプを停止さ
せ、各水溶液の供給を中止する。In the oxidation-reduction potential / hydrogen chloride concentration / specific gravity and temperature detecting section (2), when the measurement result of the oxidation-reduction potential becomes equal to or less than a set value, the signal from the control device (20) is oxidized. The ferric chloride aqueous solution is sent to a ferric chloride aqueous solution feed pump (7) via a control signal wiring (A) relating to the reduction potential, and the pump is operated to remove the ferric chloride aqueous solution from the ferric chloride aqueous solution storage tank (3). It is supplied to the etching tank (1) through a ferrous aqueous solution supply pipe (17). Similarly, the hydrogen chloride aqueous solution feed pump (8) is operated, and the hydrogen chloride aqueous solution is supplied from the hydrogen chloride aqueous solution storage tank (4) to the etching tank (1) through the hydrogen chloride aqueous solution supply pipe (18). Further, the chlorate aqueous solution feed pump (9) is operated, and the chlorate aqueous solution is supplied from the chlorate aqueous solution storage tank (5) to the chlorate aqueous solution supply pipe (1).
6) and supplied to the etching tank (1). When the measured value of the oxidation-reduction potential becomes equal to or higher than the set value, the control signal wiring (A) relating to the oxidation-reduction potential is used, each pump is stopped, and the supply of each aqueous solution is stopped.
【００３４】塩化水素濃度の測定結果が設定値以下とな
ったら、制御装置(20)からの信号を塩化水素濃度に拘わ
る制御信号配線(Ｂ)を介して塩化第二鉄水溶液送りポン
プ(7)に送り、該ポンプを稼働させ、塩化第二鉄水溶液
貯槽(3)から塩化第二鉄水溶液を塩化第二鉄水溶液供給
配管(17)を通してエッチング槽(1)に供給する。同様
に、塩化水素水溶液送りポンプ(8)を稼働させ、塩化水
素水溶液を塩化水素水溶液貯槽(4)から塩化水素水溶液
供給配管(18)を通しエッチング槽(1)へ供給する。塩化
水素濃度の設定値が設定値以上となったら、塩化水素濃
度に拘わる制御信号配線(Ｂ)を使用し、各ポンプを停止
させ、各水溶液の供給を中止する。When the measurement result of the hydrogen chloride concentration becomes equal to or less than the set value, the signal from the control device (20) is transferred to the ferric chloride aqueous solution feed pump (7) via the control signal wiring (B) relating to the hydrogen chloride concentration. And the pump is operated to supply the ferric chloride aqueous solution from the ferric chloride aqueous solution storage tank (3) to the etching tank (1) through the ferric chloride aqueous solution supply pipe (17). Similarly, the hydrogen chloride solution feed pump (8) is operated to supply the hydrogen chloride solution from the hydrogen chloride solution storage tank (4) to the etching tank (1) through the hydrogen chloride solution supply pipe (18). When the set value of the hydrogen chloride concentration becomes equal to or more than the set value, each pump is stopped using the control signal wiring (B) relating to the hydrogen chloride concentration, and the supply of each aqueous solution is stopped.
【００３５】なお、酸化還元電位・塩化水素濃度・比重
及び温度検出部（２）においては、常時温度の変化が測
定されており、温度変化に伴う酸化還元電位の測定結果
や塩化水素濃度の測定結果の変化においては、上記各水
溶液の供給は行われないような手段が制御装置（２０）
に設けられている。The oxidation-reduction potential / hydrogen chloride concentration / specific gravity
In the temperature detector (2), a change in temperature is always measured, and in the change in the measurement result of the oxidation-reduction potential or the measurement result of the hydrogen chloride concentration accompanying the temperature change, the supply of each of the above aqueous solutions is performed. Control means (20)
It is provided in.
【００３６】また、比重の測定結果が設定値以上となっ
たら、制御装置(20)からの信号を比重に拘わる制御信号
配線(Ｃ)を介して水供給配管電磁弁(11)へ送り、該弁を
開き、水供給配管(16)を通して水を供給する。比重の測
定結果が設定値以下となったら、比重に拘わる制御信号
配線(Ｃ)を使用し、水供給配管電磁弁(11)を閉じ、水の
供給を中止する。When the specific gravity measurement result is equal to or greater than the set value, a signal from the control device (20) is sent to the water supply pipe solenoid valve (11) via the control signal wiring (C) relating to the specific gravity. Open the valve and supply water through the water supply pipe (16). When the specific gravity measurement result becomes equal to or less than the set value, the water supply pipe solenoid valve (11) is closed using the control signal wiring (C) related to the specific gravity, and the water supply is stopped.
