JP2616272B2 - Measurement method of chelating agent concentration, hydroxide ion concentration and reducing agent concentration in chemical copper plating solution - Google Patents
Measurement method of chelating agent concentration, hydroxide ion concentration and reducing agent concentration in chemical copper plating solutionInfo
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- JP2616272B2 JP2616272B2 JP7995191A JP7995191A JP2616272B2 JP 2616272 B2 JP2616272 B2 JP 2616272B2 JP 7995191 A JP7995191 A JP 7995191A JP 7995191 A JP7995191 A JP 7995191A JP 2616272 B2 JP2616272 B2 JP 2616272B2
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- concentration
- ion
- copper plating
- plating solution
- chelating agent
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Description
【０００１】[0001]
【産業上の利用分野】本発明は、化学銅めっき液中のキ
レート剤濃度と水酸化物イオン濃度と還元剤濃度の測定
方法に関する。The present invention relates to a method for measuring the concentration of a chelating agent, the concentration of a hydroxide ion and the concentration of a reducing agent in a chemical copper plating solution.
【０００２】[0002]
【従来の技術】近年、プリント配線板の多くは化学銅め
っきにより絶縁基板上に回路導体を設けて製造されてい
る。この場合、回路導体である化学銅めっき皮膜は電気
特性と機械特性が良好であることを要求される。2. Description of the Related Art In recent years, most printed wiring boards have been manufactured by providing circuit conductors on an insulating substrate by chemical copper plating. In this case, the chemical copper plating film as the circuit conductor is required to have good electrical and mechanical properties.
【０００３】一般に、化学銅めっき液は、銅イオン、銅
イオンのキレート剤等の錯化剤、銅イオンの還元剤及び
アルカリ金属の水酸化物を主成分としている。そして、
アルカリ金属の水酸化物と還元剤はめっき反応によって
消費され濃度が低下する。また銅イオン濃度などの変動
によりキレート剤の一部が銅イオンとキレートを形成す
るので、銅イオンとキレートを形成していないキレート
剤濃度が変動する。In general, a chemical copper plating solution contains copper ion, a complexing agent such as a chelating agent for copper ions, a reducing agent for copper ions, and a hydroxide of an alkali metal as main components. And
The alkali metal hydroxide and the reducing agent are consumed by the plating reaction and the concentration decreases. In addition, since a part of the chelating agent forms a chelate with the copper ion due to a change in the concentration of the copper ion or the like, the concentration of the chelating agent not forming a chelate with the copper ion changes.
【０００４】ところで、化学銅めっき皮膜の機械的特性
はめっき液中のアルカリ金属の水酸化物濃度と還元剤や
銅イオンとキレートを形成していないキレート剤濃度に
著しく影響を受ける。このため、化学銅めっき皮膜の特
性を良好に保つためには、これらの成分の濃度管理が必
要となる。そこで、従来は化学銅めっき液中のキレート
剤濃度と水酸化物濃度還元剤の測定を各々別途に行って
いた。[0004] The mechanical properties of a chemical copper plating film are significantly affected by the concentration of alkali metal hydroxide in the plating solution and the concentration of a reducing agent or a chelating agent that does not form a chelate with copper ions. For this reason, in order to maintain good properties of the chemical copper plating film, it is necessary to control the concentration of these components. Therefore, conventionally, the concentration of the chelating agent and the concentration of the hydroxide in the chemical copper plating solution have been separately measured.
【０００５】従来のキレート剤濃度の測定方法は、一定
濃度の硫酸銅水溶液をアンモニウム水によりアルカリ性
にしてこの中にムレキシド指示薬を入れ、この溶液を化
学銅めっき液によって滴定して青緑から青紫への液の色
の変化により反応の終点を求め、このときの滴定量から
化学銅めっき液中の銅イオンとキレートを形成していな
いキレート剤濃度を求めるものであった。また、水酸化
物イオン濃度の測定方法は、ガラス電極法によって化学
銅めっき液中の水素イオン濃度を測定し、水のイオン積
より計算によって水酸化物イオン濃度を間接的に求める
ものであった。A conventional method for measuring the concentration of a chelating agent is to make a copper sulfate aqueous solution of a certain concentration alkaline with ammonium water, add a murexide indicator therein, titrate the solution with a chemical copper plating solution, and turn the solution from blue-green to blue-violet. The end point of the reaction was determined from the change in the color of the solution, and the concentration of the chelating agent that did not form a chelate with copper ions in the chemical copper plating solution was determined from the titration amount at this time. The method of measuring the hydroxide ion concentration was to measure the hydrogen ion concentration in the chemical copper plating solution by the glass electrode method and indirectly determine the hydroxide ion concentration by calculation from the ion product of water. .
