JP5116068B2 - Method for stabilizing electroless gold plating solution - Google Patents
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- JP5116068B2 JP5116068B2 JP2004259576A JP2004259576A JP5116068B2 JP 5116068 B2 JP5116068 B2 JP 5116068B2 JP 2004259576 A JP2004259576 A JP 2004259576A JP 2004259576 A JP2004259576 A JP 2004259576A JP 5116068 B2 JP5116068 B2 JP 5116068B2
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Description
本発明は、無電解金めっき液、特にめっき液中のシアンイオンの濃度低下による分解性の無電解金めっき液の安定化方法に関する。 The present invention relates to a method for stabilizing an electroless gold plating solution, particularly a degradable electroless gold plating solution by reducing the concentration of cyanide ions in the plating solution.
従来より、金源としての金のシアン化合物、還元剤などを含む無電解金めっき液は、電子部品などの金めっきに利用されている。
この無電解金めっき液を利用して金めっきを行う場合、めっきの進行につれてめっき液中の金濃度が低下するので、これを補うため金のシアン化合物を補給しているが、このためめっきの進行につれて次第にめっき液中には遊離シアンイオンが蓄積されていく。遊離シアンイオンは適正値を超えてその濃度が高まると、金の析出速度を低下させる。
この対策として、特許文献１（特開昭６４−８３６７２号公報）には、この遊離シアンイオンの過剰分をシアンと反応して金属シアン化合物を形成し得る金属化合物を添加することにより抑制することが提案されている。
Conventionally, an electroless gold plating solution containing a gold cyanide compound as a gold source, a reducing agent, and the like has been used for gold plating of electronic parts and the like.
When gold plating is performed using this electroless gold plating solution, the gold concentration in the plating solution decreases as the plating progresses. To compensate for this, gold cyanide is replenished. As the process progresses, free cyanide ions gradually accumulate in the plating solution. Free cyanide ions decrease the deposition rate of gold when their concentration exceeds the appropriate value and increases.
As a countermeasure, Patent Document 1 (Japanese Patent Application Laid-Open No. Sho 64-83672) suppresses this excess cyanide ion by adding a metal compound capable of reacting with cyanide to form a metal cyanide compound. Has been proposed.
一方、例えば置換還元型無電解金めっき液においては、遊離のシアンイオンの存在は同めっき液の安定化に寄与している。すなわち、この遊離シアンイオンは、めっき液の自己分解を防止する作用があることも知られている。
したがって、無電解金めっき液中には、その安定性を維持するために所定の濃度で遊離シアンイオンを確保することが必要である。ところで、置換還元型無電解金めっき液を使用する無電解金めっき法においては、ニッケル表面の置換反応をマイルドにし、ニッケル表面の孔食を発生させないように、比較的マイルドなめっき条件にしている。例えば、還元剤も還元力の弱いロンガリットなどのホルマリン系の還元剤もしくはヒドラジン等が使用され、ｐＨも中性付近の条件が採用されている。又、遊離シアン濃度も孔食発生を防止するために低濃度である。その上、遊離のシアンが蒸発し、または溶存酸素により酸化され、いずれにしても遊離のシアンは消費される。めっき中は、遊離のシアンがシアン金イオンの析出反応により供給されるが、めっき物がなくなるとシアンの消費が増加する。 Therefore, in the electroless gold plating solution, it is necessary to secure free cyanide ions at a predetermined concentration in order to maintain the stability. By the way, in the electroless gold plating method using the substitution reduction type electroless gold plating solution, the nickel surface substitution reaction is mild, and the plating conditions are relatively mild so as not to cause pitting corrosion on the nickel surface. . For example, as the reducing agent, a formalin-based reducing agent such as Rongalite having a weak reducing power, hydrazine, or the like is used, and the pH is near neutral. The free cyan density is also low to prevent pitting corrosion. Moreover, free cyan is evaporated or oxidized by dissolved oxygen, and in any case free cyan is consumed. During plating, free cyan is supplied by the precipitation reaction of cyan gold ions. However, if the plated product disappears, the consumption of cyan increases.