【００３７】また、制御装置(20)に、上記各水溶液や水
を供給した後、所定時間次の供給を休止するような手段
を設けられており、供給された水溶液や水をある期間撹
拌してエッチング液の組成を均一とし、それでもなおエ
ッチング液組成が設定値と相違する場合には更に各水溶
液や水を供給することができる。Further, the controller (20) is provided with a means for stopping the next supply for a predetermined time after supplying each of the aqueous solutions and water to the control device (20), and stirring the supplied aqueous solutions and water for a certain period of time. If the composition of the etching solution is still uniform, and the composition of the etching solution is still different from the set value, each aqueous solution or water can be further supplied.
【００３８】更に、制御装置(20)には、エッチング温度
の変更に対応して酸化還元電位及び塩化水素濃度の制御
設定値を補正する手段が設置されており、これによりエ
ッチング温度の変更に対応して自動的に制御設定値を変
更することができる。Further, the control device (20) is provided with a means for correcting the control set values of the oxidation-reduction potential and the hydrogen chloride concentration in response to the change of the etching temperature. Then, the control set value can be automatically changed.
【００３９】なお、制御装置(20)には、エッチング液送
り、スプレーポンプ(6)やエッチング液循環ポンプ(10)
のどちらか一方が停止した場合には、各水溶液や水の供
給を禁止する手段が組み込まれており、これによりポン
プの停止中の各水溶液や水の供給が供給され、過剰供給
等を防止することができる。The control device (20) includes an etchant feed, a spray pump (6) and an etchant circulation pump (10).
When either one of the pumps is stopped, a means for inhibiting the supply of each aqueous solution and water is incorporated, whereby the supply of each aqueous solution and water while the pump is stopped is supplied to prevent excessive supply and the like. be able to.
【００４０】[0040]
【実施例】以下の実施例及び比較例における原料配合比
は重量比であり、百分率は重量百分率である。 実施例１ スプレー式エッチング槽（エッチング有効距離２ｍ×
２、液保有量６００リットル）と酸化還元電位、塩化水
素濃度、比重及び温度の検出部、制御装置を組み合わせ
た図１の設備を使用し、プリント配線板銅箔のエッチン
グを行った。制御設定値は以下の通りとした：酸化還元
電位：５３０ｍＶ、塩化水素濃度：２７５ｍＶ（ｐＨ電
極からの発生電位を電圧計で測定、制御）、比重：１．
３６０また、新液の供給禁止温度は４２℃以下とし、新
液供給ポンプは６０秒間稼働後、酸化還元電位、塩化水
素濃度が設定値以下でも９０秒間停止するように制御し
た。薬液としては４０°Ｂｅの塩化第二鉄水溶液１００
部と塩化アンモニウム３部の混合溶液（これをＡ液とす
る）、３５％塩酸（これをＢ液とする）、３８％塩素酸
ナトリウム１００部とジエチレントリアミン０．１部の
混合溶液（これをＣ液とする）を使用し、酸化還元電位
の検出結果に従いＡ液、Ｂ液、Ｃ液を塩化第二鉄：塩化
水素：塩素酸ナトリウムのモル比が４．７：６．０：１
になるように供給し、塩化水素濃度の検出結果に従いＡ
液、Ｂ液を上記と同比率で供給し、比重の検出結果に従
い水を供給した。エッチング液温度は４５℃、スプレー
圧力１．８ｋｇ／ｃｍ2、コンベア速度４．０ｍ／分と
し、銅箔厚さ４５μｍ、銅箔除去率６０％の両面板（こ
れをＤ板とする）、銅箔厚さ４５μｍ、銅箔除去率１８
％の両面板（これをＥ板とする）を８時間かけ、それぞ
れ１００ｍ2処理した。この間、それぞれの制御設定値
に従い、各薬液、水が自動供給され塩化第一鉄濃度は
０．４２〜０．４４モル／リットル、塩化水素濃度は
０．５２〜０．５３％、比重は１．３５９〜１．３６１
に制御され、エッチングに拘わる不良は発生しなかっ
た。線幅１００μｍ、線間１００μｍの回路のエッチフ
ァクターは３．９となり、回路幅のバラツキは±２μｍ
となった。なお、塩化水素濃度の検出結果に基づき供給
されるＡ液、Ｂ液の量はＤ板処理時に比較し、Ｅ板処理
時の方が多かった。３カ月同条件で運転を継続したが、
スラッジ発生などのトラブルはなく、エッチング槽の洗
浄、液交換を必要としなかった。EXAMPLES In the following Examples and Comparative Examples, the mixing ratios of the raw materials are by weight, and the percentages are by weight. Example 1 Spray etching tank (Effective etching distance 2m ×
2, the printed circuit board copper foil was etched using the equipment shown in FIG. 1 in which a detection unit for the oxidation-reduction potential, hydrogen chloride concentration, specific gravity and temperature , and a control device were combined. The control set values were as follows: redox potential: 530 mV, hydrogen chloride concentration: 275 mV (potential generated from the pH electrode was measured and controlled by a voltmeter), specific gravity: 1.