【０００６】さらに、従来の化学銅めっき液中の還元剤
であるホルムアルデヒド濃度を測定するには、先ず濃度
を測定する化学銅めっき液とこの化学銅めっき液に混合
する亜硫酸塩溶液のｐＨが等しくなるように調整し、次
に両液を混合してこの混合溶液のｐＨ変化が終わった
後、この混合溶液に酸を混合前のｐＨになるまで加え
て、加えた酸の容量より還元剤であるホルムアルデヒド
の濃度を求めていた。Further, in order to measure the concentration of formaldehyde as a reducing agent in a conventional chemical copper plating solution, first, the chemical copper plating solution whose concentration is to be measured and the sulfite solution mixed with the chemical copper plating solution have the same pH. After adjusting the pH of the mixed solution, the acid was added to the mixed solution until the pH before mixing was reached, and the volume of the added acid was reduced with a reducing agent. A formaldehyde concentration was being sought.
【０００７】[0007]
【発明が解決しようとする課題】しかし、上記の従来の
方法は、キレート剤濃度と水酸化物濃度と還元剤濃度の
測定操作が別々であり、複雑で時間がかかった。また、
それぞれの方法にも問題があった。すなわち、上記のキ
レート剤濃度の測定では反応の終点の色の変化を精度よ
く検知するのに熟練を要することや、終点検知の化学反
応が遅いために一度変化した色が１〜２分後に戻ってし
まうなどの問題があった。また、上記の水酸化物イオン
濃度の測定方法はガラス電極法であるため、ｐＨ１１以
上ではアルカリ誤差が大きく正確さに欠けることや、電
極の劣化などの問題があった。However, in the above-mentioned conventional method, the operation of measuring the concentration of the chelating agent, the concentration of the hydroxide, and the concentration of the reducing agent are separate, and are complicated and time-consuming. Also,
There were problems with each method. That is, in the above-described measurement of the chelating agent concentration, skill is required to accurately detect the color change at the end point of the reaction, and the color once changed due to the slow chemical reaction at the end point detection returns after 1-2 minutes. And other problems. Further, since the method for measuring the hydroxide ion concentration is a glass electrode method, there are problems such as a large alkali error at pH 11 or higher, lack of accuracy, and deterioration of the electrode.
【０００８】さらに上記の如き化学銅めっき液と亜硫酸
塩との反応を利用して、この反応により生成する水酸化
物イオン酸で滴定することによってホルムアルデヒド濃
度を測定する方法では、化学銅めっき液中の銅イオンと
キレートを形成していないキレート剤の影響を受けて、
化学銅めっき液中の還元剤であるホルムアルデヒド濃度
を正確に測定することができなかった。Further, the method of measuring the formaldehyde concentration by utilizing the reaction between a chemical copper plating solution and a sulfite as described above and titrating with a hydroxide ionic acid generated by this reaction involves the following steps. Under the influence of a chelating agent that has not formed a chelate with copper ions of
The concentration of formaldehyde as a reducing agent in the chemical copper plating solution could not be accurately measured.
【０００９】[0009]
【課題を解決するための手段】本発明者らは前記課題を
解決するために鋭意研究を重ねた結果、重金属イオンの
塩の水溶液で化学銅めっき液を滴定することにより、そ
の目的が達成されていることを見出し、この知見に基づ
いて本発明を完成するに至った。Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, the object has been achieved by titrating a chemical copper plating solution with an aqueous solution of a salt of a heavy metal ion. And completed the present invention based on this finding.
【００１０】すなわち本発明は、銅イオン、銅イオンの
キレート剤、銅イオンの還元剤及びアルカリ金属の水酸
化物を主成分とする化学銅めっき液の一定量の試料液を
重金属イオンの塩の水溶液で滴定して試料液のｐＨ変化
を検出し、経時的に記録する。That is, according to the present invention, a certain amount of a chemical copper plating solution containing copper ions, a chelating agent for copper ions, a reducing agent for copper ions, and an alkali metal hydroxide as main components is used to prepare a salt of heavy metal ions. The change in pH of the sample solution is detected by titration with an aqueous solution, and the change is recorded over time.