こうした現象により、遊離シアンイオンがなくなると自己分解する無電解金めっき液にあっては、経時的な安定性を確保するために、めっき液中の遊離シアンイオンの濃度を把握することが重要となる。そのことによりめっき液の安定度を把握することができ、必要なシアンイオンの補給時期、およびその添加量を知ることができる。
しかしながら、低濃度のシアンイオンの分析は滴定では極めて困難であり、蒸留法によりシアンを分離回収し全シアン濃度を測定する方法はあるが、その作業は繁雑であり時間も要する。より簡便で、かつ迅速な遊離シアンの測定技術が望まれる。
本発明は、こうした状況の下に、無電解金めっき液の経時安定性を確保するために、その金めっき液中のシアンイオンの存在量を簡便に、かつ迅速に把握して、必要なシアンイオンの補給時期、補給量を決定する方法を提供し、また、その方法を利用して無電解金めっき液を安定化する方法を提供することを目的とするものである。
For electroless gold plating solutions that self-decompose when free cyanide ions disappear due to these phenomena, it is important to know the concentration of free cyanide ions in the plating solution in order to ensure stability over time. Become. As a result, the stability of the plating solution can be grasped, and the necessary cyan ion replenishment timing and the amount of addition thereof can be known.
However, analysis of low-concentration cyan ions is extremely difficult by titration, and there is a method of separating and recovering cyan by a distillation method and measuring the total cyan concentration, but this operation is complicated and requires time. A simpler and quicker technique for measuring free cyanide is desired.
Under such circumstances, the present invention can easily and quickly grasp the amount of cyanide ions in the gold plating solution in order to ensure the stability over time of the electroless gold plating solution. It is an object of the present invention to provide a method for determining the replenishment timing and amount of ions, and to provide a method for stabilizing an electroless gold plating solution using the method.
本発明者らは、無電解金めっき中のシアンイオンを簡便に、迅速に検出する方法について鋭意検討した結果、無電解めっき液中の酸化還元電位をＯＲＰ計で検出しこの値がめっき液中の遊離シアンイオンの存在量と相関していることを見出し、したがって、その値に基づいてめっき液の安定度を評価することができることを見出し、本発明に至った。
すなわち、本発明は、
As a result of intensive studies on a method for simply and rapidly detecting cyanide ions in electroless gold plating, the present inventors detected an oxidation-reduction potential in an electroless plating solution with an ORP meter, and this value was found in the plating solution. Thus, the present inventors have found that there is a correlation with the abundance of free cyanide ions, and thus found that the stability of the plating solution can be evaluated based on the value, leading to the present invention.
That is, the present invention
（１） めっき液中の遊離シアンイオンの濃度低下により分解性をもつ無電解金めっき液の安定化方法であって、無電解金めっき液のシアンイオン濃度の変化を該めっき液の酸化還元電位をＯＲＰ計により検出することにより評価し、そのシアンイオン濃度の変化に基づきシアンイオンの補給時期、および補給量を決定し、無電解金めっき液にシアンイオンを補給することを特徴とする無電解金めっき液の安定化方法。
（２） 該無電解金めっき液が置換還元型無電解金めっき液である前記（１）記載の無電解金めっき液の安定化方法。
に関する。
(1) A method for stabilizing an electroless gold plating solution that is decomposable due to a decrease in the concentration of free cyanide ions in the plating solution, wherein the change in cyan ion concentration of the electroless gold plating solution is determined by the oxidation-reduction potential of the plating solution. In which the amount of cyanide is replenished based on the change in the cyanide concentration, the amount and time of replenishment of cyanide are determined, and the electroless gold plating solution is replenished with cyanide. Method for stabilizing the gold plating solution.
(2) The method for stabilizing an electroless gold plating solution according to (1), wherein the electroless gold plating solution is a substitution reduction type electroless gold plating solution.
About.
本発明によれば、遊離シアンイオンの濃度低下により分解性の無電解金めっき液について、その濃度変化を該めっき液の酸化還元電位値を測定することにより把握して、めっき液の安定性を確保するために必要なシアンイオンの補給時期、補給量を知ることができるので、迅速、簡便な方法により、該無電解金めっき液の経時的安定化を図ることができる。 According to the present invention, regarding the electroless gold plating solution that is decomposable due to a decrease in the concentration of free cyanide ions, the concentration change is grasped by measuring the oxidation-reduction potential value of the plating solution, and the stability of the plating solution is determined. Since it is possible to know the replenishment timing and the replenishment amount of cyanide necessary for securing, the electroless gold plating solution can be stabilized over time by a quick and simple method.
