JPS6143660B2 - - Google Patents
Info
- Publication number
- JPS6143660B2 JPS6143660B2 JP59137118A JP13711884A JPS6143660B2 JP S6143660 B2 JPS6143660 B2 JP S6143660B2 JP 59137118 A JP59137118 A JP 59137118A JP 13711884 A JP13711884 A JP 13711884A JP S6143660 B2 JPS6143660 B2 JP S6143660B2
- Authority
- JP
- Japan
- Prior art keywords
- concentration
- chelating agent
- copper
- potential
- plating solution
- 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
Links
- 239000002738 chelating agent Substances 0.000 claims description 36
- 238000007747 plating Methods 0.000 claims description 33
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 29
- 229910001431 copper ion Inorganic materials 0.000 claims description 29
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 15
- 229910052802 copper Inorganic materials 0.000 claims description 15
- 239000010949 copper Substances 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 239000013522 chelant Substances 0.000 claims description 4
- -1 iron ions Chemical class 0.000 claims description 4
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 3
- 239000003638 chemical reducing agent Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000000691 measurement method Methods 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- 238000004448 titration Methods 0.000 description 8
- 238000001514 detection method Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 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 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KCQUJORJVXQRST-UHFFFAOYSA-N acetic acid;ethane-1,2-diamine Chemical compound CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.NCCN KCQUJORJVXQRST-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
- G01N31/16—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using titration
- G01N31/162—Determining the equivalent point by means of a discontinuity
- G01N31/164—Determining the equivalent point by means of a discontinuity by electrical or electrochemical means
Landscapes
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Electrochemistry (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Chemically Coating (AREA)
Description
〔発明の利用分野〕
本発明は、化学銅めつき液中のキレート剤濃度
の測定方法に関する。
〔発明の背景〕
最近、プリント配線板は、化学銅めつきにより
絶縁基板上に回路導体を設けて製造している。
この場合、回路導体であるめつき皮膜は、電気
特性と機械特性が良好であることが要求される。
一般に化学銅めつき液は、銅イオン、銅イオン
のキレート剤もしくは錯化剤、還元剤およびアル
カリ金属の水酸化物からなつている。そして、化
学銅めつき液中の銅イオンはめつき反応によつて
消費され、キレート剤は被めつき体に付着して、
無視できない程度に槽外に持ち出され濃度が低下
する。
なお、化学銅めつき皮膜の機械特性は、めつき
剤中の銅イオン濃度、キレート剤もしくは錯化剤
の濃度に著しく影響を受ける。このため、これら
成分の濃度管理が必要となる。
従来、銅イオンのキレート剤はめつき反応で消
費されるものではないとして、濃度測定が行なわ
れていなかつた。
〔発明の目的〕
本発明の目的は、上記した従来技術の欠点をな
くし、化学銅めつき液中のキレート剤濃度を精度
良く測定する方法を提供するにある。
〔発明の概要〕
上記目的は、銅イオンと、銅イオンのキレート