【００１１】次に、同じ化学銅めっき液の一定量の試料
液に試料液中の還元剤量よりも過剰当量のアルカリ金属
の亜硫酸塩を加えた後に、重金属イオンの塩で水溶液で
滴定し、試料液のｐＨの変化を検出し、経時的に記録す
る。これら２度の滴定からキレート剤濃度と水酸化物イ
オン濃度と還元剤濃度を求めることを特徴とする化学銅
めっき液中のキレート剤濃度と水酸化物イオン濃度と還
元剤濃度の測定方法を提供するものである。Then, after adding an equivalent amount of alkali metal sulfite in excess of the amount of the reducing agent in the sample solution to a certain amount of the sample solution of the same chemical copper plating solution, titration with a heavy metal ion salt in an aqueous solution is performed. The change in pH of the sample solution is detected and recorded over time. A method for measuring a concentration of a chelating agent, a concentration of a hydroxide ion, and a concentration of a reducing agent in a chemical copper plating solution, wherein a concentration of a chelating agent, a concentration of a hydroxide ion, and a concentration of a reducing agent are obtained from these two titrations. Is what you do.
【００１２】本発明の対象となる化学銅めっき液は、銅
イオン、銅イオンのキレート剤、銅イオンの還元剤及び
アルカリ金属の水酸化物を主成分とするものである。The chemical copper plating solution to be used in the present invention contains copper ions, a chelating agent for copper ions, a reducing agent for copper ions, and a hydroxide of an alkali metal as main components.
【００１３】この化学銅めっき液に含まれる銅イオンの
キレート剤としては、化学銅めっき液の安定性より、エ
チレンジアミン四酢酸又はその塩が好ましい。また、化
学銅めっき液には、上記の成分の他に添加剤としてシア
ン化合物、界面活性剤、α，α’−ジピリジル、金属酸
化物イオンなどを含んでいてもよい。As a chelating agent for copper ions contained in the chemical copper plating solution, ethylenediaminetetraacetic acid or a salt thereof is preferable from the viewpoint of the stability of the chemical copper plating solution. In addition, the chemical copper plating solution may contain a cyan compound, a surfactant, α, α′-dipyridyl, a metal oxide ion, and the like as additives in addition to the above components.
【００１４】本発明では、上記の化学銅めっき液の一定
量の試料液を重金属イオンの塩の水溶液で滴定する。滴
定に使用する重金属イオンの塩としては、キレート剤と
の反応性より、アルカリ土類金属、遷移金属、アルミニ
ウム、スズ又は鉛等のイオンの塩が好ましい。In the present invention, a fixed amount of the above-mentioned chemical copper plating solution is titrated with an aqueous solution of a salt of a heavy metal ion. As a salt of a heavy metal ion used for titration, a salt of an ion such as an alkaline earth metal, a transition metal, aluminum, tin or lead is preferred from the viewpoint of reactivity with a chelating agent.
【００１５】上記の化学銅めっき液の一定量の試料液の
重金属イオンの塩の水溶液で滴定すると、化学銅めっき
液中のキレート剤（Ｙ4-）と水酸化物イオン（ＯＨ- ）
は重金属イオン（Ｍ2+）と以下のように順次反応する。 Ｍ2+＋ Ｙ4- →ＭＹ2- 〔Ｉ〕 Ｍ2+＋２ＯＨ- →Ｍ（ＯＨ）2 〔II〕When a certain amount of the above-described chemical copper plating solution is titrated with an aqueous solution of a salt of a heavy metal ion, the chelating agent (Y 4− ) and the hydroxide ion (OH − ) in the chemical copper plating solution are titrated.
Reacts sequentially with the heavy metal ion (M 2 +) as follows. M 2 ++ Y 4- → MY 2- [I] M 2 ++ 2OH - → M ( OH) 2 (II)
【００１６】ここで、式〔Ｉ〕の反応は速く、式〔II〕
の反応より起こりやすい。また、この反応により試料液
のｐＨの変化はほとんどない。一方、式〔II〕の反応は
式〔Ｉ〕の反応が終了した段階で始まり、この反応によ
りＯＨ- が減少するため、試料液のｐＨの変化は大き
い。よって、ガラス電極等によりｐＨを測定し記録しつ
つ、濃度が既知である重金属イオンの水溶液を化学銅め
っき液に滴下すると、試料液のｐＨの変化の様子から式
〔Ｉ〕及び〔II〕の反応の終点を知ることができる。Here, the reaction of the formula [I] is fast, and the reaction of the formula [II]
More likely to occur than the reaction. Further, there is almost no change in the pH of the sample solution due to this reaction. On the other hand, the reaction of the formula [II] starts at the stage when the reaction of the formula [I] is completed, and the pH of the sample solution is largely changed because OH - is reduced by this reaction. Therefore, while measuring and recording the pH with a glass electrode or the like, when an aqueous solution of a heavy metal ion having a known concentration is dropped on the chemical copper plating solution, the changes in the pH of the sample solution are expressed by the formulas (I) and (II). You can know the end point of the reaction.
