JP3455705B2 - Electro-copper plating apparatus and copper plating method using said apparatus - Google Patents
Electro-copper plating apparatus and copper plating method using said apparatusInfo
- Publication number
- JP3455705B2 JP3455705B2 JP31629299A JP31629299A JP3455705B2 JP 3455705 B2 JP3455705 B2 JP 3455705B2 JP 31629299 A JP31629299 A JP 31629299A JP 31629299 A JP31629299 A JP 31629299A JP 3455705 B2 JP3455705 B2 JP 3455705B2
- Authority
- JP
- Japan
- Prior art keywords
- copper
- anode
- plating
- exchange membrane
- cation exchange
- 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 - Lifetime
Links
Description
【０００１】[0001]
【発明の属する技術分野】本発明は印刷用ロール、プリ
ント配線基盤のスルーホール、半導体、電解銅箔等に対
し硫酸銅めっき液からの銅めっきを施すための装置なら
びに方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an apparatus and method for applying copper plating from a copper sulfate plating solution to printing rolls, through holes of printed wiring boards, semiconductors, electrolytic copper foils and the like.
【０００２】[0002]
【従来の技術】硫酸銅めっき技術において、銅陽極の溶
解効率はほぼ100％であるのに対して、陰極ではめっき
液の必須成分として添加されている有機化合物が還元さ
れてめっき電流の一部を消耗するので、銅めっきの析出
効率は100％以下である。このため操業時間とともに、
めっき液の硫酸銅濃度が増大するので、定期的に液の一
部を廃棄するか或いは別槽に移して不溶性陽極を用いて
銅を電解除去する必要がある。さらに、銅めっき添加剤
として加えられている塩化物イオンは約40〜100ppmの範
囲内で管理することが不可欠であるが、夏場など水道水
の塩化物濃度が高くなると容易に100ppmを超過し、塩化
物イオンの作用によってしばしばアノードを不動態化す
るなどの問題がある。2. Description of the Related Art In the copper sulfate plating technology, the dissolution efficiency of the copper anode is almost 100%, whereas at the cathode, the organic compound added as an essential component of the plating solution is reduced and a part of the plating current is reduced. Therefore, the deposition efficiency of copper plating is 100% or less. Therefore, along with the operating time,
Since the concentration of copper sulfate in the plating solution increases, it is necessary to periodically discard a part of the solution or transfer it to another tank to electrolytically remove copper using an insoluble anode. Furthermore, it is essential to control the chloride ion added as a copper plating additive within the range of about 40 to 100 ppm, but when the chloride concentration of tap water is high in summer, it easily exceeds 100 ppm, There are often problems such as passivation of the anode due to the action of chloride ions.
【０００３】ところで、硫酸銅溶液めっき液に浸漬した
ときの陽極銅の表面には10-3MのオーダーのCu+イオンが
存在しており、めっき時銅溶解時にはCu+イオンが電極
電位に依存して増加することが知られている。この１価
のCu+イオンは不安定なため不均化反応を起こしてめっ
き液中に銅の微粒子或いは亜酸化銅の微粒子を形成す
る。そしてめっき液中を浮遊し、めっき皮膜に悪影響を
もたらすに至る。従ってCu+イオンは酸化除去するため
に、通常めっき液は強く空気撹拌されている。By the way, Cu + ions of the order of 10 -3 M exist on the surface of the anodic copper when immersed in a copper sulfate solution plating solution, and the Cu + ions depend on the electrode potential during dissolution of copper during plating. And is known to increase. Since this monovalent Cu + ion is unstable, it causes a disproportionation reaction to form fine particles of copper or fine particles of cuprous oxide in the plating solution. Then, it floats in the plating solution and adversely affects the plating film. Therefore, in order to remove Cu + ions by oxidation, the plating solution is usually strongly agitated with air.
【０００４】また、銅陽極には大別して含リン銅陽極、
電気銅陽極、無酸素銅陽極の3種類が知られているが、
そのうち電気銅や無酸素銅陽極は、銅が溶解すると、め
っき液中に多量の銅の微粒子や亜酸化銅の微粒子の陽極
スライムを形成し、これがめっき皮膜中に取り込まれて
皮膜に重大な損傷を与えるために、従来、安価であるに
も係らず使用できなかった。他方、含リン銅陽極はめっ
き時にはめっき液を空気撹拌することが必須であるが、
前記電気銅や無酸素銅よりはCu+イオンを生成しにく
く、スライムを発生しにくいので、一般に広く使用され
ている。しかしながら含リン銅陽極は、溶解時電解表面
にリン化銅を主成分とする黒いヘドロ状膜を形成し、陽
極スライムの形成も完全には回避できない。それゆえ従
来、含リン銅陽極は布袋等で包んでいわゆるアノードバ
ッグの形で使用されているが、そのバッグはヘドロ状の
スライムにより目詰まりを起こすので、手間のかかる定
期的洗浄を行わなければならない煩わしさがあった。ま
た、陽極からの微粒子はアノードバッグによっても完全
に除去できず、頻繁にめっき皮膜にピットやざらつきな
どの損傷を与えていた。そこでろ過器等で微粒子を循環
ろ過することも行われていた。さらには含リン銅はコス
トがかかる点も不利であった。The copper anodes are roughly classified into phosphorus-containing copper anodes,
Three types are known, an electric copper anode and an oxygen-free copper anode.
