JPH0115819B2 - - Google Patents
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- Publication number
- JPH0115819B2 JPH0115819B2 JP52063339A JP6333977A JPH0115819B2 JP H0115819 B2 JPH0115819 B2 JP H0115819B2 JP 52063339 A JP52063339 A JP 52063339A JP 6333977 A JP6333977 A JP 6333977A JP H0115819 B2 JPH0115819 B2 JP H0115819B2
- Authority
- JP
- Japan
- Prior art keywords
- plating solution
- copper plating
- chemical copper
- solution
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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- 239000000243 solution Substances 0.000 claims description 64
- 238000007747 plating Methods 0.000 claims description 63
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 50
- 229910052802 copper Inorganic materials 0.000 claims description 50
- 239000010949 copper Substances 0.000 claims description 50
- 239000000126 substance Substances 0.000 claims description 49
- 239000011521 glass Substances 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 10
- 239000008139 complexing agent Substances 0.000 claims description 10
- 229910001431 copper ion Inorganic materials 0.000 claims description 10
- 238000006386 neutralization reaction Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000005259 measurement Methods 0.000 claims description 5
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 5
- -1 hydrogen ions Chemical class 0.000 description 5
- 235000011121 sodium hydroxide Nutrition 0.000 description 5
- 239000012670 alkaline solution Substances 0.000 description 4
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical group OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 2
- 238000001139 pH measurement Methods 0.000 description 2
- 229960003330 pentetic acid Drugs 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical class OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical compound [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
Landscapes
- Chemically Coating (AREA)
Description
【発明の詳細な説明】
〔発明の利用分野〕
本発明は高アルカリ性化学銅めつき液のPHを精
度よく基準のPHに調節する方法に関するものであ
る。DETAILED DESCRIPTION OF THE INVENTION [Field of Application of the Invention] The present invention relates to a method for accurately adjusting the pH of a highly alkaline chemical copper plating solution to a reference pH.
化学銅めつきの反応はめつき液のPHに大きく影
響されるものである。すなわち、銅イオンの還元
剤として、一般にホルムアルデヒドが用いられ
る。ホルムアルデヒドはPH：13となると急速に反
応性が増大すること、主成分である２価の銅イオ
ンが高アルカリ性溶液中では上記ホルムアルデヒ
ドに還元を受けて金属銅として析出する以外に１
価銅イオンで停止し１価の銅酸化物を発生する
が、この１価銅酸化物がめつき皮膜の機械的性質
を劣化すること、めつき液を分解すること等から
めつき液の適正なPH管理は極めて重要である。
The reaction of chemical copper plating is greatly influenced by the pH of the plating solution. That is, formaldehyde is generally used as a reducing agent for copper ions. The reactivity of formaldehyde rapidly increases when the pH reaches 13, and divalent copper ions, which are the main component, are reduced to formaldehyde and precipitated as metallic copper in highly alkaline solutions.
It stops with valent copper ions and generates monovalent copper oxide, but since monovalent copper oxide degrades the mechanical properties of the plating film and decomposes the plating solution, it is important to maintain the appropriate pH of the plating solution. Management is extremely important.
従来、PH測定は、一般に市販されている実験室
用、工業用のガラス電極で行なつていた。そし
て、ガラス電極は、室温付近に冷却された測定液
に浸漬するのみで迅速にPH測定ができるために、
極めて取り扱いが容易であつた。 Conventionally, PH measurements have been carried out using commercially available glass electrodes for laboratory and industrial use. Glass electrodes can quickly measure pH by simply immersing them in a measurement solution cooled to around room temperature.
It was extremely easy to handle.
しかし、ガラス電極は、被測定液のPHが10以上
のアルカリ性溶液ではアルカリ誤差、塩誤差が著
しく大きくなり、正しいPHを測定できないばかり
か、長時間の測定では、それらの誤差がより増大
する欠点があつた。 However, glass electrodes have the drawback that when using an alkaline solution with a pH of 10 or higher, the alkaline error and salt error become significantly large, which not only makes it impossible to measure the correct pH, but also increases these errors over long periods of measurement. It was hot.
化学銅めつき液のPHは、11.5〜13.5の高アルカ
リ性液であるために、上記の原因によつて生ずる
誤差は著しく大きいものであつた。さらに、化学
銅めつきはめつき速度が遅く、厚いめつき皮膜を
得る場合には、長時間のめつきを必要とし化学銅
めつき液の主成分を自動濃度管理することによつ
て無人化し、コストの低減をはからねばならない
が、最も基本的に管理されるべきめつき液のPH
が、上記理由によつて無人化できないものであつ
た。 Since the chemical copper plating solution is a highly alkaline solution with a pH of 11.5 to 13.5, the error caused by the above causes was extremely large. Furthermore, chemical copper plating has a slow plating speed and requires long plating to obtain a thick plating film. Although efforts must be made to reduce costs, the pH of the plating solution must be controlled most fundamentally.