本発明においては、無電解金めっき液の酸化還元電位をＯＲＰ計により測定し、その値によって、めっき液中の遊離シアンイオンの濃度変化を監視することが重要である。
すでに述べているように、無電解金めっき液には、置換還元型金めっき液のように、めっき反応が起こっていない状態では、めっき液中の遊離シアンイオンは消費されやすく、次第にその濃度が低下していく。そして、その濃度変化につれてめっき液の安定度は低下し、そのまま放置すれば、めっき液は分解し、金が不用意に浴の壁面などに析出することとなる。
In the present invention, it is important to measure the oxidation-reduction potential of the electroless gold plating solution with an ORP meter and monitor the change in the concentration of free cyanide ions in the plating solution based on the measured value.
As already mentioned, in electroless gold plating solutions, free cyanide ions in the plating solution are easily consumed in a state where no plating reaction occurs like the substitution reduction type gold plating solution, and the concentration gradually increases. It goes down. As the concentration changes, the stability of the plating solution decreases. If left as it is, the plating solution is decomposed and gold is inadvertently deposited on the wall of the bath.
この現象はめっき液中に遊離シアンイオンを補給することにより防止することができる。そして、その無電解金めっき液中の遊離シアンイオンの濃度は、ＯＲＰ計により測定した酸化還元電位とよく相関しているので、ＯＲＰ計によって、その濃度変化を把握することができる。すなわち、無電解金めっき液の初期から（建浴時から）分解の生起するまでの遊離シアンイオンの濃度変化を、めっき液の酸化還元電位の変化として、把握しておけば、ＯＲＰ計により測定した酸化還元電位の値をもって、めっき液への遊離シアンイオンの補給の時期、及びその補給量を決定することができる。 This phenomenon can be prevented by supplying free cyanide ions to the plating solution. And since the density | concentration of the free cyanide ion in the electroless gold plating solution correlates well with the oxidation-reduction potential measured with the ORP meter, the concentration change can be grasped with the ORP meter. That is, if the change in free cyanide concentration from the initial stage of electroless gold plating solution (from the time of building bath) to the occurrence of decomposition is grasped as the change in oxidation-reduction potential of the plating solution, it can be measured with an ORP meter. The timing of replenishment of free cyanide ions to the plating solution and the replenishment amount can be determined from the value of the redox potential.
ＯＲＰ計による測定は、遊離シアンイオンが非操業時の初期において消費されやすいので、１，２日目は３時間毎に１回、３日目からは６時間毎に行うことでよい。シアンイオンの補給は、シアン化ナトリウム、シアン化カリウムを使用することが好ましい。この補給作業は、ＯＲＰ値が−３０ｍｖ以上にならないようなタイミングで行うことが好ましい。
本発明の安定化方法は、直接シアンイオンを滴定する方法に比べて遙かに迅速、かつ簡便であり、しかも的確である。
Since the measurement by the ORP meter is likely to consume free cyanide ions at the initial stage of non-operation, it may be performed once every 3 hours on the 1st and 2nd days and every 6 hours from the 3rd day. It is preferable to use sodium cyanide or potassium cyanide for the supply of cyanide ions. This replenishment operation is preferably performed at a timing such that the ORP value does not exceed -30 mv.
The stabilization method of the present invention is much faster, simpler and more accurate than the method of directly titrating cyan ions.
本発明の方法が適用されるのは、無電解金めっき液であって、めっき液中に存在する遊離シアンイオンの濃度低下により分解性をもつめっき液である。この代表的なものは、置換還元型無電解金めっき液である。このほか
等を挙げることができる。
The method of the present invention is applied to an electroless gold plating solution having a decomposability due to a decrease in the concentration of free cyanide ions present in the plating solution. A typical example is a substitution reduction type electroless gold plating solution. other than this
Etc.
実施例
以下に実施例を示し、本発明を更に詳細に説明する。
なお、以下に示す試験においては、ＯＲＰ計として東亜ディーケーケー（株）製ＯＲＰ電極ＰＳ−５１１１Ｃを使用し、４７℃で測定した。
使用しためっき液の組成
シアン金カリウム ： ２ｇ／ｌ
EDTA ：１０
燐酸２水素ナトリウム：３４
ホルマリン系還元剤 ： ２
アミン系錯化剤 ： １
ｐＨ ：７．０
温度 ：８０℃
Examples The following examples are given to further illustrate the present invention.
In the tests shown below, ORP electrode PS-5111C manufactured by Toa DKK Co., Ltd. was used as the ORP meter, and measurement was performed at 47 ° C.
