JPS6070180A - Method and device for adjusting automatically concentration of alpha,alpha'-dipyridyl in chemical copper plating liquid - Google Patents

Abstract

PURPOSE:To adjust automatically the concn. of alpha,alpha'-dipyridyl in a chemical copper plating liquid with good accuracy by detecting the absorbancy of the complex salt formed by the ferrous ion and alpha,alpha'-dipyridyl in said liquid and replenishing the alpha,alpha'- dipyridyl soln. thereto if necessary. CONSTITUTION:A chemical copper plating liquid (table 1) 2 contained in a plating cell 1 is dispensed by a prescribed amt. by the 1st dispenser 5 and is fed into a cell 6 for detecting concn. of alpha,alpha'-dipyridyl. A chemical liquid (table 3) 8 for detection is dispensed by a prescribed amt. by the 2nd dispenser 7 and is fed into the cell 6. After the liquid 2 and the liquid 8 are thoroughly stirred 9, the liquids are allowed to stand for 5min and the detection signal voltage corresponding to the concn. of the alpha,alpha'-dipyridyl is obtd. by an absorbance meter 10. The detection signal voltage is converted to a digital signal by an AD converter 11 and is converted to the concn. of the alpha,alpha'-dipyridyl by an arithmetic control device 12. The concn. is compared with a preset control target value and if the concn. is lower than said value, a driving signal is outputted from the device 12 to a replenishing pump 13 which replenishes a prescribed amt. of the alpha,alpha'- dipyridyl from a tank 14.

Description

【発明の詳細な説明】 ［発明の技術分野］ 本発明は、化学銅めっき液中のα、α′−ジピリジルの
自動濃度調整方法およびそのための装置に関する。DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention relates to a method for automatically adjusting the concentration of α, α'-dipyridyl in a chemical copper plating solution and an apparatus therefor.

［発明の技術的背景とその問題点］ 化学銅めっきは、溶液中の銅イオンを還元剤により、触
媒活性な表面に還元゛析出させる化学的プロセスであり
、最近、プラスチックの金属被覆、プリント配線板の製
造等に広く利用されている。[Technical background of the invention and its problems] Chemical copper plating is a chemical process in which copper ions in a solution are reduced and deposited on a catalytically active surface using a reducing agent. Widely used for manufacturing plates, etc.

このような化学銅めっき液において、良好な性質を有す
る銅めっき皮膜を得るためには、めっき液の各成分濃度
、特に添加剤の濃度を常に適正濃度範囲に維持する必要
がある。In such a chemical copper plating solution, in order to obtain a copper plating film with good properties, it is necessary to always maintain the concentration of each component of the plating solution, especially the concentration of additives, within an appropriate concentration range.

しかしながら、化学銅めっき液中の添加剤は、めっき液
の汲み出し、めっき反応等により減少するため、液中の
添加剤濃度を簡易にしかも高い精度で検出し、補充する
必要がある。However, since the additives in the chemical copper plating solution decrease due to pumping out of the plating solution, plating reaction, etc., it is necessary to detect the additive concentration in the solution easily and with high accuracy and replenish the solution.

化学鋼めっき液の添加剤であるα、α′−ジピリジルの
濃度測定は、従来エーテル抽出後回光度法により手作業
で行なわれていた。すなわち、一定時間毎に一定量のめ
っき液を分液ロートに分取し、これに一定量のエチルエ
ーテルを加えて充分振とうし、α、α′−ジピリジルを
エーテル層に抽出した後、エーテル層を取り出し、エー
テルを加えて一定量にした後、分光光度計にて２８Ｏｒ
１ｍでの吸光度を測定することにより吸光度−濃度曲線
からα、α′−ジピリジル濃度をめていた。Conventionally, the concentration of α,α'-dipyridyl, an additive in chemical steel plating solutions, has been measured manually by ether extraction followed by photometry. That is, a fixed amount of plating solution is taken into a separating funnel at fixed time intervals, a fixed amount of ethyl ether is added thereto, and the mixture is thoroughly shaken to extract α,α′-dipyridyl into the ether layer. After taking out the layer and adding ether to make it a constant amount, it was measured with a spectrophotometer at 28 Or
By measuring the absorbance at 1 m, the α,α'-dipyridyl concentration was calculated from the absorbance-concentration curve.