360. Also, the supply prohibition temperature of the new liquid was set to 42 ° C. or lower, and the new liquid supply pump was operated for 60 seconds, and then controlled to stop for 90 seconds even if the oxidation-reduction potential and the hydrogen chloride concentration were lower than the set values. The chemical solution is a 40 ° Be ferric chloride aqueous solution 100
A mixed solution of 35 parts hydrochloric acid (referred to as liquid B), a mixed solution of 100 parts of 38% sodium chlorate and 0.1 part of diethylenetriamine (referred to as C) Solution, solution A, solution B and solution C in a molar ratio of ferric chloride: hydrogen chloride: sodium chlorate of 4.7: 6.0: 1 according to the detection result of the oxidation-reduction potential.
And supply according to the detection result of the hydrogen chloride concentration.
Liquid and liquid B were supplied at the same ratio as above, and water was supplied according to the result of detection of the specific gravity. The temperature of the etchant is 45 ° C., the spray pressure is 1.8 kg / cm 2 , the conveyor speed is 4.0 m / min, the copper foil thickness is 45 μm, and the copper foil removal rate is 60%. Foil thickness 45μm, Copper foil removal rate 18
% Of a double-sided board (this is referred to as an E-board) for 8 hours, and each was treated with 100 m 2 . During this time, each chemical solution and water are automatically supplied according to the respective control set values, the ferrous chloride concentration is 0.42 to 0.44 mol / liter, the hydrogen chloride concentration is 0.52 to 0.53%, and the specific gravity is 1 .359-1.361
And no defects related to etching occurred. The etch factor of a circuit having a line width of 100 μm and a line interval of 100 μm is 3.9, and the variation of the circuit width is ± 2 μm.
It became. The amounts of the solution A and the solution B supplied based on the detection result of the hydrogen chloride concentration were larger in the E plate treatment than in the D plate treatment. I continued driving under the same conditions for three months,
There was no trouble such as sludge generation, and no cleaning of the etching tank and no liquid exchange were required.
【００４１】実施例２ エッチング設備は実施例１と同様なものを使用した。実
施例１のＡ液とＢ液を塩化第二鉄：塩化水素のモル比が
５：６になるように混合した(これをＦ液とする)。Ｆ液
とＣ液の供給比を塩化第二鉄：塩化水素：塩素酸塩のモ
ル比が５：６：１となるようにし、塩化水素濃度の制御
設定値を２６０ｍＶとし、コンベア速度を４.９ｍ／分
とし、他の条件は実施例１と同じとした。銅箔厚さ３５
μｍの両面板を１５日間かけ７０００ｍ2処理した。エ
ッチング液の酸化還元電位が設定値以下になると６０秒
間Ｆ液、Ｃ液が供給され１２０秒間供給を休止した。こ
の休止時間中に酸化還元電位が設定値以上となることが
多々見られたが、その幅は４ｍＶと小さく新液の過剰供
給は最低量に抑えられた。また、塩化水素濃度に拘わる
電位が設定値以下になるとＦ液が上記と同様の経緯で供
給された。エッチング液組成のうち、塩化水素濃度は
０.３８〜０.４０％、銅濃度は７５〜７７ｇ／リットル
となり、他は実施例１と同様になった。スラッジ発生な
どのトラブルはなく、エッチング状態はエッチング開始
から終了するまで均一な仕上がりとなった。線幅７０μ
ｍ回路のエッチファクターは３.９であり、回路幅のバ
ラツキは±１.５μｍであった。なお、始業時のエッチ
ング液の温度は３０℃以下であり、酸化還元電位、塩酸
濃度に拘わる電位は制御設定値以下であったが、制御装
置の電源を入れても新液の供給は行われなかった。Example 2 The same etching equipment as in Example 1 was used. The solution A and the solution B of Example 1 were mixed so that the molar ratio of ferric chloride: hydrogen chloride was 5: 6 (this is referred to as solution F). The supply ratio of the solution F and the solution C is adjusted so that the molar ratio of ferric chloride: hydrogen chloride: chlorate is 5: 6: 1, the control set value of the hydrogen chloride concentration is 260 mV, and the conveyor speed is 4. The condition was 9 m / min, and the other conditions were the same as in Example 1. Copper foil thickness 35
