JPH01119678A - Apparatus for administrating chemical copper plating liquid - Google Patents
Apparatus for administrating chemical copper plating liquidInfo
- Publication number
- JPH01119678A JPH01119678A JP27891787A JP27891787A JPH01119678A JP H01119678 A JPH01119678 A JP H01119678A JP 27891787 A JP27891787 A JP 27891787A JP 27891787 A JP27891787 A JP 27891787A JP H01119678 A JPH01119678 A JP H01119678A
- Authority
- JP
- Japan
- Prior art keywords
- copper
- chamber
- ions
- plating solution
- replenishment
- 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.)
- Pending
Links
- 239000010949 copper Substances 0.000 title claims abstract description 92
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 91
- 238000007747 plating Methods 0.000 title claims abstract description 90
- 239000000126 substance Substances 0.000 title claims abstract description 46
- 239000007788 liquid Substances 0.000 title abstract 8
- 238000000909 electrodialysis Methods 0.000 claims abstract description 35
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 30
- 230000008929 regeneration Effects 0.000 claims abstract description 30
- 238000011069 regeneration method Methods 0.000 claims abstract description 30
- -1 hydrogen ions Chemical class 0.000 claims abstract description 27
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 12
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- 230000001172 regenerating effect Effects 0.000 claims abstract description 6
- 239000012528 membrane Substances 0.000 claims description 14
- 239000003957 anion exchange resin Substances 0.000 claims description 10
- 238000004090 dissolution Methods 0.000 claims description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 31
- 238000004458 analytical method Methods 0.000 abstract description 11
- 150000002500 ions Chemical class 0.000 abstract description 10
- 238000000502 dialysis Methods 0.000 abstract description 4
- 239000003011 anion exchange membrane Substances 0.000 abstract 2
- 238000005341 cation exchange Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 60
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000007864 aqueous solution Substances 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 229910000365 copper sulfate Inorganic materials 0.000 description 7
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 7
- 239000005749 Copper compound Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 5
- 150000001880 copper compounds Chemical class 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 4
- 238000005705 Cannizzaro reaction Methods 0.000 description 4
- 238000009825 accumulation Methods 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 239000003729 cation exchange resin Substances 0.000 description 4
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000008139 complexing agent Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- BQJTUDIVKSVBDU-UHFFFAOYSA-L copper;sulfuric acid;sulfate Chemical compound [Cu+2].OS(O)(=O)=O.[O-]S([O-])(=O)=O BQJTUDIVKSVBDU-UHFFFAOYSA-L 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
- B01D61/44—Ion-selective electrodialysis
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1617—Purification and regeneration of coating baths
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Urology & Nephrology (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemically Coating (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は化学銅めっき液の管理装置に関し、詳しくは化
学めっき反応によって生成されるめっき反応阻害成分の
蓄積を抑え、化学銅めっき液の組成を一定に管理する装
置に関するものである。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a chemical copper plating solution management device, and more specifically, it suppresses the accumulation of plating reaction inhibiting components produced by a chemical plating reaction, and controls the composition of the chemical copper plating solution. The invention relates to a device that manages the
銅イオン、銅イオンの錯化剤、銅イオンの還元剤および
ＰＨ調整剤を主成分として含む化学銅めっき液は、化学
銅めっき液中で化学めっき反応により消費される銅イ゛
オン、銅イオンの還元剤およびＰＨ調整剤をそれら各成
分の最適濃度を維持゛するために、それらの成分を補充
しながら長時間使用される。A chemical copper plating solution containing copper ions, a complexing agent for copper ions, a reducing agent for copper ions, and a PH adjuster as main components is a chemical copper plating solution that contains copper ions, copper ion complexing agents, copper ion reducing agents, and PH adjusters as main components. The reducing agent and pH adjuster are used for extended periods of time while replenishing their respective components to maintain optimal concentrations of each component.
一般に、広く用いられている化学銅めっき液は、銅イオ
ンは硫酸銅等の銅化合物として、銅イオンの錯化剤はエ
チレンジアミン四酢酸のナトリウム塩等を、銅イオンの
還元剤はホルムアルデヒド等を、ＰＨ調整剤は水酸化ナ
トリウム等のアルカリ金属の水酸化物として含んでいる
。In general, the widely used chemical copper plating solution uses a copper compound such as copper sulfate as the copper ion, a sodium salt of ethylenediaminetetraacetic acid as the complexing agent for the copper ion, and formaldehyde as the reducing agent for the copper ion. The pH adjuster is contained as an alkali metal hydroxide such as sodium hydroxide.