However, for the reasons mentioned above, it was not possible to make it unmanned.
さらに、高アルカリ性溶液中で、上記のガラス
電極のごとき劣化を生じないアンチモン電極もあ
るが、PH変化に対する応答速度が遅く、自動濃度
管理には適さないものであつた。 Furthermore, although there are antimony electrodes that do not deteriorate in highly alkaline solutions like the glass electrodes mentioned above, they have a slow response speed to pH changes and are not suitable for automatic concentration control.
本発明は、上記した従来の化学銅めつき液のPH
を調節する方法の欠点を解決するためになされた
もので、ガラス電極でもPHを精度良く調節する方
法を提供するにある。
The present invention improves the pH of the conventional chemical copper plating solution mentioned above.
This was done to solve the drawbacks of methods for adjusting PH, and to provide a method for accurately adjusting PH even with glass electrodes.
上記目的を達成するために発明者は、化学銅め
つき液のPHを調節する方法につき種々検討した結
果銅イオンと、銅イオンの錯化剤と、銅イオンの
還元剤と、アルカリ金属の水酸化物よりなる化学
銅めつき液から一定容量の化学銅めつき液を採取
し、採取した化学銅めつき液に一定濃度及び一定
容量の酸を加えて混合液とし、ガラス電極と参照
電極で該混合液のPHを測定し、該PHに基いて、予
め実測して求めておいてあつた混合液のPHと化学
銅めつき液のPHとの対応から該化学銅めつき液の
PHを求め、該化学銅めつき液のPHが基準のPHとな
るように該化学銅めつき液のPHを調節すること
で、PHを精度良く調節することが出来ることを明
らかにした。さらに、本方法によればガラス電極
の寿命が長くなるし、連続測定が出来る。
In order to achieve the above object, the inventor investigated various ways to adjust the pH of a chemical copper plating solution, and as a result, the inventors developed a method using copper ions, a complexing agent for copper ions, a reducing agent for copper ions, and an alkali metal water solution. Collect a certain volume of chemical copper plating solution from a chemical copper plating solution made of oxides, add a certain concentration and a certain volume of acid to the sampled chemical copper plating solution to make a mixed solution, and use it with a glass electrode and a reference electrode. The PH of the mixed solution is measured, and based on the PH, the PH of the chemical copper plating solution is calculated based on the correspondence between the PH of the mixed solution and the PH of the chemical copper plating solution, which was actually measured in advance.
It was revealed that the PH can be adjusted accurately by determining the PH and adjusting the PH of the chemical copper plating solution so that the PH of the chemical copper plating solution becomes the reference PH. Furthermore, according to this method, the life of the glass electrode becomes longer and continuous measurements can be performed.
以下に、本発明の原理を説明する。ガラス電極
は、PH２〜10で劣化しない。このため、化学銅め
つき液に酸を加えてPHを２〜10にするがPHが４よ
り小さいと、加えた酸の水素イオンがめつき反応
の進行に伴つて蓄積した硫酸イオン、ギ酸イオン
と反応するため、PH値が正確に調整できない。 The principle of the present invention will be explained below. Glass electrodes do not deteriorate at pH 2-10. For this reason, acid is added to the chemical copper plating solution to adjust the pH to 2 to 10, but if the pH is lower than 4, the hydrogen ions of the added acid will be mixed with sulfate and formate ions that accumulate as the plating reaction progresses. Because of the reaction, the pH value cannot be adjusted accurately.
このため、PHを測定するときの化学銅めつき液
のPHは４〜10にするのが良い。 For this reason, it is best to set the pH of the chemical copper plating solution to 4 to 10 when measuring the pH.
また、銅イオンの錯化剤にエチレンジアミン四
酢酸ナトリウム（EDTA）塩を用いた化学銅め
つき液では、この溶液10mlを0.15規定硫酸で中和
すると、第１図の中和曲線となる。化学銅めつき
液のPH値が7.5、4.5付近においては、それぞれ下
記(1)、(2)式の反応が起こり、少量の酸でPH値が大
きく変化する。 In addition, in a chemical copper plating solution using sodium ethylenediaminetetraacetate (EDTA) salt as a complexing agent for copper ions, when 10 ml of this solution is neutralized with 0.15N sulfuric acid, the neutralization curve shown in Figure 1 is obtained. When the PH value of the chemical copper plating solution is around 7.5 and 4.5, the following reactions (1) and (2) occur, respectively, and the PH value changes significantly with a small amount of acid.