【００１７】図１は、本発明の測定方法に基づいて化学
銅めっき液を重金属イオンの塩の水溶液で滴定した場合
の滴定曲線の一例を示すグラフである。横軸は重金属イ
オンの塩の水溶液の滴定量（ｍｌ）、縦軸はｐＨを示
す。FIG. 1 is a graph showing an example of a titration curve when a chemical copper plating solution is titrated with an aqueous solution of a salt of a heavy metal ion based on the measuring method of the present invention. The horizontal axis indicates the titer (ml) of the aqueous solution of the heavy metal ion salt, and the vertical axis indicates the pH.
【００１８】図１に示すように、横軸に重金属イオンの
塩の水溶液の滴定量、縦軸にｐＨををとって滴定曲線を
描くと、式〔Ｉ〕の反応中と式〔II〕の反応中とでｐＨ
の変化量が異なるので、滴定曲線が折れ曲がる。式
〔Ｉ〕の反応の終点は、ほぼ直線的に緩やかに減少して
いたｐＨが急激に減少を始める点（図１中のＡ点）であ
る。この点は同時に式〔II〕の反応の始点でもある。式
〔II〕の反応の終点は、ｐＨの急激な減少が緩やかとな
る変曲点（図１中のＢ点）である。従って、滴定曲線の
傾きの変化から式〔Ｉ〕及び〔II〕の反応の終点を知る
ことができる。As shown in FIG. 1, the abscissa plots the titration amount of the aqueous solution of the heavy metal ion and the ordinate plots the pH, and the titration curve is plotted between the reaction of formula [I] and the reaction of formula [II]. PH during and after the reaction
, The titration curve is bent. The end point of the reaction of the formula [I] is a point at which the pH that has been gradually decreasing linearly and gradually starts to decrease rapidly (point A in FIG. 1). This point is also the starting point of the reaction of the formula [II]. The end point of the reaction of the formula [II] is an inflection point (point B in FIG. 1) at which the rapid decrease in pH becomes gentle. Therefore, the end points of the reactions of the formulas [I] and [II] can be known from the change in the slope of the titration curve.
【００１９】このようにして得た式〔Ｉ〕及び〔II〕の
反応の終点までの重金属イオンの塩の水溶液の滴定量と
重金属イオンの塩の水溶液の濃度から、化学銅めっき液
中のキレート剤濃度と水酸化物イオン濃度を求めること
ができる。From the titration of the aqueous solution of the heavy metal ion salt up to the end of the reaction of the formulas [I] and [II] and the concentration of the aqueous solution of the heavy metal ion salt, the chelate in the chemical copper plating solution was determined. The agent concentration and hydroxide ion concentration can be determined.
【００２０】次に、別に同じ化学銅めっき液の一定量の
試料液に試料液中の還元剤量よりも過剰当量のアルカリ
金属の亜硫酸塩を加える。ここで試料液中の還元剤と亜
硫酸イオンで下記の式〔III〕 のような反応がおこる。 Ｎａ2 ＳＯ3 ＋ＣＨ2 Ｏ＋Ｈ2 Ｏ→ＣＨ3 ＯＳＯ3 ＋ＮａＯＨ 〔III〕 この反応によって試料液中の水酸化物イオンは、上記の
式〔III〕 によるもので還元剤量と等量のものと試料液
に最初から含まれているものの合計になる。そこで、亜
硫酸塩添加後の試料液に対して最初の滴定と同様に重金
属イオンの塩の水溶液で滴定を行う。試料液中のキレー
ト剤と水酸化物イオンは〔Ｉ〕〔II〕のように順次反応
し、反応によるｐＨの変化から最初の滴定と同様にして
終点を検出でキレート剤濃度と水酸化物イオン濃度を求
めることができる。Next, an alkali metal sulfite in excess of the amount of the reducing agent in the sample solution is added to a certain amount of the sample solution of the same chemical copper plating solution. Here, a reaction represented by the following formula [III] occurs with the reducing agent and the sulfite ion in the sample solution. Na 2 SO 3 + CH 2 O + H 2 O → CH 3 OSO 3 + NaOH [III] By this reaction, the hydroxide ion in the sample solution is the same as the amount of the reducing agent in the sample according to the above formula [III]. It is the sum of what is initially contained in the liquid. Therefore, titration is performed on the sample solution after addition of the sulfite with an aqueous solution of a salt of a heavy metal ion in the same manner as in the first titration. The chelating agent and the hydroxide ion in the sample solution react sequentially as in [I] and [II], and the end point is detected in the same manner as in the first titration from the pH change due to the reaction, and the chelating agent concentration and the hydroxide ion are detected. The concentration can be determined.