しかしながら、このような操作は極めて煩雑であり、又
、連続検出・自動補充が困難である等の問題点があった
。However, such operations are extremely complicated, and there are problems such as continuous detection and automatic replenishment being difficult.

［発明の目的］ 本発明は上記した問題点を解消し、化学銅めっき液中の
α、α′−ジピリジル濃度の検出及び補充を自動的に精
度高く行なう自動濃度調整方法およびそのための装置を
提供することを目的とするものである。[Object of the invention] The present invention solves the above-mentioned problems and provides an automatic concentration adjustment method and apparatus for automatically and accurately detecting and replenishing the α,α′-dipyridyl concentration in a chemical copper plating solution. The purpose is to

［発明の概要］ すなわち、本発明は化学鋼めっき液中のα、α′−ジピ
リジル濃度を自動的に検出し、必要に応じてα、α′−
ジピリジルを補充してめっき液中の濃度を自動的に一定
に維持調整するにあたり、一定量のめっき液を濃度検出
用セルに分注する第１の分注器と、前記セルに第１鉄の
塩を主成分とする検出用薬液を一定量分注する第２の分
注器と、前記セルに配置された吸光度計と、α、α′−
ジピリジル溶液補給手段とを具備し、第１鉄イオンとα
、α′−ジピリジルとで形成される錯塩の５２０　ｎｍ
での吸光度を測定することにより、α′、α′−ジピリ
ジル濃度を検出し、必要に応じてα、α′−ジピリジル
溶液を補給することを特徴とするものである。[Summary of the invention] That is, the present invention automatically detects the concentration of α, α′-dipyridyl in a chemical steel plating solution, and adjusts the concentration of α, α′-dipyridyl as necessary.
To automatically maintain and adjust the concentration in the plating solution at a constant level by replenishing dipyridyl, a first dispenser dispenses a certain amount of the plating solution into a concentration detection cell, and a ferrous iron dispenser is placed in the cell. a second dispenser for dispensing a fixed amount of a detection chemical solution containing salt as a main component; an absorbance meter disposed in the cell;
dipyridyl solution replenishment means, ferrous ion and α
, 520 nm of the complex formed with α'-dipyridyl
The method is characterized in that the concentration of α',α'-dipyridyl is detected by measuring the absorbance at , and the α,α'-dipyridyl solution is replenished as necessary.

かかる自動濃度調整方法は次のような装置により、容易
に実現しうるものである。Such an automatic density adjustment method can be easily realized using the following device.

すなわち本発明の化学銅めっき液中のα、α′−ジピリ
ジルの自動濃度調整装置は、めっき液を収容するめっき
槽と、めっき液中のα、α′−ジピリジル濃度を検出す
るためのセルと、前記セルに化学銅めづき液を一定量分
注する第１の分注器と、前記セルに第１鉄の塩を主成分
とする検出用薬液を一定量分注する第２の分注器と、前
記セルに配置された吸光度計と、前記吸光度計で検出さ
れたα、α′−ジビリジル濃度検出信号電圧を入力し、
予め膜装置とを具備して成ることを特徴とするものであ
るＯ 吸光度計は、発光部（ランプ及び定電圧電源）％受光部
（フォトダイオード、又はフォトトランジスタ及び増幅
器、対数変換器）、選択透過性光学フィルタ（λｍａｘ
　＝　５２０ｎｍ　）及び吸光度セルから成り、必要な
ら光ファイバ等の光導波路を含んでもよい。That is, the automatic concentration adjustment device for α,α'-dipyridyl in a chemical copper plating solution of the present invention includes a plating tank for storing a plating solution, and a cell for detecting the concentration of α,α'-dipyridyl in the plating solution. , a first dispenser for dispensing a fixed amount of a chemical copper plating solution into the cell, and a second dispensing device for dispensing a fixed amount of a detection chemical solution containing ferrous salt as a main component into the cell. inputting the α, α′-diviridyl concentration detection signal voltage detected by the absorbance meter, the absorbance meter disposed in the cell, and the absorbance meter;
The absorbance meter is characterized by being equipped with a membrane device in advance, a light emitting part (lamp and constant voltage power supply), a light receiving part (a photodiode or a phototransistor and an amplifier, a logarithmic converter), a selection Transparent optical filter (λmax
= 520 nm) and an absorbance cell, and may include an optical waveguide such as an optical fiber if necessary.