Among them, electrolytic copper and oxygen-free copper anodes, when copper is dissolved, form a large amount of anodic slime of copper fine particles and cuprous oxide fine particles in the plating solution, which is taken into the plating film and seriously damages the film. In the past, it was not possible to use it, though it was inexpensive. On the other hand, the phosphorus-containing copper anode is essential to stir the plating solution with air during plating.
Since it is less likely to generate Cu + ions and less likely to generate slime than the electrolytic copper or oxygen-free copper, it is widely used. However, the phosphorus-containing copper anode forms a black sludge-like film containing copper phosphide as a main component on the electrolytic surface during melting, and formation of the anode slime cannot be completely avoided. Therefore, conventionally, the phosphorus-containing copper anode is wrapped in a cloth bag or the like and used in the form of a so-called anode bag, but the bag causes clogging due to sludge-like slime, so it is necessary to perform time-consuming regular cleaning. There was annoyance. Further, fine particles from the anode could not be completely removed by the anode bag, and the plating film was frequently damaged such as pits and roughness. Therefore, circulation filtration of fine particles has also been performed with a filter or the like. Furthermore, phosphorus-containing copper is also disadvantageous in that it is costly.
【０００５】[0005]
【発明が解決しようとする課題】従って本発明は従来の
硫酸銅めっき方法における前記欠点ないし問題点に鑑み
て、めっきプロセスに伴う硫酸銅濃度の増加の抑制、塩
化物イオンによる陽極不動態化現象の防止、硫酸銅めっ
き皮膜の陽極スライムによるざらつきやピット生成の防
止、含リン銅陽極使用に伴うヘドロ生成の阻止、従って
廃棄物ゼロ化とヘドロ除去作業のような余計な作業の免
除を図ろうとするものである。さらには、従来使用でき
なかった安価な電気銅、無酸素銅陽極の使用を可能にす
るような装置と方法を提供することも目的とする。Therefore, in view of the above-mentioned drawbacks and problems in the conventional copper sulfate plating method, the present invention suppresses an increase in the copper sulfate concentration accompanying the plating process, and an anode passivation phenomenon due to chloride ions. To prevent roughening and pit formation due to the anode slime of the copper sulfate plating film, to prevent sludge formation associated with the use of phosphorus-containing copper anodes, and to eliminate unnecessary work such as zero waste and sludge removal work. To do. Furthermore, it aims at providing the apparatus and method which enable the use of the cheap electrolytic copper and oxygen free copper anode which were not able to be used conventionally.
【０００６】[0006]
【課題を解決するための手段】上記課題に適合する本発
明による電気銅めっき装置は、硫酸銅めっき液を装填し
た銅めっき槽内に、被めっき物としての陰極ならびに銅
陽極と不溶性陽極を内部に併設した陽極室を設置すると
ともに、前記めっき液から陽極室を隔離、区画するため
のカチオン交換膜を陽極室壁に装着してなることを特徴
とする。The electrolytic copper plating apparatus according to the present invention, which meets the above-mentioned problems, has a cathode as a material to be plated and a copper anode and an insoluble anode inside a copper plating tank filled with a copper sulfate plating solution. And an cation exchange membrane for separating and partitioning the anode chamber from the plating solution is attached to the wall of the anode chamber.