【００２１】図２は本発明の基づいて亜硫酸塩を加えた
めっき液試料を重金属イオンの塩の水溶液で滴定した場
合の一例を示す。横軸と縦軸は図１と同様である。この
２回目の滴定から求められた水酸化物イオン濃度から１
回目の滴定から求められた水酸化物イオン濃度を差し引
くと上記の式〔III〕 に基づく水酸化物イオン濃度から
求めることができ、よって還元剤濃度がより得ることが
できる。FIG. 2 shows an example in which a plating solution sample to which a sulfite is added according to the present invention is titrated with an aqueous solution of a salt of a heavy metal ion. The horizontal axis and the vertical axis are the same as in FIG. From the hydroxide ion concentration obtained from the second titration, 1
By subtracting the hydroxide ion concentration obtained from the second titration, it can be obtained from the hydroxide ion concentration based on the above formula [III], so that the reducing agent concentration can be obtained more.
【００２２】[0022]
【作用】本発明において、化学銅めっき液の一定量の試
料液に重金属イオンの塩の水溶液が加えられると、先
ず、銅イオンとキレートを形成していないキレート剤と
重金属イオンとの反応が進行し、この反応が終了すると
同時に重金属イオンと水酸化物イオンとの反応が進行す
る。前者の反応はｐＨの変化が小さく、後者の反応はｐ
Ｈの変化が大きいことから、化学銅めっき液の一定量を
重金属イオンの塩の水溶液で滴定し、それと同時に混合
溶液のｐＨを検出することによって前者の反応と後者の
反応の両方の終点を知り得、一度にキレート剤濃度と水
酸化物イオン濃度を測定することができる。In the present invention, when an aqueous solution of a salt of a heavy metal ion is added to a certain amount of a sample solution of a chemical copper plating solution, first, a reaction between a chelating agent not forming a chelate with the copper ion and the heavy metal ion proceeds. However, at the same time as the completion of this reaction, the reaction between heavy metal ions and hydroxide ions proceeds. The former reaction has a small change in pH, and the latter reaction has p
Since the change in H is large, a certain amount of the chemical copper plating solution is titrated with an aqueous solution of a salt of a heavy metal ion, and at the same time, the end points of both the former reaction and the latter reaction are known by detecting the pH of the mixed solution. Thus, the chelating agent concentration and the hydroxide ion concentration can be measured at once.
【００２３】次に、化学銅めっき液の一定量の試料液に
亜硫酸塩を加えた後に最初の滴定と同様に重金属イオン
の塩の水溶液で滴定する。この滴定ではｐＨの変化の様
子は最初の滴定と同じであり、この結果から求められる
キレート剤濃度も同一試料であるため同じである。しか
し水酸化物イオン濃度は還元剤と亜硫酸塩の反応〔II
I〕 に基づく量だけ多くなっているため、２回目の結果
から求めた水酸化物イオン濃度と１回目の結果から求め
た水酸化物イオン濃度の差から還元剤濃度を求めること
ができる。Next, sulfite is added to a certain amount of the sample solution of the chemical copper plating solution, and then titrated with an aqueous solution of a salt of a heavy metal ion in the same manner as in the first titration. In this titration, the state of the pH change is the same as in the first titration, and the chelating agent concentration obtained from the result is also the same because the same sample is used. However, the hydroxide ion concentration depends on the reaction between the reducing agent and the sulfite [II
I], the reducing agent concentration can be determined from the difference between the hydroxide ion concentration determined from the second result and the hydroxide ion concentration determined from the first result.