演算制御装置は、吸光度計の検出信号電圧を入力し、予
め設定された管理目標値と比較し、管理目標以下の場合
には、α、α′−ジピリジル溶液補給手段を駆動する信
号を出力するものであり、アナログコンパレータあるい
は、信号電圧をディジタル信号に変換するＡＤ変換器を
前置した汎用コンピュータ、マイクロコンビ具−タ、デ
ィジタル論理回路等により構成される。The arithmetic and control unit inputs the detection signal voltage of the absorbance meter, compares it with a preset management target value, and outputs a signal to drive the α, α′-dipyridyl solution replenishing means if it is below the management target. It is composed of a general-purpose computer, a microcomputer, a digital logic circuit, etc., which is equipped with an analog comparator or an AD converter that converts a signal voltage into a digital signal.

α、α′−ジピリジル溶液補給手段は、α、α′−ジピ
リジル補給液タンク及び演算制御装置からの信号により
駆動される補給用ポンプから構成される。The α,α'-dipyridyl solution replenishment means includes an α,α'-dipyridyl replenishment liquid tank and a replenishment pump driven by a signal from the arithmetic and control unit.

検出用薬液は、第１鉄の塩、塩酸ヒドロキシルアミン及
びＰＨ調整剤から構成される。化学銅めっき液中のα、
α′−ジピリジル濃度が低い場合には検出用薬液中に更
に既知量のα、α′−ジピリジルを添加することにより
、低濃度領域での検出感度をより高くすることができる
。The detection chemical solution is composed of a ferrous salt, hydroxylamine hydrochloride, and a pH adjuster. α in chemical copper plating solution,
When the α'-dipyridyl concentration is low, the detection sensitivity in the low concentration region can be further increased by adding a known amount of α,α'-dipyridyl to the detection chemical solution.

第１鉄の塩は、α、α′−ジビリジルト５２０ｎｍ　ニ
吸収極大を持つ錯塩を形成させるだめのもので、硫酸第
１鉄、塩化第１鉄、硫酸第１鉄アンモニウム等、第１鉄
の塩ならばいずれも使用できるが、安定性、潮確性等取
扱の面から硫酸第１鉄アンモニウムが最も好ましい。Ferrous salts are those that do not form complex salts with α,α'-dipyridyl absorption maximum at 520 nm, such as ferrous sulfate, ferrous chloride, ferrous ammonium sulfate, etc. Although any of these can be used, ferrous ammonium sulfate is most preferred from the viewpoint of handling such as stability and tidal stability.

塩酸ヒドロキシルアミンは薬液中の第２鉄イオンを、第
１鉄イオンに還元するもので、これは、α、α′−ジピ
リジルと第１鉄イオンとの錯塩は５２０ｎｍ　に吸収極
大を持つが、第２鉄イオンとの錯塩は吸収極大を持たな
いためである。Hydroxylamine hydrochloride reduces ferric ions in a chemical solution to ferrous ions, and this is because the complex salt of α,α'-dipyridyl and ferrous ions has an absorption maximum at 520 nm; This is because complex salts with diiron ions do not have an absorption maximum.

ＰＨ調整剤は、めっき液に添加した後のＰＨを第１鉄イ
オンとの錯塩の発色が最も鋭敏であシ、かつ遊離の鉄イ
オンが水酸化鉄となって沈澱、しない範囲である３から
５にするものである。The pH of the pH adjuster after being added to the plating solution is within a range from 3 to 3, where the color development of complex salts with ferrous ions is most sensitive, and free iron ions do not turn into iron hydroxide and precipitate. This makes it a 5.