上記の化学銅めっき液を管理する装置としては、各成分
を分析する分析機構と分析値を基にして各成分の補充を
行う補充機構から成り、一般には、ＰＨ，銅濃度、銅イ
オンの還元剤の濃度をそれぞれ分析し最適濃度からの不
足分をそれぞれの補充液よりポンプを通して直接化学銅
めっき液中に添加するという一連の操作のくり返しで行
われている。これら化学めっき反応で消費される水酸イ
オン、銅イオン、ｆ１イオンの還元剤の各成分の補充液
としては、一般に水酸イオンは水酸化ナトリウム等のア
ルカリ金属の水酸化物の水溶液が、銅イオンは硫酸銅等
の銅化合物の水溶液が、銅イオンの°還元剤は、例えば
ホルムアルデヒドの場合は、３７重景％ホルマリンが用
いられている。The equipment for managing the above chemical copper plating solution consists of an analysis mechanism that analyzes each component and a replenishment mechanism that replenishes each component based on the analysis values. This is done by repeating a series of operations in which the concentration of each agent is analyzed and the amount lacking from the optimum concentration is directly added to the chemical copper plating solution from each replenisher solution through a pump. As a replenisher for each component of the reducing agent of hydroxide ions, copper ions, and f1 ions consumed in these chemical plating reactions, hydroxide ions are generally used in an aqueous solution of an alkali metal hydroxide such as sodium hydroxide. The ions are an aqueous solution of a copper compound such as copper sulfate, and the reducing agent for copper ions is formaldehyde, for example, 37% formalin.
しかし、上記従来技術では銅イオンの補充方法として銅
化合物の水溶液を直接化学銅めっき液中に補充している
ため、化学銅めっき液の長時間の使用により、銅イオン
の対陰イオンが化学銅めっき液中に蓄積されることにな
る。また、銅イオンの還元剤の酸化反応生成物イオンも
同様に化学銅めっき液の長時間の使用により、化学銅め
っき液中に蓄積される。銅化合物として主として硫酸銅
が用いられるので銅イオンの対陰イオンである硫酸イオ
ンが化学銅めっき液中に蓄積する。また銅イオンの還元
剤として主としてホルムアルデヒドが用いられ、この酸
化反応生成物イオンはギ酸イオンであり、これが化学銅
めっき液中に蓄積される。However, in the above conventional technology, as a method of replenishing copper ions, an aqueous solution of a copper compound is directly replenished into the chemical copper plating solution. It will accumulate in the plating solution. Furthermore, ions produced by the oxidation reaction of the copper ion reducing agent are similarly accumulated in the chemical copper plating solution due to long-term use of the chemical copper plating solution. Since copper sulfate is mainly used as the copper compound, sulfate ions, which are counter anions to copper ions, accumulate in the chemical copper plating solution. Further, formaldehyde is mainly used as a reducing agent for copper ions, and the oxidation reaction product ions are formate ions, which are accumulated in the chemical copper plating solution.
硫酸イオン、ギ酸イオン等の副生成物イオンが化学銅め
っき液中に蓄積し、増加すると化学銅めっき液の状態は
不安定になり、分解されやすくなる。また、めっき皮膜
の抗張力、伸び率等の物性の低下および異常析出等の問
題が生じる。When by-product ions such as sulfate ions and formate ions accumulate in the chemical copper plating solution and increase, the state of the chemical copper plating solution becomes unstable and becomes easily decomposed. Further, problems such as a decrease in physical properties such as tensile strength and elongation of the plated film and abnormal precipitation occur.
また、従来の化学銅めっき液の管理装置では、分析して
から補充を行うため、補修方法が間欠であり、化学銅め
っき液中の各成分の濃度の変動が大きくなってしまうと
いう問題がある。In addition, with conventional chemical copper plating solution management equipment, replenishment is performed after analysis, which means that the repair method is intermittent, resulting in large fluctuations in the concentration of each component in the chemical copper plating solution. .
本発明の目的は、硫酸イオン、ギ酸イオン等の副生成物
イオンの蓄積を抑え、水酸イオンの補充液を必要とせず
、化学めっき反応によって消費される各成分の消費量と
同等の量を連続的に補充することができる化学銅めっき
液の管理装置を提供することにある。The purpose of the present invention is to suppress the accumulation of by-product ions such as sulfate ions and formate ions, eliminate the need for a hydroxide ion replenisher, and reduce the amount of each component consumed in a chemical plating reaction. An object of the present invention is to provide a chemical copper plating solution management device that can be continuously replenished.