【００２４】[0024]
【実施例】以下、本発明を実施例に基づいて詳細に説明
するが、本発明はこれに限定されるものではない。化学
銅めっき液として以下の組成のものを用いた。 硫酸銅 １０ ｇ／ｌ （ＣｕＳＯ4 ・５Ｈ2 Ｏ）（０．０４モル／ｌ） エチレンジアミン四酢酸四ナトリウム ５４．２ｇ／ｌ （ＥＤＴＡ・４Ｎａ） （０．０２モル／ｌ） ホルマリン ３ ｍｌ／ｌ （３７％ホルムアルデヒド水溶液） 水酸化ナトリウム ２ ｇ／ｌ （ＮａＯＨ） （０．０５モル／ｌ） 添加剤 少量The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples. The chemical copper plating solution having the following composition was used. Copper sulfate 10 g / l (CuSO 4 · 5H 2 O) (0.04 mol / l) of tetrasodium ethylenediamine tetraacetate 54.2g / l (EDTA · 4Na) (0.02 mol / l) formalin 3 ml / l (37% formaldehyde aqueous solution) Sodium hydroxide 2 g / l (NaOH) (0.05 mol / l) Additive small amount
【００２５】上記化学銅めっき液１０ｍｌをビーカーに
とり、純水を加えて約５０ｍｌ程度にした。このビーカ
ーにｐＨメーターと、記録計と接続したガラス電極（堀
場製作所 複合ガラス電極Ｎｏ６３６６）を浸した。こ
の中へ、ビュレットを用いて０．１モル／ｌの硫酸銅水
溶液を滴下させ、このときのｐＨの変化を経時的に検
出、記録した。この結果を図１に示した。横軸は硫酸銅
水溶液の滴定量（ｍｌ）、縦軸はｐＨを示す。10 ml of the above chemical copper plating solution was placed in a beaker, and pure water was added to make about 50 ml. A glass electrode (Composite glass electrode No. 6366, Horiba, Ltd.) connected to the pH meter and the recorder was immersed in this beaker. To this, a 0.1 mol / l aqueous solution of copper sulfate was dropped using a burette, and a change in pH at this time was detected and recorded with time. The result is shown in FIG. The horizontal axis indicates the titer (ml) of the aqueous copper sulfate solution, and the vertical axis indicates the pH.
【００２６】この図１中のＡ点は、キレート剤と銅イオ
ンの反応の終点であると同時に水酸化物イオンと銅イオ
ンの反応の開始点である。また、Ｂ点は銅イオンと水酸
化物イオンとの反応の終点である。このことから、Ａ点
における硫酸銅水溶液の滴定量が８．０ｍｌであったこ
とにより、化学銅めっき液のキレート剤の中で銅イオン
と錯体を形成していないキレート剤濃度０．０８モル／
ｌを得た。また、Ｂ点とＡ点における硫酸銅水溶液の滴
定量の差が２．５ｍｌであり、銅イオンと水酸化物イオ
ンの反応比が１：２であることから、水酸化物イオン濃
度０．０５モル／ｌを得た。なお。濃度の計算方法はキ
レート剤濃度の場合、下記の式〔III〕に従い、水酸化
物イオンの場合、下記の式〔IV〕に従った。 ＣＶ ＝ Ｃ’Ｖ’ 〔 〕 Ｃ1 Ｖ ＝ ２Ｃ’Ｖ1 〔 〕 〔ただし、Ｃは化学銅めっき液液中のキレート剤濃度、
Ｖは化学銅めっき液の分取量（１０ｍｌ）、Ｃ’は滴定
に用いた硫酸銅水溶液の濃度（０．１モル／ｌ）、Ｖ’
はＡ点における硫酸銅水溶液の滴定量、Ｃ1 は化学銅め
っき液中の水酸化物イオンの濃度、Ｖ1 はＢ点とＡ点に
おける硫酸銅水溶液の滴定量の差を示す。〕The point A in FIG. 1 is the end point of the reaction between the chelating agent and the copper ion and the start point of the reaction between the hydroxide ion and the copper ion. Point B is the end point of the reaction between the copper ion and the hydroxide ion. From this, the titer of the aqueous solution of copper sulfate at point A was 8.0 ml, and the concentration of the chelating agent not forming a complex with copper ions in the chelating agent of the chemical copper plating solution was 0.08 mol / mol.