The μm double-sided board was treated for 7000 m 2 over 15 days. When the oxidation-reduction potential of the etching solution became equal to or lower than the set value, the solution F and the solution C were supplied for 60 seconds, and the supply was stopped for 120 seconds. It was often observed that the oxidation-reduction potential was higher than the set value during the pause time, but the width was as small as 4 mV, and the excessive supply of the new solution was suppressed to the minimum. When the potential related to the hydrogen chloride concentration became equal to or less than the set value, the solution F was supplied in the same manner as described above. In the composition of the etching solution, the concentration of hydrogen chloride was 0.38 to 0.40% and the concentration of copper was 75 to 77 g / liter. There was no trouble such as sludge generation, and the etching state was uniform from the start to the end of the etching. Line width 70μ
The etch factor of the m circuit was 3.9, and the variation of the circuit width was ± 1.5 μm. The temperature of the etching solution at the start of operation was 30 ° C. or less, and the oxidation-reduction potential and the potential related to the hydrochloric acid concentration were below the control set values. However, even when the control device was turned on, the supply of the new solution was performed. Did not.
【００４２】実施例３ 実施例１と同様のエッチング設備を使用し、リードフレ
ームほかのエッチングを実施した。制御装置にエッチン
グ温度を変更するに際して、酸化還元電位、塩酸濃度に
拘わる電位の制御設定値を自動的に変更する電気回路及
びエッチング液の循環ポンプが停止した場合新液供給を
禁止する手段を組み込んだ。各制御設定値は以下の値と
した： 酸化還元電位 ５０℃：６００ｍＶ、４５
℃：５９６ｍＶ 塩酸濃度に拘わる電位 ５０℃：２４５ｍＶ、４５
℃：２３１ｍＶ 比重 １.４９０ 薬剤としては４８°Ｂｅの塩化第二鉄と３５％塩酸水溶
液を塩化第二鉄と塩化水素のモル比が１６：６.２にな
るように混合した溶液(これをＧ液とする)、３８％塩素
酸ナトリウム水溶液１００部とトリエチレンテチラミン
０.１部の混合溶液を使用した。酸化還元電位の検出結
果に従いＧ液、Ｈ液を塩化第二鉄、塩化水素、塩素酸ナ
トリウムのモル比が１６：６.２：１になるよう供給
し、塩化水素濃度の検出結果に従いＧ液を供給した。エ
ッチング温度５０℃、スプレー圧力１.８ｋｇ／ｃｍ2と
し、４２−アロイ材、厚さ０.２ｍｍのリードフレー
ム、ＳＵＳ−３０４材のカメラ部品などをエッチング処
理した。コンベア速度はエッチングの対象物により適宜
変更した。エッチング速度の遅いＳＵＳ−３０４材でエ
ッチング面積の小さいものの処理時には塩化水素検知器
が働き、Ｇ液のみの供給が頻繁に行われた。エッチング
温度を４５℃に変更した際には各制御設定値は自動的に
変更され、新液の過剰供給は起こらず、エッチング液の
組成は一定に維持された。また、エッチング液の循環ポ
ンプが停止した際は新液供給が停止され、循環ポンプが
再稼働すると新液が供給された。１０日間の運転期間中
のエッチング液の分析結果は塩化第一鉄濃度０.２３〜
０.２５モル／リットル、塩化水素濃度０.０９〜０.１
１％、比重１.４８８〜１.４９１となった。各製品の仕
上がり寸法、エッチングの直線性、金属表面の平滑性は
すべて良好でエッチングに拘わる不良は発生しなかっ
た。Example 3 Using the same etching equipment as in Example 1, etching of the lead frame and the like was performed. When the etching temperature is changed, an electric circuit for automatically changing the control set value of the potential relating to the oxidation-reduction potential and the concentration of hydrochloric acid when changing the etching temperature and a means for inhibiting the supply of a new solution when the circulation pump for the etching solution is stopped are incorporated. It is. Each control set value was as follows: Redox potential 50 ° C .: 600 mV, 45
° C: 596 mV Potential depending on hydrochloric acid concentration 50 ° C: 245 mV, 45