本発明の化学銅めっき液の管理装置は、２枚の陰イオン
交換樹脂膜によって陽極室、めっき液再生室および陰極
室の３室に仕切ってなるめっき液再生用の電気透析槽と
、めっき液再生用電気透析槽の前記陽極室および前記陰
極室にそれぞれ設置した陽極電極および陰極電極と、両
電極間に直流電圧を印加する直流電源とを有するめっき
液再生機構と、陽イオン交換樹脂膜によって陽極室と銅
補充室とに、かつ陰イオン交換樹脂膜によって前記銅補
充室と陰極室とに仕切ってなる銅補充用の電気透析槽と
、銅補充用の電気透析槽の陽極室にアノード溶解によっ
て銅イオンを発生させるための銅電極、水素イオンを発
生させるための電極の２種類の設置された陽極電極と、
前記銅補充用の電気透析槽の陰極室に設置した陰極電極
と、両電極間に直流電圧を印加する直流電源と、銅イオ
ンを発生させるための銅電極と水素イオンを発生させる
ための電極に流す電流をコントロールする機構とを有す
る銅補充機構と、銅イオンの還元剤を補充する機構と、
化学銅めっ゛き液の各成分を分析し、めっき液再生用お
よび銅補充用の電気透析槽のそれぞれの電極間に流す電
流値をコントロールする機構とを備えたことを特徴とす
る。The chemical copper plating solution management device of the present invention comprises an electrodialysis tank for plating solution regeneration, which is partitioned into three chambers, an anode chamber, a plating solution regeneration chamber, and a cathode chamber, by two anion exchange resin membranes; A plating solution regeneration mechanism includes an anode electrode and a cathode electrode installed in the anode chamber and the cathode chamber of the regeneration electrodialysis tank, respectively, and a DC power source that applies a DC voltage between the two electrodes, and a cation exchange resin membrane. An electrodialysis tank for copper replenishment is formed into an anode chamber and a copper replenishment chamber, and is partitioned into the copper replenishment chamber and a cathode chamber by an anion exchange resin membrane, and an anode is dissolved in the anode chamber of the electrodialysis tank for copper replenishment. Two types of anode electrodes are installed: a copper electrode for generating copper ions and an electrode for generating hydrogen ions,
A cathode electrode installed in the cathode chamber of the electrodialysis tank for copper replenishment, a DC power source that applies a DC voltage between both electrodes, a copper electrode for generating copper ions, and an electrode for generating hydrogen ions. a copper replenishment mechanism having a mechanism for controlling the flowing current; a mechanism for replenishing a copper ion reducing agent;
It is characterized by having a mechanism that analyzes each component of the chemical copper plating solution and controls the current value flowing between the respective electrodes of the electrodialysis tank for regenerating the plating solution and for copper replenishment.
化学鋼めっき液中における主な反応としては、反応式（
１）に示す銅が析出する主反応と反応式（２）に示すホ
ルムアルデヒドの自己酸化還元反応であるカニッツアロ
反応がある。The main reactions in the chemical steel plating solution are expressed by the reaction formula (
There are two main reactions: the main reaction in which copper is precipitated as shown in 1), and the Cannizzaro reaction, which is an autooxidation-reduction reaction of formaldehyde, as shown in reaction formula (2).
Ｃｕ２” ＋２８ＣＨＯ＋４０Ｈ−
→Ｃｕ ＋ ２ ＨＣＯＯ−＋Ｈ２＋ ２ Ｈ２０・・
・（１）２ＨＣＨＯ＋０Ｈ−−ＣＨ３０Ｈ＋ＨＣＯＯ−
・・・（２）
主反応において、銅が１モル析出すると、水酸イオンが
４モル消費され、ギ酸イオンが２モル生成される。また
、カニッツァロ反応では水酸イオンが１モル消費される
と、ギ酸イオンが１モル生成される。２枚の陰イオン交
換樹脂膜を用いて陽極室、めっき液再生室、陰極室の３
つの小部屋に仕切っためっき液再生用の電気透析槽と、
陽イオン交換樹脂膜および陰イオン交換樹脂膜を用いて
陽極室、銅補充室、陰極室の３つの小部屋に仕切った銅
補充用の電気透析槽を用いて、化学銅めっき液の再生お
よび銅補充を行うと、主反応で生成されるギ酸イオン２
モルを再生で除去を行うと水酸イオンが２モル補充され
、銅補充で銅イオンを１モル補充されると、水酸イオン
も２モル補充される。また、カニッツァロ反応で生成さ
れるギ酸イオンを１モルを再生で除去すると水酸イオン
が１モル補充される。つまり、めっき主反応、カニッツ
ァロ反応によって消費される銅イオンを補充し、生成さ
せるギ酸イオンを除去すれば、反応に必要な水酸イオン
が補充されることになる。Cu2” +28CHO+40H- →Cu + 2 HCOO-+H2+ 2 H20...