1 was obtained. The difference between the titration amounts of the copper sulfate aqueous solution at the points B and A is 2.5 ml, and the reaction ratio between copper ions and hydroxide ions is 1: 2. Mol / l were obtained. In addition. The concentration was calculated according to the following formula [III] for the chelating agent concentration, and according to the following formula [IV] for the hydroxide ion. CV = C′V ′ [] C 1 V = 2C′V 1 [] [where C is the concentration of the chelating agent in the chemical copper plating solution,
V is the amount of the chemical copper plating solution collected (10 ml), C 'is the concentration of the copper sulfate aqueous solution used for the titration (0.1 mol / l), V'
Represents the titer of the aqueous copper sulfate solution at point A, C 1 represents the concentration of hydroxide ion in the chemical copper plating solution, and V 1 represents the difference between the titer of the aqueous copper sulfate solution at points B and A. ]
【００２７】次に同一の化学銅めっき液の一定量（１０
ｍｌ）の試料液に０．１モル／ｌの亜硫酸ナトリウムの
水溶液を約５０ｍｌ加え、２分間攪拌した。この試料液
に対して上記の滴定と同一の手順と条件で重金属イオン
の塩の水溶液で滴定してキレート剤濃度と水酸化物イオ
ン濃度を求めた。この滴定でのｐＨの変化の様子を図２
に示した。Ｃ点、Ｄ点は図１のＡ点、Ｂ点に対応するも
のである。この結果より上記の式〔Ｖ〕〔VI〕より求め
たキレート剤の濃度は０．０８モル／ｌ（滴定量８ｍ
ｌ）であり、１回目の滴定の結果から求めたものと同じ
であったが、水酸化物イオン濃度は、０．０９モル／ｌ
（滴定量４．５ｍｌ）であった。このことから２回目の
水酸化物イオン濃度（０．０９モル／ｌ）から、１回目
の水酸化物イオン濃度（０．０５モル／ｌ）を差し引く
ことによって還元剤濃度は０．０４モル／ｌであった。
この還元剤濃度をｍｌ／ｌで示すと下記の式〔VI〕より
３ｍｌ／ｌである。 Ｍ＝７５Ｍ’ 〔VI〕 ここでＭはｍｌ／ｌ表示の還元剤濃度であｌ、Ｍ’はモ
ル／ｌ表示の還元剤濃度である。Next, a certain amount of the same chemical copper plating solution (10
ml) of the sample solution, about 50 ml of a 0.1 mol / l aqueous solution of sodium sulfite was added, followed by stirring for 2 minutes. The sample solution was titrated with an aqueous solution of a salt of a heavy metal ion in the same procedure and under the same conditions as in the above-mentioned titration to determine the chelating agent concentration and the hydroxide ion concentration. Figure 2 shows how the pH changes during this titration.
It was shown to. Points C and D correspond to points A and B in FIG. From these results, the concentration of the chelating agent determined from the above formulas [V] and [VI] was 0.08 mol / l (titration 8 m
l), which was the same as that obtained from the result of the first titration, except that the hydroxide ion concentration was 0.09 mol / l.
(Titration 4.5 ml). From this, by subtracting the first hydroxide ion concentration (0.05 mol / l) from the second hydroxide ion concentration (0.09 mol / l), the reducing agent concentration becomes 0.04 mol / l. l.
The concentration of the reducing agent in ml / l is 3 ml / l according to the following formula [VI]. M = 75M '[VI] Here, M is the reducing agent concentration in ml / l, and M' is the reducing agent concentration in mol / l.
【００２８】[0028]
【発明の効果】本発明によると、化学銅めっき液中のキ
レート剤濃度と水酸化物イオン濃度を一度に化学銅めっ
き液に重金属イオンの塩の水溶液を添加するたけで簡便
に、かつ、正確に測定することができる。また、上記同
様の滴定を亜硫酸塩と試料液を混合後に行うだけで上記
の結果との差から簡便かつ、正確に還元剤濃度を測定す
ることができる。According to the present invention, the concentration of the chelating agent and the concentration of hydroxide ion in the chemical copper plating solution can be easily and simply determined by simply adding an aqueous solution of a salt of a heavy metal ion to the chemical copper plating solution at once. Can be measured. Further, simply by performing the same titration after mixing the sulfite and the sample solution, the concentration of the reducing agent can be simply and accurately measured from the difference from the above result.
【図１】 本発明の測定方法に基づいて化学銅めっき液
を重金属イオンの塩の水溶液で滴定した場合の滴定曲線
の一例を示すグラフである。横軸は重金属イオンの塩の
水溶液の滴定量（ｍｌ）、縦軸はｐＨを示す。FIG. 1 is a graph showing an example of a titration curve when a chemical copper plating solution is titrated with an aqueous solution of a salt of a heavy metal ion based on the measurement method of the present invention. The horizontal axis indicates the titer (ml) of the aqueous solution of the heavy metal ion salt, and the vertical axis indicates the pH.
【図２】 本発明の測定方法に基づいて化学銅めっき液
に亜硫酸ナトリウムを加えた試料液を重金属の塩の水溶
液で滴定した場合の滴定曲線の一例を示すグラフであ
る。横軸は、縦軸は図１と同じ。FIG. 2 is a graph showing an example of a titration curve when a sample solution obtained by adding sodium sulfite to a chemical copper plating solution based on the measurement method of the present invention is titrated with an aqueous solution of a salt of a heavy metal. The horizontal axis is the same as the vertical axis in FIG.