化学銅めっき液中のα、α′−ジピリジル濃度が低い場
合吸光度と添加剤濃度との間の直線関係が失なわれ、検
出誤差が多くなるため、検出用薬液中に予め、既知量の
α、α′−ジピリジルを加え、直線関係を有する部分で
検出し、精度を高めるためである。If the concentration of α, α′-dipyridyl in the chemical copper plating solution is low, the linear relationship between absorbance and additive concentration will be lost and detection errors will increase. , α'-dipyridyl is added to detect the portion having a linear relationship, thereby increasing accuracy.

［発明の実施例］ 以下本発明の実施例を図にもとすいて説明する。[Embodiments of the invention] Embodiments of the present invention will be described below with reference to the drawings.

実施例１゜ めっき液として、表１に示しためっき液組成及びめっき
条件のめっき液が準備される、又、補給液、検出用薬液
もそれぞれ表２及び表３に示したものが準備される。Example 1゜ A plating solution with the plating solution composition and plating conditions shown in Table 1 is prepared, and the replenishment solution and detection chemical solution shown in Tables 2 and 3 are also prepared, respectively. .

表２　α、α′−ジピリジル補給液組成表３　検出用薬
液組成 第１図のめっき槽１に収容されためっき液２は抽出路３
を通り、第１の分注器５により８０ｍ１分取され、α、
α′−ジピリジル濃度検出用セル６に注入される。との
抽出路３には、冷却器４が配置されている。次いで検出
用薬液８は第２の分注器７によｐ２０ｍ／分取され、前
記セル６に注入される。Table 2 Composition of α,α'-dipyridyl replenishment solution Table 3 Composition of chemical solution for detection Plating solution 2 stored in plating tank 1 in Fig.
, 80ml is collected by the first dispenser 5, α,
It is injected into the α'-dipyridyl concentration detection cell 6. A cooler 4 is disposed in the extraction path 3. Next, the detection chemical solution 8 is fractionated at 20 m/p by the second dispenser 7 and injected into the cell 6.

めっき液及び検出用薬液は、攪拌機９によシ充分混合さ
れた後、５分間静置して吸光度計１０によシα、α′−
ジピリジル濃度に対応した検出信号電圧を得る。After the plating solution and the detection chemical solution are sufficiently mixed by the stirrer 9, they are allowed to stand for 5 minutes and then measured by the absorbance meter 10.
Obtain a detection signal voltage corresponding to the dipyridyl concentration.

前記検出信号電圧はＡＤ変換器１】によシ、ディジタル
信号に変換され、演算制御装置１２でα、α′−ジピリ
ジル濃度に変換される。第２図にブロック図で示した吸
光度計を用い波長５２Ｑｎｍ、光路長１０朋でα、α′
−ジピリジルを検出した場合、濃度と検出信号電圧との
関係は第３図−（１）のようになる。The detection signal voltage is converted into a digital signal by an AD converter 1, and converted into an α, α'-dipyridyl concentration by an arithmetic and control unit 12. Using the absorbance meter shown in the block diagram in Figure 2, α and α' were measured at a wavelength of 52 Qnm and an optical path length of 10 mm.
- When dipyridyl is detected, the relationship between the concentration and the detection signal voltage is as shown in FIG. 3-(1).

α、α′−ジピリジル濃度が５０ｍｇ／Ａ付近では検出
信号電圧と濃度との間には（１）式の関係が成り立ち、
検出信号電圧から濃度が算出できる。When the α, α′-dipyridyl concentration is around 50 mg/A, the relationship of equation (1) holds between the detection signal voltage and the concentration.
The concentration can be calculated from the detection signal voltage.