・(1) 2HCHO+0H--CH30H+HCOO-
(2) In the main reaction, when 1 mole of copper is precipitated, 4 moles of hydroxide ions are consumed and 2 moles of formate ions are produced. Furthermore, in the Cannizzaro reaction, when 1 mole of hydroxide ion is consumed, 1 mole of formate ion is produced. Three anode chambers, a plating solution regeneration chamber, and a cathode chamber are constructed using two anion exchange resin membranes.
An electrodialysis tank for plating solution regeneration divided into two small rooms,
An electrodialysis tank for copper replenishment, which is divided into three small chambers, an anode chamber, a copper replenishment chamber, and a cathode chamber, using a cation exchange resin membrane and an anion exchange resin membrane, is used to regenerate chemical copper plating solution and remove copper. When replenishment is performed, formate ion 2 produced in the main reaction
When moles are removed by regeneration, 2 moles of hydroxide ions are replenished, and when 1 mole of copper ions are replenished by copper replenishment, 2 moles of hydroxide ions are also replenished. Furthermore, when 1 mole of formate ions produced in the Cannizzaro reaction is removed by regeneration, 1 mole of hydroxide ions are replenished. In other words, by replenishing the copper ions consumed by the main plating reaction, the Cannizzaro reaction, and removing the generated formate ions, the hydroxide ions necessary for the reaction will be replenished.
したがって、化学銅めっき液の銅濃度、ＰＨ。Therefore, the copper concentration and pH of the chemical copper plating solution.
ホルムアルデヒド濃度の分析値より再生および銅補充で
の電解電流値を設定することにより連続的に銅、水酸イ
オンを補充することが可能であり、水酸イオンの補充は
必要なくなる。また、銅イオンの対陰イオンの蓄積はさ
れない。By setting the electrolytic current value for regeneration and copper replenishment based on the analytical value of formaldehyde concentration, it is possible to continuously replenish copper and hydroxide ions, and replenishment of hydroxide ions is no longer necessary. Further, counteranions of copper ions are not accumulated.
このときめっき液再生用の電気透析槽の陽極室に導入す
る溶液として水酸化ナトニウム水溶液か、または硫酸水
溶液が適当であり、銅補充用の電気透析槽の陽極室に導
入する溶液としては、水素イオン濃度を一定範囲内に管
理された銅化合物の水溶液、例えば硫酸銅水溶液等を用
いる。At this time, a sodium hydroxide aqueous solution or a sulfuric acid aqueous solution is suitable as the solution introduced into the anode chamber of the electrodialysis tank for regenerating the plating solution, and hydrogen An aqueous solution of a copper compound whose ion concentration is controlled within a certain range, such as an aqueous copper sulfate solution, is used.
また、めっき液再生用および銅補充用の電気透析槽の両
方の陰極室に導入する溶液として水酸化ナトリウム水溶
液が適当である。In addition, an aqueous sodium hydroxide solution is suitable as the solution introduced into the cathode chambers of both the electrodialysis tank for plating solution regeneration and copper replenishment.
次に、本発明の実施例について図面を参照して説明する
。第１図は本発明の実施例１を示す化学銅めっき液の管
理装置の回路図付きの断面図である０図中２は、ポリプ
ロピレン等の合成樹脂製の再生用電気透析槽であり、゛
この再生用電気透析槽２は陰イオン交換樹脂膜２４によ
って陽極室２１、めっき液再生室２２、陰極室２３の３
つの小部屋に分割される。Ｅｌは陽極電極２５、陰極電
極２６からそれぞれ導出されたリード線により接続され
た直流電源であり、両電極間に流す電流値は分析機構５
によって設定される。Next, embodiments of the present invention will be described with reference to the drawings. FIG. 1 is a sectional view with a circuit diagram of a chemical copper plating solution management device showing Embodiment 1 of the present invention. 2 in FIG. 1 is a regenerating electrodialysis tank made of synthetic resin such as polypropylene. This regeneration electrodialysis tank 2 has three anode chambers 21, a plating solution regeneration chamber 22, and a cathode chamber 23 by an anion exchange resin membrane 24.