フロントページの続き (72)発明者 岡村 寿朗 茨城県下館市大字小川1500番地 日立化 成工業株式会社 下館研究所内 (72)発明者 磯野 雅司 茨城県下館市大字小川1500番地 日立化 成工業株式会社 下館研究所内 (72)発明者 渡辺 智子 茨城県下館市大字小川1500番地 日立化 成工業株式会社 下館研究所内Continuing on the front page (72) Inventor, Toshiro Okamura 1500 Ogawa, Shimodate-shi, Ibaraki Pref.Hitachi Chemical Industry Co., Ltd. Inside the laboratory (72) Inventor Tomoko Watanabe 1500 Ogawa, Oaza, Shimodate City, Ibaraki Pref.Hitachi Chemical Industry Co., Ltd.
Claims (3)
オンの還元剤及びアルカリ金属の水酸化物を主成分とす
る化学銅めっき液から一定量の試料液を採取し、この液
を重金属イオンの塩の水溶液で滴定して試料液のｐＨ変
化を検出し、経時的に記録する。次に、同じ化学銅めっ
き液から一定量の試料液を採集し、この試料液中の還元
剤量よりも過剰当量のアルカリ金属の亜硫酸塩を加えた
後に、重金属イオンの塩の水溶液で滴定し、試料液のｐ
Ｈの変化を検出し、記録する。これらの２度の滴定から
キレート剤濃度と水酸化物イオン濃度と還元剤濃度を求
めることを特徴とする化学銅めっき液中のキレート剤濃
度と水酸化物イオン濃度と還元剤濃度の測定方法。1. A certain amount of a sample solution is collected from a chemical copper plating solution containing copper ions, a chelating agent for copper ions, a reducing agent for copper ions and an alkali metal hydroxide as main components, and this solution is used as a heavy metal ion. The pH change of the sample solution is detected by titration with an aqueous solution of a salt of the above, and the change is recorded over time. Next, a certain amount of a sample solution is collected from the same chemical copper plating solution, an excess amount of an alkali metal sulfite is added in excess of the reducing agent in the sample solution, and titration is performed with an aqueous solution of a heavy metal ion salt. , P of the sample solution
Detect and record changes in H. A method for measuring the concentration of a chelating agent, the concentration of a hydroxide ion, and the concentration of a reducing agent in a chemical copper plating solution, wherein the concentration of a chelating agent, the concentration of a hydroxide ion, and the concentration of a reducing agent are determined from these two titrations.
ミン四酢酸又はその塩である請求項１記載の化学銅めっ
き液中のキレート剤濃度と水酸化物イオン濃度と還元剤
濃度の測定方法。2. The method for measuring the concentration of a chelating agent, the concentration of a hydroxide ion, and the concentration of a reducing agent in a chemical copper plating solution according to claim 1, wherein the copper ion chelating agent is ethylenediaminetetraacetic acid or a salt thereof.
属、遷移金属、アルミニウム、スズ又は鉛のイオンの塩
である請求項１又は２記載の化学銅めっき液中のキレー
ト剤濃度と水酸化物イオン濃度と還元剤濃度の測定方
法。3. The chelating agent concentration and hydroxide in a chemical copper plating solution according to claim 1, wherein the salt of a heavy metal ion is a salt of an ion of an alkaline earth metal, a transition metal, aluminum, tin or lead. Method for measuring ion concentration and reducing agent concentration.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7995191A JP2616272B2 (en) | 1991-04-12 | 1991-04-12 | Measurement method of chelating agent concentration, hydroxide ion concentration and reducing agent concentration in chemical copper plating solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7995191A JP2616272B2 (en) | 1991-04-12 | 1991-04-12 | Measurement method of chelating agent concentration, hydroxide ion concentration and reducing agent concentration in chemical copper plating solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04314869A JPH04314869A (en) | 1992-11-06 |
| JP2616272B2 true JP2616272B2 (en) | 1997-06-04 |
Family
ID=13704618
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7995191A Expired - Lifetime JP2616272B2 (en) | 1991-04-12 | 1991-04-12 | Measurement method of chelating agent concentration, hydroxide ion concentration and reducing agent concentration in chemical copper plating solution |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2616272B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2780585B2 (en) * | 1992-12-18 | 1998-07-30 | 松下電工株式会社 | Electroless copper plating method and apparatus |
| CA2323584C (en) * | 1998-03-17 | 2009-04-28 | James R. Johnson | Method and apparatus for testing surfaces |
| US6890758B2 (en) * | 2003-06-13 | 2005-05-10 | Eci Technology, Inc. | Measurement of complexing agent concentration in an electroless plating bath |
-
1991
- 1991-04-12 JP JP7995191A patent/JP2616272B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04314869A (en) | 1992-11-06 |
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