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に、このめつき液中
に存在する全キレート剤のモル濃度を少し越える
モル濃度の三価鉄イオンを加え、この溶液の酸化
還元電位を不溶性の電極と、参照電極とで測定し
て全キレート剤濃度を求めることを特徴とする化
学銅めつき液中のキレート剤濃度測定方法を提供
するにある。
以下に、本発明の測定原理を説明する。キレー
ト剤であるエチレンジアミン四酢酸（以後EDTA
と略記）、エチレンジアミン五酢酸（以後EDPA
と略記）と、二価の銅イオンは１：１のモル濃度
比で反応する。この反応がキレート生成反応であ
り、反応生成物が銅のキレート化合物である。
今、化学銅めつき液中の銅イオン濃度をＣモ
ル、キレート剤のモル濃度をｎ倍のnCモルとす
れば（一般に、キレート剤は銅イオン濃度の1.5
〜５倍加える）、二価銅イオンは完全にキレート
化される。そして、白金、金などの不溶性の主電
極と、参照電極を用いて、めつき液に微量存在す
る一価銅イオン（以後ＣＩ ｕと略記）と二価銅イオ
ンのキレート化合物（Ｃ〓ｕと略記）との間の電位
を測定すると(1)式のようになる。
Ｅ（１）＝0.153−0.0592log
｛Ｋ（ｎ−１）〔Ｃ〓ｕ〕｝…(1)
（但し、(1)式中ＫはＣ〓ｕとEDTA間の安定度定
数〔Ｃ〓ｕ〕はめつき液中のＣ〓ｕのモル濃度であ
る）上記(1)式の濃度関係にある化学銅めつき液に
三価鉄イオン（以後Ｆ〓ｅと略記）を加えた場合を
考える。三価鉄イオンは、キレート剤と極めて安
定なキレート化合物を形成する。これは多くの二
価金属イオンより安定である。従つて、Ｆ〓ｅの添
加量がＣ〓ｕとキレート剤との濃度差である（ｎ−
１）Ｃモルを少し越えると、キレート化していた
Ｃ〓ｕはキレート剤から解離して、遊離のＣ〓ｕを生
成する。そして、上記と同じ電極でＣ〓ｕとＣ〓ｕ間
の電位を測定すると(2)式のようになる。
Ｅ（２）＝0.153＋0.0592log
｛〔Ｃ〓ｕ〕／〔Ｃ〓ｕ〕｝…(2)
Ｆ〓ｅの添加量がキレート剤濃度（nCモル）を
少し越えると、遊離のＦ〓ｅが存在することにな
り、めつき液中に微量存在する二価鉄イオン（以
後Ｆ〓ｅと略記）との間の電位を、前記と同じ電極
で測定すると(3)式のようになる。
Ｅ（３）＝0.771＋0.0592log
｛〔Ｆ〓ｅ〕／〔Ｆ〓ｅ〕…(3)
すなわち、電位がＥ(1)からＥ(3)に変化したとき
の全Ｆ〓ｅ量は、全キレート剤の量nCモルに等し
い。
〔発明の実施例〕
以下、本発明を実施例を用いて詳細に説明す
る。
実施例 １
めつき液の組成とめつき条件
CuSO4・5H2O …14ｇ
EDTA−2Na …41.5ｇ
NaOH …12ｇ
37％ホルマリン …10ml
添加量 …少量
水 …全体を１とする量
めつき温度 70℃
めつき面積 1dm2／
めつき速度 2.5μ／ｈ
サンプリング速度 20ml／ｈ
滴定液組成と滴定条件
滴定液組成 FeCl3 9.1ｇ
HCl 10ml
水 …全体を１とする量
第１回目の滴定条件
設定電位 ＋0.28V
主電極 0.3φ白金線
参照電極 飽和甘汞電極
滴定速度 20ml／ｈ
第２回目の滴定条件
設定電位 ＋0.54V
主電極 0.3φ白金線
参照電極 飽和甘汞電極
滴定速度 20ml／ｈ
前記めつき液と前記滴定数を、それぞれ多連チ
ユーブポンプ２で20ml／ｈの割合でめつき槽１と
第１滴定槽３から採取した。この両液は、Ｔ字管
４−１で混合した。ついでこの混合液を白金電極
６−１と飽和甘汞電極５−１をそなえた銅イオン
検出セル７に入れ、電極電位を測定した。この測
定電位は、銅イオン濃度制御装置８へ入力した。
この入力が設定電位0.28Vより低いと、電磁弁９
−１（電磁弁のかわりに、補給用ポンプを用いて
も良い）が開き、銅イオン補給槽１０から銅イオ
ン溶液がめつき槽に補給された。入力が0.28Vよ
り高くなると、電磁弁６が閉じて補給が中止され
た。
上記銅イオン濃度測定方法において、めつき液
中のCuSO4・5H2Oに換算した銅イオン濃度と測
定電位の関係を求めた結果、第１表のようであつ
た。設定濃度（14ｇ／）において設定電位
（0.28V）を示し、これを当量点とするＳ字状の
関係が得られた。測定電位が0.3Vを示したとき
銅イオン濃度は14.15ｇ／であり、0.25Vを示し
たとき13.75ｇ／であつた。すなわち、設定電
位0.28Vより測定電位が大きいか、小さいかを検
出すれば、銅イオン濃度の測定ができることがわ
かつた。
[Field of Application of the Invention] The present invention relates to a method for measuring the concentration of a chelating agent in a chemical copper plating solution. [Background of the Invention] Recently, printed wiring boards have been manufactured by providing circuit conductors on an insulating substrate by chemical copper plating. In this case, the plating film, which is a circuit conductor, is required to have good electrical and mechanical properties. Generally, chemical copper plating solutions consist of copper ions, a chelating or complexing agent for copper ions, a reducing agent, and an alkali metal hydroxide. Then, the copper ions in the chemical copper plating solution are consumed by the plating reaction, and the chelating agent adheres to the plated body.