Divided into two small rooms. El is a DC power supply connected by lead wires derived from the anode electrode 25 and the cathode electrode 26, respectively, and the value of the current flowing between the two electrodes is determined by the analysis mechanism 5.
Set by.
また、図中３は、ポリプロピレン等の合成樹脂製の銅補
充用電気透析槽であり、この銅補充用電気透析槽３は、
陽イオン交換樹脂膜３４、陰イオン交換樹脂膜３５によ
って、陽極室３１、銅補充室３２、陰極室３３の３つの
小部屋に分割される。陽極室３１に、金属銅から成る銅
イオン発生用の電極３６と、水素イオン発生用の電極３
８との２種類の陽極電極を設置し、リード線によって電
流コントロール器３９に接続され、さらにリード線によ
り電流コントロール器３９から直流電源Ｅ２に接続され
る。一方、陰極室３３に陰極電極３７が設置され、リー
ド線により直流電源Ｅ２に接続される０両電極間に流す
電流値は、再生の場合と同様、分析機構５によって設定
される。図中４はホルマリンの補充用タンクであり、ホ
ルムアルデヒドはポンプＰ５によって補充される。分析
機構５は、めつき槽１中の化学銅めっき液の主成分を分
析し、直流電源Ｅｌ、Ｅ２で流す電流値の設定およびポ
ンプＰ５のスイッチの０Ｎ１０ＦＦ’を行うものである
。In addition, 3 in the figure is an electrodialysis tank for copper replenishment made of synthetic resin such as polypropylene, and this electrodialysis tank 3 for copper replenishment is
The cation exchange resin membrane 34 and the anion exchange resin membrane 35 divide the chamber into three small chambers: an anode chamber 31 , a copper replenishment chamber 32 , and a cathode chamber 33 . In the anode chamber 31, an electrode 36 for generating copper ions made of metallic copper and an electrode 3 for generating hydrogen ions are provided.
Two types of anode electrodes 8 and 8 are installed and connected to a current controller 39 by a lead wire, and further connected from the current controller 39 to a DC power source E2 by a lead wire. On the other hand, a cathode electrode 37 is installed in the cathode chamber 33, and the value of the current flowing between the two electrodes connected to the DC power source E2 by a lead wire is set by the analysis mechanism 5, as in the case of regeneration. In the figure, 4 is a formalin replenishment tank, and formaldehyde is replenished by a pump P5. The analysis mechanism 5 analyzes the main components of the chemical copper plating solution in the plating tank 1, sets the current value to be passed by the DC power supplies El and E2, and switches the pump P5 to 0N10FF'.
めっき槽１．めっき液再生室２２および銅補充室３２に
、硫酸銅１０ｇ／ｅ、エリレンジアミン四酢酸４０ｇ／
ｆｆ、ホルムアルデヒド２ｇ／ｅを主成分として含むＰ
Ｈ＝１２の化学銅めっき液を入れ、ポンプＰ３．Ｐ４に
よってめつき槽１より化学銅めっき液をくみあげ熱交換
器６ｃ、６ｄにより冷却し、めっき液再生室２２および
銅補充室３２に入れる。ポンプＰＬ、Ｐ２によりそれぞ
れめっき液再生室２２、銅補充室３２の化学銅めっき液
をくみあげ熱交換器６ ａ 、’６ ｂにより加温し、
めっき槽１に入れ、常時循環させる。再生用電気透析槽
２の陽極室２１に１０ｇ／ｌ！硫酸水溶液を入れ、銅補
充用透析槽３の陽極室３１に硫酸銅２００ｇ／Ｖ、硫酸
Ｂｏｇ／ｌの硫酸−硫酸銅水溶液を入れる。Plating tank 1. In the plating solution regeneration chamber 22 and copper replenishment chamber 32, 10 g/e of copper sulfate and 40 g/e of erylenediaminetetraacetic acid were added.
ff, P containing 2 g/e of formaldehyde as the main component
Pour the chemical copper plating solution of H=12 and pump P3. At P4, the chemical copper plating solution is pumped up from the plating tank 1, cooled by heat exchangers 6c and 6d, and put into the plating solution regeneration chamber 22 and copper replenishment chamber 32. The chemical copper plating solution is pumped up from the plating solution regeneration chamber 22 and copper replenishment chamber 32 by the pumps PL and P2, respectively, and heated by the heat exchangers 6a and '6b.