PH：7.5付近（錯化剤の中和当量点付近、即ち、
酸解離会合当量点付近、以下単に錯化剤の中和
当量点付近と云う）
L4-＋H+＝LH3- ……(1)
PH：4.5付近（錯化剤の中和当量点付近）
LH3-＋H+＝LH2 2- ……(2)
（但し、(1)式中L4-は遊離のエチレンジアミン四
酢酸イオンである。）
そして、この際めつき液中に蓄積されている硫
酸イオン、ギ酸イオンが上記(1)、(2)式の反応を妨
害することはない。PH: around 7.5 (near the neutralization equivalent point of the complexing agent, i.e.
(near the acid dissociation association equivalent point, hereinafter simply referred to as the neutralization equivalent point of the complexing agent) L 4- +H + =LH 3- ...(1) PH: around 4.5 (near the neutralization equivalent point of the complexing agent) LH 3- +H + =LH 2 2- ...(2) (However, in formula (1), L 4- is a free ethylenediaminetetraacetic acid ion.) At this time, the ions accumulated in the plating solution Sulfate ions and formate ions do not interfere with the reactions of formulas (1) and (2) above.
錯化剤がジエチレントリアミン５酢酸
（DTPA）の場合はPH5.7、ニトリロ三酢酸
（NTA）の場合はPH6.0、イミノ二酢酸（IDA）
の場合はPH5.5が中和当量点であり、ロツセル塩、
酒石酸の場合は、PH4.0が中和当量点である。し
たがつてこれらPH値の付近では少量の酸でPH値が
大きく変化する。したがつて、化学銅めつき液の
PH調節をPH４〜10の範囲内に存在する錯化剤の中
和当量点近傍のPH値で行なえば、精度よく調節で
きる。 PH5.7 if the complexing agent is diethylenetriaminepentaacetic acid (DTPA), PH6.0 if nitrilotriacetic acid (NTA), iminodiacetic acid (IDA)
In the case of , PH5.5 is the neutralization equivalent point, and Rotussel salt,
In the case of tartaric acid, PH4.0 is the neutralization equivalent point. Therefore, in the vicinity of these PH values, a small amount of acid causes a large change in the PH value. Therefore, chemical copper plating solution
If the pH is adjusted to a pH value near the neutralization equivalent point of the complexing agent within the range of pH 4 to 10, the pH can be adjusted with high precision.
還元剤としてはホルムアルデヒド、水素化ホウ
酸アルカリ金属塩、有機ホウ素化合物などが良
い。 Preferred reducing agents include formaldehyde, alkali metal borate hydride, and organic boron compounds.
アルカリ金属の水酸化物としては苛性ソーダ、
苛性カリなどが良い。 As alkali metal hydroxides, caustic soda,
Caustic potash is good.
以下、実施例により本発明を更に具体的に説明
する。 Hereinafter, the present invention will be explained in more detail with reference to Examples.
実施例
化学銅めつき液組成
CuSO4・5H2O ……15ｇ
EDTA−2Na ……44ｇ
NaOH ……11.6ｇ（PH：12.2）
37％ホルマリン ……９ml
添加剤 ……少量
水 ……全体を１とする量
酸溶液（0.15規定硫酸）
H2SO4 ……2.42ml
水 ……全体を１とする量
上記の溶液、をそれぞれ多連チユーブポン
プで流速20ml／ｈの割合でそれぞれ10ml、9.6ml
採取し、これを均一に混合すると第１図からわか
るようにPH7.5の溶液となる。この溶液をPH測定
セルに導びき、GCT−155型電極（東亜電波工業
株式会社製、主電極：ガラス電極、参照電極：
1N、HgCl、この電極では、PHが７のとき0mV、
PHが７以下を負、７以上を正とし、±100ｍＶ／PH
の出力電圧を示す。）で測定すると、デジタルボ
ルトメーターの出力は＋50ｍＶとなる。つまり、
元の化学銅めつき液から採取した溶液に対してデ
ジタルボルトメータの出力が＋50ｍＶであれば、
その採取した溶液はPH7.5であることがわかり、
それに対応して元の化学銅めつき液のPHが12.2で
あることがわかるのである。元の化学銅めつき液
のPHを変えて、元のめつき液10mlに0.15規定硫酸
を9.6ml加えたときに、その採取前後の化学銅め
つき液のPHの対応関係を実測して求めたのが第２
図である。採取した化学銅めつき液のPHをデジタ
ルボルトメータにより求めることにより、第２図
から元の化学銅めつき液のPHを求めることができ
るのである。次に、本発明に係わる化学銅めつき
液のPHを調節する実施例について以下に説明す
る。
Example Chemical copper plating liquid composition CuSO 4・5H 2 O ...15g EDTA-2Na ...44g NaOH ...11.6g (PH:12.2) 37% formalin ...9ml Additives ...a small amount of water ...total Amount of acid solution (0.15N sulfuric acid) H 2 SO 4 ...2.42ml Water ...Amount taking the total as 1 The above solutions were pumped with multiple tube pumps at a flow rate of 20ml/h to 10ml and 9.6ml, respectively.