た管理目標値と比較し、低い場合には、演算制御装置１
２からα、α′−ジピリジル補給用ポンプ１３に対し、
駆動信号が出力され、α、α′−ジピリジル補給用タン
ク１４から所定量の補給液が供給される。なお、検出さ
れたα、α′−ジピリジル濃度は、印字装置１５忙よシ
記録される。濃度検出が終了した検出セル内のめっき液
及び検出用薬液は、電磁弁１６を作動させることにより
排出される。この後、検出用セルには、ポンプ１７によ
りイオン交換水（又は蒸留水）１８が供給され、セルの
洗浄が行なわれる。Compare it with the management target value, and if it is low, the arithmetic and control unit 1
2 to α, α′-dipyridyl replenishment pump 13,
A drive signal is output, and a predetermined amount of replenishment liquid is supplied from the α,α'-dipyridyl replenishment tank 14. Note that the detected α,α'-dipyridyl concentration is recorded by the printing device 15. The plating solution and detection chemical solution in the detection cell whose concentration has been detected are discharged by operating the solenoid valve 16. Thereafter, ion exchange water (or distilled water) 18 is supplied to the detection cell by a pump 17, and the cell is cleaned.

洗浄水の排出が終わった後、電磁弁１６は非作動状態に
なり、上記一連の検出補充動作を一定の時間間隔で繰返
す。After the washing water has been discharged, the solenoid valve 16 becomes inactive, and the series of detection and replenishment operations described above are repeated at regular time intervals.

本装置を使用することにより、めっき液中のα。By using this device, α in the plating solution can be reduced.

α′−ジピリジル濃度は第４図−（１）Ｋ示すように、
一定の幅で維持管理できることが確認された。The α'-dipyridyl concentration is as shown in Figure 4-(1)K.
It was confirmed that maintenance can be done within a certain range.

実施例２゜ めっき液として、表４に示しためっき液組成及びめっき
条件のものを、又、補給液、検出用薬液として、それぞ
れ表５及び表６に示したものを用い、実施例１と同様に
してα、α′−ジピリジルの検出、補充を行なっ、た。Example 2゜As the plating solution, the plating solution composition and plating conditions shown in Table 4 were used, and as the replenishing solution and the detection chemical solution, those shown in Tables 5 and 6, respectively, were used. α,α'-dipyridyl was detected and supplemented in the same manner.

表２　α、α′−ジピリジル補給液組成表３　検出用薬
液組成 この場合α、α′−ジピリジル濃度と検出電圧との関係
は第３図−（２）のようになり、低濃度でも直線関係を
示す。又、濃度は（２）式のようになり、低濃度でも直
線関係を示す。又、濃度は（２）式を用いて検出信号電
圧から算出できる。Table 2 Composition of α,α'-dipyridyl replenishment solution Table 3 Composition of chemical solution for detection In this case, the relationship between α, α'-dipyridyl concentration and detection voltage is as shown in Figure 3-(2), and there is a linear relationship even at low concentrations. shows. Further, the concentration is as shown in equation (2), which shows a linear relationship even at low concentrations. Further, the concentration can be calculated from the detection signal voltage using equation (2).

ジピリジル濃度は第４図−（２）に示すように、一定の
幅で維持管理できることが確認された。As shown in Figure 4-(2), it was confirmed that the dipyridyl concentration could be maintained within a certain range.

上記実施例１及び２においては、検出信号電圧をディジ
タル信号に変換し、更に演算処理によりα、α′−ジピ
リジル濃度に変換した後、管理目標値と比較したが、デ
ィジタル信号のまま、ディジタル論理回路により比較す
る、或は、検出信号電圧のままアナログコンパレータに
より比較する等の方法によっても本発明の目的である濃
度調整が可能ガことは明らかである。In Examples 1 and 2 above, the detection signal voltage was converted into a digital signal and further converted into α, α'-dipyridyl concentration through arithmetic processing, and then compared with the control target value. It is clear that the concentration adjustment, which is the object of the present invention, can also be achieved by comparing using a circuit or using an analog comparator to compare the detection signal voltage as it is.

又、検出用のセル及び吸光度計の例を第５図から第７図
に示すが、その構造はとれらに限定されるものではない
。Furthermore, although examples of a detection cell and an absorbance meter are shown in FIGS. 5 to 7, the structure thereof is not limited thereto.