° C: 231 mV Specific gravity 1.490 As a drug, a solution obtained by mixing ferric chloride at 48 ° Be with a 35% hydrochloric acid aqueous solution so that the molar ratio of ferric chloride to hydrogen chloride was 16: 6.2 (this was A mixed solution of 100 parts of a 38% aqueous sodium chlorate solution and 0.1 part of triethylene tetramine was used. Solution G and solution H are supplied according to the detection result of the oxidation-reduction potential so that the molar ratio of ferric chloride, hydrogen chloride, and sodium chlorate becomes 16: 6.2: 1, and solution G according to the detection result of the hydrogen chloride concentration. Was supplied. At an etching temperature of 50 ° C. and a spray pressure of 1.8 kg / cm 2 , a 42-alloy material, a lead frame having a thickness of 0.2 mm, and camera parts made of SUS-304 material were subjected to an etching treatment. The conveyor speed was appropriately changed depending on the object to be etched. At the time of processing a SUS-304 material having a low etching rate and a small etching area, a hydrogen chloride detector was operated, and only the G solution was frequently supplied. When the etching temperature was changed to 45 ° C., each control set value was automatically changed, no excessive supply of new solution occurred, and the composition of the etching solution was kept constant. Further, when the circulation pump for the etching solution was stopped, the supply of the new solution was stopped, and when the circulation pump was restarted, the new solution was supplied. The analysis result of the etching solution during the operation period of 10 days shows that the ferrous chloride concentration is 0.23 to
0.25 mol / l, hydrogen chloride concentration 0.09-0.1
1%, specific gravity 1.488 to 1.491. The finished dimensions of each product, the linearity of the etching, and the smoothness of the metal surface were all good, and no defects related to the etching occurred.
【００４３】比較例１ 実施例１のエッチング設備を使用し、所定温度以下で新
液の供給を禁止する制御機能及び新液供給ポンプを所定
時間稼働後、所定時間休止する制御機能を停止した以外
は制御設定値、エッチング条件を実施例１と同じとし、
実施例１のＤ板２０ｍ2、Ｆ板２０ｍ2を処理した。この
間、酸化還元電位が設定値以下となり、Ａ液、Ｂ液、Ｃ
液の供給が行われ、設定値で供給が停止されたが、その
後も酸化還元電位は上昇し５４１ｍＶとなった。また、
塩酸濃度検知で供給されるＡ液、Ｂ液も同様の経緯とな
った。エッチング液の分析結果は塩化第一鉄濃度０.３
５〜０.４５モル／リットル、塩化水素濃度は０.５３〜
０.７５％となった。また、線幅１００μｍ、線間１０
０μｍの回路幅のバラツキは±１０μｍとなった。新液
の過剰供給が起こり、エッチング液組成、エッチング性
能が一定に維持されていないことがわかる。また、始業
時のエッチング液の温度は３２℃であり、制御装置の電
源を入れたところ新液供給が行われ、塩化第一鉄濃度は
０.１８モル／リットル、塩化水素濃度は１.５％とな
り、制御目標値を大幅に上回った。このエッチング液を
使用し、実施例１と同条件でＤ板を処理したところオー
バエッチとなり、レジスト剥がれが見られた。COMPARATIVE EXAMPLE 1 A control function for inhibiting the supply of a new liquid below a predetermined temperature and a control function for stopping a predetermined time after operating a new liquid supply pump for a predetermined time using the etching equipment of Example 1 were stopped. Is the same as the control set value and the etching conditions in the first embodiment,
It was treated with D board 20 m 2, F plate 20 m 2 of Example 1. During this time, the oxidation-reduction potential becomes equal to or lower than the set value, and the solutions A, B, C
The supply of the liquid was performed, and the supply was stopped at the set value. However, the oxidation-reduction potential further increased to 541 mV. Also,
The liquid A and the liquid B supplied by the hydrochloric acid concentration detection have the same background. The analysis result of the etching solution shows a ferrous chloride concentration of 0.3.
5 to 0.45 mol / l, hydrogen chloride concentration 0.53 to
It was 0.75%. Also, the line width is 100 μm, and the line interval is 10 μm.