Place it in plating tank 1 and constantly circulate it. 10g/l in the anode chamber 21 of the electrodialysis tank 2 for regeneration! A sulfuric acid aqueous solution is put in, and a sulfuric acid-copper sulfate aqueous solution of 200 g/V of copper sulfate and Bog/l of sulfuric acid is put into the anode chamber 31 of the dialysis tank 3 for copper replenishment.
また、再生用電気透析槽２と銅補充用電気透析槽３の陰
極室２３．３３に４ｇ／！水酸化ナトリウム水溶液を入
れる。Also, 4g/! in the cathode chambers 23.33 of the regeneration electrodialysis tank 2 and the copper replenishment electrodialysis tank 3! Add sodium hydroxide aqueous solution.
再生用電気透析槽２の陽極室２１、陰極室２３にそれぞ
れ陽極電極２５、陰極電極２６を配置し、この両電極間
に直流電源Ｅ１によって直流電圧を印加する。陽極電極
２５、陰極電極２６として白金めっきチタンが適当であ
る。銅補充用透析槽３の陽極室３１には、アノード溶解
によって銅イオンを供給するために陽極電極３６に銅を
用い、水素イオン発生用電極に白金めっきチタンを用い
、電流コントロール器３つによって陽極室３１の硫酸−
硫酸銅水溶液中の水素イオン濃度、銅イオン濃度を一定
範囲内に管理する。陰極室３３に配置する陰極電極３７
としては白金めつきチタンが適当である。Ｅ２は陽極電
極３６および水素イオン発生用電極３８と陰極電極３７
との間に直流電圧を印加する直流電源である。An anode electrode 25 and a cathode electrode 26 are arranged in the anode chamber 21 and cathode chamber 23 of the regenerating electrodialysis tank 2, respectively, and a DC voltage is applied between these electrodes by a DC power source E1. Platinum-plated titanium is suitable for the anode electrode 25 and the cathode electrode 26. In the anode chamber 31 of the dialysis tank 3 for copper replenishment, copper is used for the anode electrode 36 to supply copper ions by anode dissolution, platinum-plated titanium is used for the hydrogen ion generation electrode, and the anode is controlled by three current controllers. Sulfuric acid in chamber 31-
The hydrogen ion concentration and copper ion concentration in the copper sulfate aqueous solution are controlled within a certain range. Cathode electrode 37 placed in cathode chamber 33
A suitable material is platinum-plated titanium. E2 is an anode electrode 36, a hydrogen ion generation electrode 38, and a cathode electrode 37.
This is a DC power supply that applies DC voltage between the
分析機構５によってめつき槽１の化学銅めっき液のＰＨ
，銅濃度、ホルムアルデヒド濃度の分析を行い、めっき
反応と同じ速さで水酸イオン、銅イオンを補充するよう
に直流電源Ｅ１．Ｅ２で流す電流値をコントロールする
。またホルムアルデヒドはホルマリン補充タンク４より
ポンプＰ５により補充する。The pH of the chemical copper plating solution in the plating tank 1 is determined by the analysis mechanism 5.
, copper concentration, and formaldehyde concentration, and the DC power source E1. Control the current value flowing with E2. Further, formaldehyde is replenished from the formalin replenishment tank 4 by a pump P5.
条件として、めっき温度７０℃、負荷量１ｄｍ２／ｅ、
めっき槽容量３０１．イオン交換膜有効面積１０００ｃ
ｍ２でめっき厚４０μｍまで析出させて１サイクルとし
３サイクルまで使用したところ、水酸イオンを補充しな
くてもめつき速度は２μｍ／ｈとほぼ一定となり、硫酸
イオン、ギ酸イオンは初期にそれぞれ０．０４ｍｏｌ／
ｆ。The conditions were a plating temperature of 70°C, a load of 1dm2/e,
Plating tank capacity 301. Ion exchange membrane effective area 1000c
When plating was performed for 1 cycle and used for up to 3 cycles, the plating rate was almost constant at 2 μm/h without replenishing hydroxide ions, and sulfate ions and formate ions were initially 0.2 μm/h. 04mol/
f.
０．０１ｍｏｌ／ｊ’であったものが３サイクル終了後
は、それぞれ０．０２ｍｏ １／ｌ、０１０１ｍ ｏ
１ ／ ｅであり、化学銅めっき液の組成を一定に維持
管理することができた。What was 0.01 mol/j' becomes 0.02 mo 1/l and 0101 mo after 3 cycles, respectively.
1/e, and the composition of the chemical copper plating solution could be kept constant.