［発明の効果コ 以上の説明及び実施例で明らかなように、本発明によれ
ば、手分析に比較してめっき液中のα、ｌ−ジビリジル
濃度を連続的にかつ高精度で検出でき、一定の幅で維持
管理できるものである。又、めっき液中のα、α′−ジ
ピリジル濃度変化による析出速度の変化がないために、
めっき厚みのコントロールが容易であると共に、めっき
液中のα、α′−ジビリジル濃度低下による析出銅物性
の低下がないことから高品質の製品が得られる等多くの
利点を有するものである。[Effects of the Invention] As is clear from the above description and examples, according to the present invention, the α,l-diviridyl concentration in the plating solution can be detected continuously and with high precision compared to manual analysis. It can be maintained and managed within a certain range. In addition, since there is no change in the precipitation rate due to changes in the α, α′-dipyridyl concentration in the plating solution,
It has many advantages, such as easy control of the plating thickness and the fact that the physical properties of the deposited copper do not deteriorate due to a decrease in the concentration of α,α'-diviridyl in the plating solution, resulting in a high-quality product.

【図面の簡単な説明】[Brief explanation of the drawing]

第１図は本発明の化学銅めっき液中のα、α′−ジピリ
ジルの自動濃度調整装置の構成図、第２図は吸光度計の
構成図、第３図はめっき液中のα、α′−ジピリジル濃
度と吸光度計での検出信号電圧の関係を示す図で（１）
及び（２）はそれぞれ本発明実施例１及び２に対応する
説明図、第４図は本発明の装置を使用した際のめっき液
中のα、α′−ジピリジル濃度の時間変化を示す図で（
１）及び（２）はそれぞれ実施例１及び２に対応する。 第５図から第７図は検出用セル及び吸光度計の模式図で
ある。 １・・めっき槽、２・・めっき液、３・・・抽出路、４
・・・冷却器、５．７・・・分注器、６．２４．５１　
、６１　、７１・・・検出用セル、８・・・検出用薬液
タンク、９・・・攪拌機、１０・・・吸光度計、１１・
・・ＡＤ変換器、１２・・・演算制御装置、１３・・・
補給用ポンプ、１４・・・補給用タンク、１５・・・印
字装置、１６・・・電磁弁、１７・・・洗浄用ポンプ、
１８・・・洗浄水タンク、２１・・・定電圧電源、ρ、
　５２　、６２　、７２・・ランプ、ム、　２５　、５
５・・・レンズ、 ２６　、５３　、６３　、７３・・・フィルタ、２７、
５４　、６４　、７４・・・フォトトランジスタ、謔・
・・増幅器、　四・・・対数変換器、６５　、７５・・
・光ファイバー、７６・・・反射鏡。 第　１　図 第２図 ／ｆ）−；Ｃ液中のべ、ぺｔジと’１／ジルｌし隻　（
竺シ全）第　４　図 嬉　７　Ｍ 日ジ　ｌ　ｌ”−Ｍ ＱＡ− １Fig. 1 is a block diagram of an automatic concentration adjustment device for α, α'-dipyridyl in a chemical copper plating solution according to the present invention, Fig. 2 is a block diagram of an absorbance meter, and Fig. 3 is a block diagram of an apparatus for automatically adjusting the concentration of α, α'-dipyridyl in a chemical copper plating solution. - A diagram showing the relationship between dipyridyl concentration and detection signal voltage in an absorbance meter (1)
and (2) are explanatory diagrams corresponding to Examples 1 and 2 of the present invention, respectively, and FIG. 4 is a diagram showing the time change of α,α'-dipyridyl concentration in the plating solution when using the apparatus of the present invention. (
1) and (2) correspond to Examples 1 and 2, respectively. 5 to 7 are schematic diagrams of a detection cell and an absorbance meter. 1... Plating tank, 2... Plating solution, 3... Extraction path, 4
... Cooler, 5.7 ... Dispenser, 6.24.51
, 61 , 71... detection cell, 8... detection chemical tank, 9... stirrer, 10... absorbance meter, 11...
...AD converter, 12... Arithmetic control device, 13...
Supply pump, 14... Supply tank, 15... Printing device, 16... Solenoid valve, 17... Cleaning pump,
18...Washing water tank, 21... Constant voltage power supply, ρ,
52, 62, 72...Lamp, Mu, 25, 5
5... Lens, 26, 53, 63, 73... Filter, 27,
54, 64, 74...phototransistor, song/
... Amplifier, 4... Logarithmic converter, 65, 75...
・Optical fiber, 76...reflector. Fig. 1 Fig. 2/f)-;
Complete text) Figure 4 7 M day l l”-M QA-1