The variation of the circuit width of 0 μm was ± 10 μm. It can be seen that the excessive supply of the new solution occurs, and the composition of the etching solution and the etching performance are not maintained constant. The temperature of the etching solution at the start of operation was 32 ° C., and when the control device was turned on, a new solution was supplied. The ferrous chloride concentration was 0.18 mol / liter and the hydrogen chloride concentration was 1.5. %, Greatly exceeding the control target value. When this etching solution was used to process the D plate under the same conditions as in Example 1, overetching occurred and peeling of the resist was observed.
【００４４】比較例２ 実施例３のエッチング設備を使用し、エッチング温度の
変更に際して、酸化還元電位、塩化水素濃度に拘わる電
位の制御設定値を自動変更する制御機能及びエッチング
液の循環ポンプが停止した場合に新液の供給を禁止する
制御機能を停止した以外は制御設定値、エッチング条件
を同じとし、リードフレームほかを処理した。エッチン
グ温度を５０℃から４５℃に変更したところ、酸化還元
電位、塩酸濃度に拘わる電位が下がり、各新液が供給さ
れた。塩化第一鉄濃度は０.２４モル／リットルから０.
１８モル／リットルになり、塩化水素濃度は０.３０％
になった。このエッチング液を使用し、４２−アロイ材
のエッチングを実施したところ、直線性が悪く、エッチ
ング表面の平滑性も悪かった。また、エッチング温度を
５０℃に変更すると、酸化還元電位、塩酸濃度に拘わる
電位はそれぞれ６０８ｍＶ、２５８ｍＶと制御設定値を
大幅に上回っており、制御設定値になるまで、エッチン
グ性能が安定しなかった。また、エッチング液循環ポン
プが停止した状態で、エッチングを継続したところ、液
組成の制御幅が大きくなり、塩化第一鉄濃度は０.１７
〜０.３５モル／リットルとなり、塩化水素濃度は０.０
５〜０.５９％となった。ピン数４００のリードフレー
ムのエッチングではピン幅の仕上がり寸法が±１５μｍ
となり、５５シートのうち２１シートが不良となった。Comparative Example 2 When the etching equipment of Example 3 was used and the etching temperature was changed, the control function for automatically changing the control set value of the potential relating to the oxidation-reduction potential and the hydrogen chloride concentration and the circulation pump for the etching solution were stopped. The control set value and etching conditions were the same except that the control function for prohibiting the supply of the new solution was stopped when the process was performed, and the lead frame and the like were processed. When the etching temperature was changed from 50 ° C. to 45 ° C., the oxidation-reduction potential and the potential related to the hydrochloric acid concentration were lowered, and each new solution was supplied. The ferrous chloride concentration ranges from 0.24 mol / l to 0.2.
18 mol / l, hydrogen chloride concentration 0.30%
Became. When the 42-alloy material was etched using this etchant, the linearity was poor and the smoothness of the etched surface was poor. When the etching temperature was changed to 50 ° C., the oxidation-reduction potential and the potential relating to the concentration of hydrochloric acid were 608 mV and 258 mV, respectively, which were significantly higher than the control set value, and the etching performance was not stabilized until the control set value was reached. . Further, when the etching was continued while the etching liquid circulation pump was stopped, the control width of the liquid composition became large, and the ferrous chloride concentration became 0.17.
~ 0.35 mol / l, and the concentration of hydrogen chloride is 0.0
It became 5 to 0.59%. In the etching of a lead frame with 400 pins, the finished dimension of the pin width is ± 15 μm
, And 21 sheets out of 55 sheets were defective.
【００４５】[0045]
【発明の効果】本発明の塩化第二鉄による各種金属のエ
ッチング方法は、酸化還元電位を検知し、塩素酸塩水溶
液、塩化水素水溶液、塩化第二鉄水溶液を自動供給し、
塩化水素濃度を検知し、塩化水素水溶液、塩化第二鉄水
溶液を供給するに際して、所定温度以下では新液の供給
を禁止する制御機能、所定時間新液を供給した後、所定
時間供給を休止する機能、エッチング温度変更時には各
制御設定値を自動的に変更する機能、エッチングのスプ
レーポンプあるいは液循環ポンプのいずれかが停止した
場合は新液の供給を禁止する機能を制御装置に組み込む
ことによりより緻密なエッチング液管理を可能にした金
属のエッチング方法を提供できるという効果を奏する。The method of the present invention for etching various metals with ferric chloride detects the oxidation-reduction potential and automatically supplies an aqueous chlorate solution, an aqueous hydrogen chloride solution and an aqueous ferric chloride solution.