It is carried out of the tank to a non-negligible extent and the concentration decreases. The mechanical properties of chemical copper plating films are significantly affected by the concentration of copper ions, chelating agents, or complexing agents in the plating agent. Therefore, it is necessary to control the concentrations of these components. Conventionally, the concentration of copper ion chelating agents has not been measured because they are not consumed in the plating reaction. [Object of the Invention] An object of the present invention is to eliminate the drawbacks of the prior art described above and to provide a method for accurately measuring the concentration of a chelating agent in a chemical copper plating solution. [Summary of the Invention] The above object is to provide a chemical copper plating solution consisting of copper ions, a copper ion chelating agent, a copper ion reducing agent, and an alkali metal hydroxide; Chemistry characterized by adding trivalent iron ions at a molar concentration slightly exceeding the molar concentration of the total chelating agent, and measuring the redox potential of this solution using an insoluble electrode and a reference electrode to determine the total chelating agent concentration. The present invention provides a method for measuring the concentration of a chelating agent in a copper plating solution. The measurement principle of the present invention will be explained below. The chelating agent ethylenediaminetetraacetic acid (hereinafter EDTA)
), ethylenediaminepentaacetic acid (hereinafter EDPA)
) and divalent copper ions react at a molar concentration ratio of 1:1. This reaction is a chelate-forming reaction, and the reaction product is a copper chelate compound. Now, if the copper ion concentration in the chemical copper plating solution is C moles, and the molar concentration of the chelating agent is nC moles (in general, the chelating agent is 1.5 times the copper ion concentration).
~5x addition), divalent copper ions are completely chelated. Then, using an insoluble main electrode such as platinum or gold and a reference electrode, a chelate compound of monovalent copper ions (hereinafter abbreviated as C I u ) and divalent copper ions (C u When measuring the potential between E(1)=0.153−0.0592log
{K(n-1)[ C〓u ]}...(1) (However, in formula (1), K is the stability constant between C〓u and EDTA [ C〓u ], C〓u in the plating solution Consider the case where trivalent iron ions (hereinafter abbreviated as Fe ) are added to a chemical copper plating solution having the concentration relationship expressed by equation (1) above. Trivalent iron ions form extremely stable chelate compounds with chelating agents. It is more stable than many divalent metal ions. Therefore, the amount of F e added is the concentration difference between C u and the chelating agent (n-
1) When the amount of C mol exceeds a little, the chelated C u dissociates from the chelating agent and generates free C u . Then, when the potential between C〓 u and C〓 u is measured using the same electrode as above, it becomes as shown in equation (2). E(2)=0.153+0.0592log
{[ C〓u ]/[ C〓u ]}...(2) When the amount of F〓e added slightly exceeds the chelating agent concentration (nC mol), free Fe〓e will be present, and the plating will be When the potential with divalent iron ions (hereinafter abbreviated as F e ) present in a small amount in the liquid is measured using the same electrode as above, the result is expressed by equation (3). E(3)=0.771+0.0592log
{[F〓 e ]/[F〓 e ]...(3) That is, the total amount of F〓 e when the potential changes from E(1) to E(3) is equal to the total amount of chelating agent nC mole . [Examples of the Invention] The present invention will be described in detail below using Examples. Example 1 Composition of plating solution and plating conditions CuSO 4・5H 2 O...14g EDTA-2Na...41.5g NaOH...12g 37% formalin...10ml Amount added...a small amount of water...Weighing the total as 1 Plating temperature 70℃ Plating area 1 dm 2 / Plating speed 2.5 μ/h Sampling speed 20 ml/h Titrant composition and titration conditions Titrant composition FeCl 3 9.1 g HCl 10 ml Water...amount where the whole is 1 First titration conditions Setting potential +0 .28V Main electrode 0.3φ platinum wire Reference electrode Saturated metal electrode Titration rate 20ml/h Second titration conditions Set potential +0.54V Main electrode 0.3φ platinum wire Reference electrode Saturated metal electrode Titration rate 20ml/h Said plating The liquid and the titration number were sampled from the plating tank 1 and the first titration tank 3 at a rate of 20 ml/h using the multiple tube pump 2, respectively. Both liquids were mixed in a T-tube 4-1. Next, this mixed solution was placed in a copper ion detection cell 7 equipped with a platinum electrode 6-1 and a saturated acetate electrode 5-1, and the electrode potential was measured. This measured potential was input to the copper ion concentration control device 8.