Claims (3)

【特許請求の範囲】[Claims] （１）添加剤として、α、α′−ジピリジルを含む化学
銅めっき液を一定量濃度検出用セルに分注する第１の分
注器と、前記セルに第１鉄の塩を主成分とする検出用薬
液を一定量分注する第２の分注器と、前記セルに配置さ
れた吸光度計と、α、α′−ジピリジル溶液補給手段と
を具備し、第１鉄イオンとα。 α′−ジピリジルとで形成される錯塩の吸光度を測定す
ることによりα、α′−ジピリジル濃度を検出し、必要
に応じてα、α′−ジピリジル溶液を補給することを特
徴とする化学銅めっき液中のα、α′−ジピリジルの自
動濃度調整方法。(1) A first dispenser for dispensing a fixed amount of a chemical copper plating solution containing α,α'-dipyridyl as an additive into a concentration detection cell; a second dispenser for dispensing a fixed amount of a detection chemical solution, an absorbance meter disposed in the cell, and an α,α'-dipyridyl solution replenishing means. Chemical copper plating characterized by detecting the α,α′-dipyridyl concentration by measuring the absorbance of a complex salt formed with α′-dipyridyl, and replenishing the α,α′-dipyridyl solution as necessary. Automatic concentration adjustment method of α,α′-dipyridyl in liquid. （２）めっき液を収容するめっき槽と、めっき液中のα
、α′−ジピリジル濃度を検出するだめのセルと前記セ
ルに化学銅めっき液を一定量分注する第１の分注器と、
前記セルに第１鉄の塩を主成分とする検出用薬液を一定
量分注する第２の分注器と。 前記セル釦配置さ些た吸光度計と、前記吸光度計で検出
され麩α、α′−ジピリジル濃度検出信号電圧を入力し
、予め設定された管理目標値と比較し、α、α′−ジピ
リジル溶液補給手段を駆動する信号を出力する演算制御
装置とを具備して成ることを特徴とする化学銅めっき液
中のα、α′−ジピリジルの自動濃度調整装置。(2) A plating tank containing a plating solution and α in the plating solution
, a cell for detecting α'-dipyridyl concentration, and a first dispenser for dispensing a certain amount of chemical copper plating solution into the cell;
a second dispenser for dispensing a fixed amount of a detection chemical solution containing a ferrous salt as a main component into the cell; The α,α′-dipyridyl concentration detection signal voltage detected by the absorbance meter is inputted to the small absorbance meter arranged in the cell button, and compared with a preset control target value, the α,α′-dipyridyl solution is 1. An automatic concentration adjustment device for α, α'-dipyridyl in a chemical copper plating solution, comprising: a calculation control device that outputs a signal for driving a replenishing means. （３）α、α′−ジピリジル検出用薬液にあらかじめ既
知量のα、α′−ジピリジルを添加し、低濃度での検出
精度を高めることを特徴とする特許請求の範囲第１項お
よび第２項記載の化学銅めっき液中のα。 α′−ジピリジル濃度の調整方法およびそのための装置
。(3) Claims 1 and 2, characterized in that a known amount of α,α′-dipyridyl is added in advance to the chemical solution for α,α′-dipyridyl detection to improve detection accuracy at low concentrations. α in the chemical copper plating solution described in section. A method for adjusting α'-dipyridyl concentration and an apparatus therefor.