第２図は本発明の実施例の２のフローシートを示すもの
である。実施例１は、再生用電気透析槽２と銅補充用電
気透析槽３を並列にめっき槽１につないだものだが、実
施例２では２つの透析槽を直列につないだものである。FIG. 2 shows a flow sheet of Example 2 of the present invention. In Example 1, an electrodialysis tank 2 for regeneration and an electrodialysis tank 3 for copper replenishment are connected in parallel to the plating tank 1, but in Example 2, two dialysis tanks are connected in series.
めっき槽１中の化学銅めっき液をポンプＰ１によってく
みあげ熱交換器６ａによって冷却し、銅補充用電気透析
槽３の銅補充室３２に入れる。ポンプＰ２より銅補充室
３２中の化学銅めっき液をくみあげ、再生用電気透析槽
２のめっき液再生室２２に入れる。ポンプＰ３によりめ
っき液再生室２２中の化学銅めっき液をくみあげ、熱交
換器６ｂによって加温しめっき槽１に入れ、常時循環さ
せる。The chemical copper plating solution in the plating tank 1 is pumped up by the pump P1, cooled by the heat exchanger 6a, and put into the copper replenishment chamber 32 of the electrodialysis tank 3 for copper replenishment. The chemical copper plating solution in the copper replenishment chamber 32 is pumped up from the pump P2 and put into the plating solution regeneration chamber 22 of the electrodialysis tank 2 for regeneration. The chemical copper plating solution in the plating solution regeneration chamber 22 is pumped up by the pump P3, put into the heated plating tank 1 by the heat exchanger 6b, and constantly circulated.
実施例１と同じ組成の溶液を用い、同じ条件でめっきを
行ったところ実施例１と同様に副生成物イオンの蓄積は
なく、化学銅めっき液の組成を一定に維持管理すること
ができた。When plating was performed using a solution with the same composition as in Example 1 under the same conditions, there was no accumulation of by-product ions as in Example 1, and the composition of the chemical copper plating solution could be maintained constant. .
実施例２は実施例１に対し、化学銅めっき液の循環用の
ポンプを１ヶ、熱交換器を２ケ省略でき、配管が容易に
なる等の利点がある。Embodiment 2 has advantages over Embodiment 1 in that one pump for circulating the chemical copper plating solution and two heat exchangers can be omitted, and piping can be simplified.
以上説明したように本発明は電気透析による化学銅めっ
き液の再生機構と、同じく電気透析による銅補充機構と
を設け、化学銅めっき液を管理することにより、硫酸イ
オン、ギ酸イオン等の副生成物イオンの蓄積を抑え、水
酸イオンの補充液を必要とせず、化学銅めっき液の組成
を一定に維持管理することができる効果がある。As explained above, the present invention includes a regeneration mechanism for chemical copper plating solution using electrodialysis and a copper replenishment mechanism using electrodialysis, and by managing the chemical copper plating solution, by-products such as sulfate ions and formate ions are produced. This has the effect of suppressing the accumulation of chemical ions, eliminating the need for a hydroxide ion replenisher, and making it possible to maintain and manage the composition of the chemical copper plating solution at a constant level.
第１図、第２図は本発明の実施例１および実施例２によ
る化学鋼めっき液の管理装置の構成説明図である。
１・・・めっき槽、２・・・再生用電気透析槽、３・・
・銅補充用電気透析槽、４・・・ホルマリン補充用タン
ク、５・・・分析機構、６ａ、６ｂ、６ｃ、６ｄ−熱交
換器、２１・・・陽極室、２２・・・めっき液再生室、
２３・・・陰極室、２４・・・陰イオン交換樹脂膜、２
５・・・陽極電極、２６・・・陰極電極、３１・・・陽
極室、３２・・・銅補充室、３３・・・陰極室、３４・
・・陽イオン交換樹脂膜、３５・・・陰イオン交換樹脂
膜、３６・・・陽極電極、３７・・・陰極電極、３８・
・・水素イオン発生用電極、３９・・・電流コントロー
ル器、Ｅｌ。
Ｅ２・・・直流電源、ＰＬ、Ｐ２．Ｐ３．Ｐ４・・・ポ
ンプ。FIG. 1 and FIG. 2 are explanatory diagrams of the configuration of a chemical steel plating solution management device according to Embodiment 1 and Embodiment 2 of the present invention. 1... Plating tank, 2... Regeneration electrodialysis tank, 3...