If this input is lower than the set potential of 0.28V, the solenoid valve 9
-1 (a replenishment pump may be used instead of the solenoid valve) was opened, and the copper ion solution was replenished from the copper ion replenishment tank 10 to the plating tank. When the input was higher than 0.28V, solenoid valve 6 was closed and replenishment was stopped. In the above copper ion concentration measurement method, the relationship between the copper ion concentration converted to CuSO 4 .5H 2 O in the plating solution and the measured potential was determined as shown in Table 1. A set potential (0.28 V) was obtained at the set concentration (14 g/), and an S-shaped relationship was obtained with this as the equivalence point. When the measured potential showed 0.3V, the copper ion concentration was 14.15 g/, and when the measured potential showed 0.25 V, it was 13.75 g/. In other words, it was found that the copper ion concentration could be measured by detecting whether the measured potential was larger or smaller than the set potential of 0.28V.
【表】
銅イオン検出セル７を出た混合液は、多連チユ
ーブポンプ２で20ml／ｈの割合で第２滴定槽１１
から採取した前記滴定液とＴ字管４−２で混合し
た。この混合液は、白金電極６−２と飽和甘汞電
極５−２をそなえたキレート剤検出セル１２に入
れ、電極電位を測定した。測定電位は、キレート
剤制御装置１３へ入力した。この入力がキレート
剤制御装置の設定電位の0.54Vより高い場合、電
磁弁９−２が開いて、キレート剤補給槽１４か
ら、キレート剤溶液がめつき槽１に補給され、
0.54Vより低くなつたとき、電磁弁９−２が閉じ
て補給が中止された。キレート剤検出セル１２を
出た混合液は、廃液槽１５に排出した。
上記キレート剤濃度測定方法において、めつき
液中のEDTA−2Naに換算したキレート剤濃度と
測定電位の関係を求めた結果、第２表のようであ
つた。設定濃度（41.5ｇ／）において、設定電
位（0.54V）を示した。測定電位が0.56Vのとき
キレート剤濃度は40.3ｇ／であり、0.52Vを示
したとき43ｇ／であつた。よつて、設定電位
0.54Vより測定電位が大きいか、小さいかを検出
すれば、キレート剤濃度の測定ができることがわ
かつた。[Table] The mixed liquid exiting the copper ion detection cell 7 is transferred to the second titration tank 11 at a rate of 20 ml/h using the multiple tube pump 2.
The titrant was mixed with the titrant solution collected from the T-tube 4-2. This mixed solution was placed in a chelating agent detection cell 12 equipped with a platinum electrode 6-2 and a saturated acetate electrode 5-2, and the electrode potential was measured. The measured potential was input to the chelating agent control device 13. When this input is higher than the set potential of 0.54 V of the chelating agent control device, the solenoid valve 9-2 opens and the chelating agent solution is replenished from the chelating agent replenishing tank 14 to the plating tank 1.
When the voltage dropped below 0.54V, solenoid valve 9-2 closed and replenishment was stopped. The mixed liquid that came out of the chelating agent detection cell 12 was discharged into a waste liquid tank 15. In the method for measuring the chelating agent concentration described above, the relationship between the chelating agent concentration converted to EDTA-2Na in the plating solution and the measured potential was determined as shown in Table 2. At the set concentration (41.5 g/), the set potential (0.54 V) was shown. When the measured potential was 0.56V, the chelating agent concentration was 40.3 g/, and when the measured potential was 0.52 V, it was 43 g/. Therefore, the set potential
It was found that the concentration of the chelating agent can be measured by detecting whether the measured potential is larger or smaller than 0.54V.