When detecting the concentration of hydrogen chloride and supplying an aqueous solution of hydrogen chloride or an aqueous solution of ferric chloride, a control function for inhibiting the supply of a new solution at a predetermined temperature or less, after supplying a new solution for a predetermined time, suspending the supply for a predetermined time. A function that automatically changes each control set value when the etching temperature is changed, and a function to prohibit the supply of a new solution when either the etching spray pump or the liquid circulation pump is stopped are incorporated into the control unit. The effect of being able to provide a metal etching method that enables precise management of the etching solution can be provided.
【図面の簡単な説明】[Brief description of the drawings]
【図１】本発明の金属のエッチング方法を実施するため
の装置の一例を示す図である。FIG. 1 is a diagram showing an example of an apparatus for performing a metal etching method of the present invention.
１ エッチング槽 ２ 酸化還元電位・塩化水素濃度・比重及び温度検出
部 ３ 塩化第二鉄水溶液貯槽 ４ 塩化水素水溶液貯槽 ５ 塩素酸塩水溶液貯槽 ６ エッチング液送り、スプレーポンプ ７ 塩化第二鉄水溶液送りポンプ ８ 塩化水素水溶液送りポンプ ９ 塩素酸塩水溶液送りポンプ １０ エッチング液循環ポンプ １１ 水供給配管電磁弁 １２ エッチング液送り配管 １３ エッチング液戻り配管 １４ スプレー用液送り配管 １５ 液循環用配管 １６ 水供給配管 １７ 塩化第二鉄供給配管 １８ 塩化水素水溶液供給配管 １９ 塩素酸塩水溶液供給配管 ２０ 制御装置 Ａ 酸化還元電位に拘わる制御信号配線 Ｂ 塩化水素濃度に拘わる制御信号配線 Ｃ 比重に拘わる制御信号配線DESCRIPTION OF SYMBOLS 1 Etching tank 2 Oxidation-reduction potential / hydrogen chloride concentration / specific gravity and temperature detecting unit 3 Ferric chloride aqueous solution storage tank 4 Hydrogen chloride aqueous solution storage tank 5 Chlorate aqueous solution storage tank 6 Etching liquid feed, spray pump 7 Ferric chloride aqueous solution feed pump Reference Signs List 8 Hydrogen chloride aqueous solution feed pump 9 Chlorate aqueous solution feed pump 10 Etching solution circulation pump 11 Water supply piping solenoid valve 12 Etching solution delivery piping 13 Etching solution return piping 14 Spraying solution delivery piping 15 Liquid circulation piping 16 Water supply piping 17 Ferric chloride supply pipe 18 Hydrogen chloride aqueous solution supply pipe 19 Chlorate aqueous solution supply pipe 20 Controller A Control signal wiring related to redox potential B Control signal wiring related to hydrogen chloride concentration C Control signal wiring related to specific gravity
───────────────────────────────────────────────────── フロントページの続き (72)発明者 石塚 義次 東京都荒川区東尾久７丁目２番35号 旭 電化工業株式会社内 (56)参考文献 特開 平６−73563（ＪＰ，Ａ) 特開 平６−33268（ＪＰ，Ａ) 特開 平４−157356（ＪＰ，Ａ) 特開 平４−122090（ＪＰ，Ａ) 特開 平３−197335（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C23F 1/00 - 1/46 H01L 21/308 ──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Yoshiji Ishizuka 7-35 Higashiogu, Arakawa-ku, Tokyo Asahi Denka Kogyo Co., Ltd. (56) References JP-A-6-73563 (JP, A) JP JP-A-6-33268 (JP, A) JP-A-4-157356 (JP, A) JP-A-4-122090 (JP, A) JP-A-3-197335 (JP, A) (58) Fields investigated (Int) .Cl. 7 , DB name) C23F 1/00-1/46 H01L 21/308
Claims (5)
塩素酸カルシウムからなる群から選択される塩素酸塩１
モルに対し、塩化水素６〜９モル、塩化第二鉄２．５〜
３０モルの割合で塩素酸塩水溶液、塩化水素水溶液、塩
化第二鉄水溶液を供給するにあたり、酸化還元電位・塩
化水素濃度・比重及び温度検出部において、エッチング
液の酸化還元電位を検知し、この検知結果に基づき上記
水溶液をエッチング液へ供給して予め設定された酸化還
元電位を連続的に維持し、比重を検知し、この検知結果
に基づき水をエッチング液へ供給して予め設定された比
重を連続的に維持することからなる塩化第二鉄水溶液を
用いる金属のエッチング方法において、制御装置が所定
温度以下では新液及び／または水の供給を禁止する手段
を備えてなることを特徴とする金属のエッチング方法。1. A chlorate 1 selected from the group consisting of sodium chlorate, potassium chlorate and calcium chlorate.