Composition of used plating solution Potassium cyanide gold: 2 g / l
EDTA: 10
Sodium dihydrogen phosphate: 34
Formalin reducing agent: 2
Amine complexing agent: 1
pH: 7.0
Temperature: 80 ° C
上記めっき液のめっき非操業時ＯＲＰ値の変化
初期（建浴時） −１５０ｍｖ
１時間後 −１００
８時間後 −７０
２４時間後 −５０
３２時間後 −３０
４８時間後 −１０
５６時間後 ０（浴分解）
上記ＯＲＰ値の変化は、めっき液中の実際のシアンイオン濃度とよく相関していることを示すため、以下にＫＣＮ濃度とＯＲＰ値（測定温度４７℃）の関係をしめす。
ＫＣＮ濃度 ＯＲＰ値
（ｇ／ｌ） （ｍｖ）
０．１６ −２４７
０．０８ −２２８
０．０４ −１９７
０．０２ −１６８
０ −１２
Change in ORP value during non-operation of the above plating solution Initial (during bathing) -150 mV
-100 hours later
-70 after 8 hours
-24 hours later
-30 hours later
48 hours later -10
56 hours later 0 (Bath decomposition)
In order to show that the change in the ORP value correlates well with the actual cyan ion concentration in the plating solution, the relationship between the KCN concentration and the ORP value (measurement temperature 47 ° C.) is shown below.
KCN concentration ORP value (g / l) (mv)
0.16 -247
0.08 -228
0.04 -197
0.02 -168
0-12
上記の試験結果から、めっき反応が行われていない無電解金めっき液においては、経時的に遊離シアンイオンが消費されており、それに伴って、ＯＲＰ値の絶対値が低下していき、建浴時から５６時間後には、分解に至ることが分かった。
この結果に基づいて、無電解金めっき液のＯＲＰ値を指標として、遊離シアンイオンを補給する時期、及びその補給量を決定することができる。
以下にその実施例を示す。
使用した無電解金めっき液は、前記と同じものである。
From the above test results, in the electroless gold plating solution in which the plating reaction is not performed, free cyanide ions are consumed over time, and accordingly, the absolute value of the ORP value is decreased. It was found that after 56 hours, decomposition occurred.
Based on this result, it is possible to determine the time and amount of replenishment of free cyanide ions using the ORP value of the electroless gold plating solution as an index.
Examples are shown below.
The electroless gold plating solution used is the same as described above.
ＯＲＰ値（ｍｖ） ＫＣＮ補給（ｇ／ｌ）
初期（建浴時） −１５０ ……
１時間後 −１００ ……
８時間後 −８０ ０．０２４
２４時間後 −１１０ ０．０２
３２時間後 −１２０ ０．０２
４８時間後 −７５ ０．０２５
５６時間後 −１０５ ０．０２
７２時間後 −８５ ０．０２３
８０時間後 −１１０ ０．０２
９６時間後 −９０ ０．０２１
以上のように、本発明の方法により建浴時から経時的に安定にめっき液を保持することができ、いつでもめっき反応を安定に行うことができる。
ORP value (mv) KCN replenishment (g / l)
Initial (when bathing) -150 ......
1 hour -100 ……
8 hours later -80 0.024
-110 0.02 after 24 hours
After 32 hours -120 0.02
48 hours later -75 0.025
56 hours later -105 0.02
72 hours later -85 0.023
80 hours later -110 0.02
96 hours later -90 0.021
As described above, according to the method of the present invention, the plating solution can be stably retained over time from the time of bathing, and the plating reaction can be stably performed at any time.
Claims (2)
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| JP2004259576A JP5116068B2 (en) | 2004-09-07 | 2004-09-07 | Method for stabilizing electroless gold plating solution |
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| JP5116068B2 true JP5116068B2 (en) | 2013-01-09 |
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| ZA775495B (en) * | 1976-11-22 | 1978-07-26 | Kollmorgen Tech Corp | Method and apparatus for control of electroless plating solutions |
| DE2917714C2 (en) * | 1979-05-02 | 1983-12-22 | Degussa Ag, 6000 Frankfurt | Procedure for measuring with redox or ion-sensitive electrodes |
| GB2225026A (en) * | 1988-11-22 | 1990-05-23 | American Chem & Refining Co | Electroless gold plating composition |
| TW200300131A (en) * | 2001-11-08 | 2003-05-16 | Nihon Parkerizing | Process for treating hydrogen ion-containing waste liquid |
| JP2003313699A (en) * | 2002-04-24 | 2003-11-06 | Okuno Chem Ind Co Ltd | Method for controlling cyanide ion concentration |
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