以上述べたように、本発明によれば、化学銅め
つき液中のキレート剤濃度を、精度良く調整でき
る。また、連続的に自動制御できる。
As described above, according to the present invention, the concentration of the chelating agent in the chemical copper plating solution can be adjusted with high precision. It can also be continuously and automatically controlled.
図は化学銅めつき液のキレート剤の自動濃度管
理装置の構成図である。
１……めつき槽、３……第１滴定液、５−１，
５−２……飽和甘汞電極、６−１，６−２……白
金電極、７……銅イオン検出セル、８……銅イオ
ン濃度制御装置、１０……銅イオン補給槽、１１
……第２滴定液、１２……キレート剤検出セル、
１３……キレート剤制御装置、１４……キレート
剤補給槽。
The figure is a configuration diagram of an automatic concentration control device for a chelating agent in a chemical copper plating solution. 1... Plating tank, 3... First titrant, 5-1,
5-2...Saturated molten metal electrode, 6-1, 6-2...Platinum electrode, 7...Copper ion detection cell, 8...Copper ion concentration control device, 10...Copper ion supply tank, 11
...second titrant, 12...chelating agent detection cell,
13...Chelating agent control device, 14...Chelating agent supply tank.
Claims (1)
オンの還元剤と、アルカリ金属の水酸化物よりな
る化学銅めつき液に、このめつき液中に存在する
全キレート剤の設定モル濃度を少し越えるモル濃
度の三価鉄イオンを加え、この溶液の酸化還元電
位を不溶性の電極と、参照電極とで測定して全キ
レート剤濃度を求めることを特徴とする化学銅め
つき液中のキレート剤濃度測定法。1. In a chemical copper plating solution consisting of copper ions, a copper ion chelating agent, a copper ion reducing agent, and an alkali metal hydroxide, set the set molar concentration of all the chelating agents present in this plating solution. A chelate in a chemical copper plating solution characterized by adding trivalent iron ions in a slightly exceeding molar concentration and measuring the redox potential of this solution using an insoluble electrode and a reference electrode to determine the total chelating agent concentration. Agent concentration measurement method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59137118A JPS60104248A (en) | 1984-07-04 | 1984-07-04 | Method for measuring concentration of chelate agent in chemical copper plating liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59137118A JPS60104248A (en) | 1984-07-04 | 1984-07-04 | Method for measuring concentration of chelate agent in chemical copper plating liquid |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6333777A Division JPS53149389A (en) | 1977-06-01 | 1977-06-01 | Measurement method of copper ions and chelating agent concentration in chemical copper plating solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60104248A JPS60104248A (en) | 1985-06-08 |
| JPS6143660B2 true JPS6143660B2 (en) | 1986-09-29 |
Family
ID=15191243
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59137118A Granted JPS60104248A (en) | 1984-07-04 | 1984-07-04 | Method for measuring concentration of chelate agent in chemical copper plating liquid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60104248A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10960708B2 (en) * | 2017-04-07 | 2021-03-30 | Kumho Tire Co., Inc. | Semi-pneumatic tire and semi-pneumatic tire manufacturing method |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6890758B2 (en) * | 2003-06-13 | 2005-05-10 | Eci Technology, Inc. | Measurement of complexing agent concentration in an electroless plating bath |
| US8118988B2 (en) * | 2008-01-31 | 2012-02-21 | Eci Technology, Inc. | Analysis of copper ion and complexing agent in copper plating baths |
| JP6644552B2 (en) * | 2016-01-07 | 2020-02-12 | 株式会社ニイタカ | Determination method of chelating agent |
| CN107202831A (en) * | 2017-06-05 | 2017-09-26 | 深圳市华星光电技术有限公司 | The assay method of copper ion concentration in a kind of copper acid etch liquid |
-
1984
- 1984-07-04 JP JP59137118A patent/JPS60104248A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10960708B2 (en) * | 2017-04-07 | 2021-03-30 | Kumho Tire Co., Inc. | Semi-pneumatic tire and semi-pneumatic tire manufacturing method |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60104248A (en) | 1985-06-08 |
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