6 to 9 mol of hydrogen chloride, 2.5 to ferric chloride
When supplying chlorate aqueous solution, hydrogen chloride aqueous solution, and ferric chloride aqueous solution at a ratio of 30 mol, the oxidation-reduction potential / salt
In the hydrogen hydride concentration / specific gravity and temperature detecting section, the oxidation-reduction potential of the etching solution is detected, and based on the detection result, the aqueous solution is supplied to the etching solution to continuously maintain a predetermined oxidation-reduction potential , In the method for etching a metal using an aqueous ferric chloride solution comprising detecting water and supplying water to the etching solution based on the detection result to continuously maintain a predetermined specific gravity, A method for etching a metal, comprising: means for inhibiting supply of a new solution and / or water.
温度検出部において、塩化水素含量を検知し、この検知
結果に基づき塩化水素を含む水溶液をエッチング液へ供
給して予め設定された塩化水素濃度を連続的に維持する
請求項１記載の金属のエッチング方法。 2. The oxidation-reduction potential / hydrogen chloride concentration / specific gravity and
The temperature detector detects the hydrogen chloride content and detects this.
Based on the results, supply an aqueous solution containing hydrogen chloride to the etching solution.
To maintain the preset hydrogen chloride concentration continuously
The metal etching method according to claim 1.
を所定の時間行った後、所定の時間休止する手段を備え
てなる請求項１または２記載の金属のエッチング方法。3. A control apparatus, new chemical and / or after the supply of the water a predetermined time, according to claim 1 or 2 etching method for a metal according consisting comprises means to pause a predetermined period of time.
応して酸化還元電位、塩化水素濃度の制御設定値を自動
的に変更できる手段を備えてなる請求項１ないし３のい
ずれか１項記載の金属のエッチング方法。4. A control device, redox potential in response to changes in the etching temperature, claims 1 becomes comprise means for automatically changing the control setting value of the hydrogen chloride concentration of 3 Neu
The method for etching a metal according to claim 1 .
ンプを設置したエッチング装置を使用し、酸化還元電位
・塩化水素濃度・比重及び温度検出部へのエッチング液
の送液を上記ポンプのいずれかを使用して行うに際し
て、制御装置が、上記検出部へのエッチング液の送液を
行わない方のポンプが停止した場合には新液の供給を禁
止する手段を備えてなる請求項１ないし４のいずれか１
項に記載の金属のエッチング方法。5. An oxidation-reduction potential using an etching apparatus provided with a spray pump and an etchant circulation pump.
- liquid feed of the etchant to the hydrogen chloride concentration, specific gravity and temperature detecting section Te <br/> in performing using one of the pump, control unit, a liquid feed of the etchant to the detection unit
One pump better not made of claims 1 becomes comprise means for inhibiting the supply of new liquid, if you stop 4 1
Item 10. The metal etching method according to item 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26472092A JP3193152B2 (en) | 1992-10-02 | 1992-10-02 | Metal etching method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26472092A JP3193152B2 (en) | 1992-10-02 | 1992-10-02 | Metal etching method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06116758A JPH06116758A (en) | 1994-04-26 |
| JP3193152B2 true JP3193152B2 (en) | 2001-07-30 |
Family
ID=17407250
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26472092A Expired - Lifetime JP3193152B2 (en) | 1992-10-02 | 1992-10-02 | Metal etching method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3193152B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103014710A (en) * | 2013-01-21 | 2013-04-03 | 哈尔滨工业大学 | Metallographic corrosive agent for invar welded joint welded by using M93 welding wires and preparation method for metallographic corrosive agent |
| CN114774920B (en) * | 2022-04-12 | 2024-03-15 | 宁波福至新材料有限公司 | Processing technology for ensuring etching speed |
-
1992
- 1992-10-02 JP JP26472092A patent/JP3193152B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06116758A (en) | 1994-04-26 |
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