When collected and mixed uniformly, it becomes a solution with a pH of 7.5, as shown in Figure 1. This solution is introduced into a PH measurement cell using a GCT-155 type electrode (manufactured by Toa Denpa Kogyo Co., Ltd., main electrode: glass electrode, reference electrode:
1N, HgCl, with this electrode, 0mV when pH is 7,
PH is 7 or less as negative, 7 or more as positive, ±100mV/PH
shows the output voltage of ), the output of the digital voltmeter will be +50mV. In other words,
If the output of the digital voltmeter is +50mV with respect to the solution taken from the original chemical copper plating solution,
The sampled solution was found to have a pH of 7.5,
Correspondingly, the pH of the original chemical copper plating solution was found to be 12.2. When the PH of the original chemical copper plating solution was changed and 9.6ml of 0.15N sulfuric acid was added to 10ml of the original plating solution, the relationship between the PH of the chemical copper plating solution before and after sampling was actually measured and determined. The second one was
It is a diagram. By determining the PH of the sampled chemical copper plating solution using a digital voltmeter, the PH of the original chemical copper plating solution can be determined from Figure 2. Next, an example of adjusting the pH of a chemical copper plating solution according to the present invention will be described below.
化学銅めつき液のPHが12.4に変動している場合
について説明する。上記と同様にして一定容量の
化学銅めつき液を採取して、一定濃度、一定容量
の酸を加える。そして、上記と同様にしてデジタ
ルボルトメータにより電圧を測定すると＋170ｍ
Ｖであつた。この値より採取された化学銅めつき
液はPH8.7であることがわかる。そして、第２図
の対応図から元の化学銅めつき液のPHは12.4にな
つていることがわかる。元の化学銅めつき液のPH
を12.2に修正するには、デジタルボルトメータの
出力と＋50ｍＶとの電位差を励動源として電磁弁
を開いて２規定硫酸をめつき液に加え、上記電位
差が零となつた時点で電磁弁を閉じて２規定硫酸
の補給を止めれば良い。 A case where the pH of the chemical copper plating solution fluctuates to 12.4 will be explained. Collect a certain volume of chemical copper plating solution in the same manner as above, and add a certain concentration and a certain volume of acid. Then, if you measure the voltage with a digital voltmeter in the same way as above, it will be +170m.
It was V. From this value, it can be seen that the chemical copper plating solution sampled has a pH of 8.7. From the correspondence diagram in Figure 2, it can be seen that the pH of the original chemical copper plating solution is 12.4. Original chemical copper plating solution PH
12.2, open the solenoid valve using the potential difference between the output of the digital voltmeter and +50 mV as an excitation source, add 2N sulfuric acid to the plating solution, and then close the solenoid valve when the potential difference becomes zero. Just close it and stop supplying 2N sulfuric acid.
化学銅めつき液のPH12.0に変動している場合も
上記と同様にして一定容量のめつき液を採取し
て、一定濃度、一定容量の酸を加え、上記と同様
にしてデジタルボルトメータの出力を測定したと
ころその値は−70ｍＶであつた。この値から上記
と同様に元の化学銅めつき液のPHが12.0であるこ
とがわかる。PHを12.2に修正するには、デジタル
ボルトメータの出力と＋50ｍＶとの電位差を励動
源として電磁弁を開いて２規定苛性ソーダを元の
化学銅めつき液に加え、上記の電位差が零となつ
た時点で電磁弁を閉じて２規定苛性ソーダの補給
を止めれば良い。 Even if the pH of the chemical copper plating solution fluctuates to 12.0, collect a certain volume of the plating solution in the same way as above, add a certain concentration and a certain volume of acid, and measure it with a digital voltmeter in the same way as above. When the output was measured, the value was -70 mV. From this value, it can be seen that the PH of the original chemical copper plating solution is 12.0, similar to the above. To correct the pH to 12.2, open the solenoid valve using the potential difference between the output of the digital voltmeter and +50 mV as the excitation source, add 2N caustic soda to the original chemical copper plating solution, and then add 2N caustic soda to the original chemical copper plating solution until the above potential difference becomes zero. At that point, close the solenoid valve to stop replenishing the 2N caustic soda.