・Electrodialysis tank for copper replenishment, 4... Tank for formalin replenishment, 5... Analysis mechanism, 6a, 6b, 6c, 6d-heat exchanger, 21... Anode chamber, 22... Plating solution regeneration room,
23... Cathode chamber, 24... Anion exchange resin membrane, 2
5... Anode electrode, 26... Cathode electrode, 31... Anode chamber, 32... Copper replenishment chamber, 33... Cathode chamber, 34...
... Cation exchange resin membrane, 35 ... Anion exchange resin membrane, 36 ... Anode electrode, 37 ... Cathode electrode, 38.
...Hydrogen ion generation electrode, 39...Current controller, El. E2...DC power supply, PL, P2. P3. P4...Pump.
Claims (1)
生室および陰極室の３室に仕切つてなるめっき液再生用
の電気透析槽と、前記めっき液再生用電気透析槽の前記
陽極室および前記陰極室にそれぞれ設置した陽極電極お
よび陰極電極と、前記両電極間に直流電圧を印加する直
流電源とを有するめっき液再生機構と、陽イオン交換樹
脂膜によって陽極室と銅補充室とに、かつ陰イオン交換
樹脂膜によって前記銅補充室と陰極室とに仕切つてなる
銅補充用の電気透析槽と、前記銅補充用の電気透析槽の
前記陽極室にアノード溶解によって銅イオンを発生させ
るための銅電極、水素イオンを発生させるための電極の
２種類の設置された陽極電極と、前記銅補充用の電気透
析槽の前記陰極室に設置した陰極電極と、前記両電極間
に直流電圧を印加する直流電源と、銅イオンを発生させ
るための前記銅電極と水素イオンを発生させるための前
記電極に流す電流をコントロールする機構とを有する銅
補充機構と、銅イオンの還元剤を補充する機構と、化学
銅めっき液の各成分を分析し、前記めっき液再生用およ
び前記銅補充用の電気透析槽のそれぞれの前記電極間に
流す電流値をコントロールする機構とを備えたことを特
徴とする化学銅めっき液の管理装置。An electrodialysis tank for plating solution regeneration, which is partitioned into three chambers, an anode chamber, a plating solution regeneration chamber, and a cathode chamber, by two anion exchange resin membranes; a plating solution regeneration mechanism having an anode electrode and a cathode electrode respectively installed in the cathode chamber, and a DC power source that applies a DC voltage between the two electrodes; an electrodialysis tank for copper replenishment which is partitioned into the copper replenishment chamber and a cathode chamber by an anion exchange resin membrane; and an electrodialysis tank for generating copper ions by anode dissolution in the anode chamber of the electrodialysis tank for copper replenishment. A DC voltage is applied between two types of anode electrodes, a copper electrode and an electrode for generating hydrogen ions, and a cathode electrode installed in the cathode chamber of the electrodialysis tank for copper replenishment, and both electrodes. a copper replenishment mechanism having a DC power source for generating copper ions, a mechanism for controlling current flowing through the copper electrode for generating copper ions and the electrode for generating hydrogen ions, and a mechanism for replenishing a reducing agent for copper ions. , a mechanism for analyzing each component of a chemical copper plating solution and controlling the current value flowing between the electrodes of each of the electrodialysis tanks for regenerating the plating solution and for replenishing copper. Copper plating solution management device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27891787A JPH01119678A (en) | 1987-11-02 | 1987-11-02 | Apparatus for administrating chemical copper plating liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27891787A JPH01119678A (en) | 1987-11-02 | 1987-11-02 | Apparatus for administrating chemical copper plating liquid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01119678A true JPH01119678A (en) | 1989-05-11 |
Family
ID=17603888
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27891787A Pending JPH01119678A (en) | 1987-11-02 | 1987-11-02 | Apparatus for administrating chemical copper plating liquid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01119678A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06316769A (en) * | 1993-01-26 | 1994-11-15 | Nippon Parkerizing Co Ltd | Device and method for intermittently removing metal ion and contaminants from chemical bath |
| JP2011514936A (en) * | 2008-03-12 | 2011-05-12 | マクダーミッド インコーポレーテッド | Method of electrolytically dissolving nickel in electroless nickel plating solution |
-
1987
- 1987-11-02 JP JP27891787A patent/JPH01119678A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06316769A (en) * | 1993-01-26 | 1994-11-15 | Nippon Parkerizing Co Ltd | Device and method for intermittently removing metal ion and contaminants from chemical bath |
| JP2011514936A (en) * | 2008-03-12 | 2011-05-12 | マクダーミッド インコーポレーテッド | Method of electrolytically dissolving nickel in electroless nickel plating solution |
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