第２図からわかるように本法によれば極めて高
精度（約７倍）でPHを測定して、めつき液中のPH
の調節ができる。また、ガラス電極の劣化がない
ので、電極寿命が延び、20時間にわたりガラス電
極を補正することなく、連続測定、自動制御が出
来た。
As can be seen from Figure 2, this method measures the PH with extremely high accuracy (approximately 7 times) and the PH in the plating solution.
can be adjusted. In addition, since there is no deterioration of the glass electrode, the electrode life is extended, and continuous measurement and automatic control can be performed for 20 hours without having to correct the glass electrode.
第１図は錯化剤にエチレンジアミン四酢酸二ナ
トリウム塩を用いた化学銅めつき液10mlを0.15規
定硫酸で中和したときの中和曲線、第２図は化学
銅めつき液10mlに0.15規定硫酸9.6mlを加えてPH
調節を行なつた際の硫酸添加前後のPH変化を示す
図である。
Figure 1 shows the neutralization curve when 10ml of a chemical copper plating solution using ethylenediaminetetraacetic acid disodium salt as a complexing agent is neutralized with 0.15N sulfuric acid, and Figure 2 shows the neutralization curve when 10ml of a chemical copper plating solution is added to 0.15N sulfuric acid. Add 9.6ml of sulfuric acid to pH
FIG. 3 is a diagram showing PH changes before and after addition of sulfuric acid during adjustment.
Claims (1)
の還元剤と、アルカリ金属の水酸化物よりなる化
学銅めつき液から一定容量の化学銅めつき液を採
取し、採取した化学銅めつき液に一定濃度及び一
定容量の酸を加えて混合液とし、ガラス電極と参
照電極で該混合液のPHを測定し、該PHに基いて、
予め実測して求めておいてあつた混合液のPHと化
学銅めつき液のPHとの対応から該化学銅めつき液
のPHを求め、該化学銅めつき液のPHが基準のPHと
なるように該化学銅めつき液のPHを調節するこを
特徴とする化学銅めつき液のペーハー調節方法。 ２ 特許請求の範囲第１項において、採取した化
学銅めつき液のPHがPH４〜10の範囲であつて化学
銅めつき液の錯化剤の中和当量点付近となるよう
に酸を加えることを特徴とする化学銅めつき液の
ペーハー調節方法。[Claims] 1. A certain volume of a chemical copper plating solution is collected from a chemical copper plating solution consisting of copper ions, a complexing agent for copper ions, a reducing agent for copper ions, and an alkali metal hydroxide. Then, add a certain concentration and a certain volume of acid to the sampled chemical copper plating solution to make a mixed solution, measure the PH of the mixed solution with a glass electrode and a reference electrode, and based on the PH,
The PH of the chemical copper plating solution is determined from the correspondence between the PH of the mixed solution and the PH of the chemical copper plating solution, which was determined by actual measurements in advance, and the PH of the chemical copper plating solution is determined to be the standard PH. 1. A method for adjusting the pH of a chemical copper plating solution, which comprises adjusting the pH of the chemical copper plating solution so that the pH of the chemical copper plating solution is adjusted. 2 In claim 1, acid is added so that the pH of the sampled chemical copper plating solution is in the range of PH4 to 10 and is near the neutralization equivalent point of the complexing agent in the chemical copper plating solution. A method for adjusting the pH of a chemical copper plating solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6333977A JPS53149388A (en) | 1977-06-01 | 1977-06-01 | Ph measuring method of chemical copper plating solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6333977A JPS53149388A (en) | 1977-06-01 | 1977-06-01 | Ph measuring method of chemical copper plating solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS53149388A JPS53149388A (en) | 1978-12-26 |
| JPH0115819B2 true JPH0115819B2 (en) | 1989-03-20 |
Family
ID=13226371
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6333977A Granted JPS53149388A (en) | 1977-06-01 | 1977-06-01 | Ph measuring method of chemical copper plating solution |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS53149388A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0440662U (en) * | 1990-07-31 | 1992-04-07 |
-
1977
- 1977-06-01 JP JP6333977A patent/JPS53149388A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0440662U (en) * | 1990-07-31 | 1992-04-07 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS53149388A (en) | 1978-12-26 |
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