【０００７】すなわち本発明は、（１）硫酸銅めっき液
を装填しためっき槽内において、被めっき物である陰極
と陽極室とを設置するとともに、陽極室内に銅陽極と不
溶性陽極とを共に内部に収納し、陽極室をめっき液から
隔てるためにカチオン交換膜を陽極室壁に取り付けてな
る電気銅めっき装置、（２）カチオン交換膜が含フッ素
系ポリマーである前記（１）に記載の電気銅めっき装
置、（３）前記銅陽極は電気銅または無酸素銅からなる
ことを特徴とする前記（１）又は（２）に記載の電気銅
めっき装置、（４）硫酸銅めっき液内に、陰極としての
被めっき物を装入し、銅陽極と不溶性陽極とを内部に併
設してなる陽極室を設置するとともに、前記陽極室をめ
っき液から隔てるためのカチオン交換膜を陰極と対向す
る側の陽極室壁に装着すること、ならびに両陽極への電
流配分比を、めっき液中の水素イオン濃度及び銅濃度を
実質的に一定に維持しうる値に調整しながら、めっきを
行うことを特徴とする銅めっき方法、（５）前記銅陽極
として、電気銅または無酸素銅を使用することを特徴と
する前記（４）に記載の銅めっき方法、（６）前記陽極
として、電気銅陽極と白金陽極とを併用するとともに、
両陽極への電流配分比を99〜9０：1〜10の範囲内に調整
しながらめっきを行うことを特徴とする前記（４）に記
載の銅めっき方法、（７）銅陽極と不溶性陽極とを共に
室の内部に収納し、かつ室壁の全部又は一部がカチオン
交換膜からなる陽極室、（８）カチオン交換膜が、含フ
ッ素ポリマーカチオン交換膜である前記（４）〜（６）
に記載の銅めっき方法、に関する。That is, according to the present invention, (1) a cathode and an anode chamber, which are objects to be plated, are installed in a plating tank filled with a copper sulfate plating solution, and a copper anode and an insoluble anode are both provided inside the anode chamber. And a cation exchange membrane attached to the wall of the anode chamber to separate the anode chamber from the plating solution, (2) The electricity according to (1) above, wherein the cation exchange membrane is a fluorine-containing polymer. Copper plating apparatus, (3) The copper anode is composed of electrolytic copper or oxygen-free copper, (1) or (2), the electrolytic copper plating apparatus, (4) in the copper sulfate plating solution, The side opposite to the cathode is charged with a material to be plated as a cathode, and an anode chamber is provided inside which a copper anode and an insoluble anode are provided side by side, and a cation exchange membrane for separating the anode chamber from the plating solution is provided. Installed on the wall of the anode chamber That, and the current distribution ratio to both anodes, while adjusting the hydrogen ion concentration and the copper concentration in the plating solution to a value that can be maintained substantially constant, the copper plating method characterized by performing the plating, (5) Electrolytic copper or oxygen-free copper is used as the copper anode, (6) The copper plating method according to (4) above, and (6) The electrolytic copper anode and the platinum anode are used in combination as the anode. With
The copper plating method according to (4), wherein the plating is performed while adjusting the current distribution ratio to both anodes within the range of 99 to 90: 1 to 10, and (7) the copper anode and the insoluble anode (8) The cation exchange membrane is a fluorine-containing polymer cation exchange membrane, wherein (4) the cation exchange membrane is a cation exchange membrane.
The copper plating method described in 1.
【０００８】本発明者らは、銅陽極と不溶性陽極とを共
に陽電極室内に設置すると、銅陽極から生成する陽極ス
ライムが陽極内にて溶解され、めっき液中でスラッジが
全く観察されないか、めっき液中でのスラッジの発生が
顕著に抑制されることを知見し、さらに検討を重ねて本
発明を完成した。When the present inventors set up a copper anode and an insoluble anode both in the positive electrode chamber, the anode slime produced from the copper anode was dissolved in the anode, and sludge was not observed at all in the plating solution. It was found that the generation of sludge in the plating solution was significantly suppressed, and further studies were conducted to complete the present invention.
【０００９】本発明の別の態様は、硫酸銅めっき液を装
填した銅めっき槽内に、陰極としての被めっき物を装入
し、銅陽極と不溶性陽極を内部に収納してなる陽極室を
設置するとともに、めっき液から前記陽極室を隔てるた
めのカチオン交換膜隔膜を陽極室壁に装着すること、な
らびに両陽極への電流配分比を銅濃度を実質的に一定に
維持しうる値に調整しながらめっきを施すことを特徴と
する銅めっき方法にある。なお、カチオン交換膜を陽極
室壁に装着するためには、陽極室壁の一部又は全部をカ
チオン交換膜で構成された陽極室容器を使用するのがよ
い。例えば図１においては、４で示される（例えば高分
子樹脂製の）陽極室容器壁に一部が５で示されるカチオ
ン交換膜で構成されている。Another aspect of the present invention is to provide an anode chamber in which a copper plating tank filled with a copper sulfate plating solution is charged with an object to be plated as a cathode and a copper anode and an insoluble anode are housed therein. Along with the installation, a cation exchange membrane diaphragm for separating the anode chamber from the plating solution is attached to the wall of the anode chamber, and the current distribution ratio to both anodes is adjusted to a value that can maintain the copper concentration substantially constant. However, the copper plating method is characterized by performing plating. In addition, in order to mount the cation exchange membrane on the wall of the anode chamber, it is preferable to use an anode chamber container in which a part or the whole of the wall of the anode chamber is composed of the cation exchange membrane. For example, in FIG. 1, a part of the cation exchange membrane indicated by 5 is formed on the wall of the anode chamber container indicated by 4 (for example, made of polymer resin).
【００１０】前記陽極室に設置される一方の銅陽極とし
ては、従来一般的な含リン銅のみならず、従来は使用で
きなかった電気銅、無酸素銅も使用することができる。
他方の不溶性陽極としては、白金、チタン、フェライ
ト、グラファイト、過酸化鉛又はRuO2もしくはOsO2など
をチタニウム板に焼きつけた酸化物電極などが挙げられ
る。また、本発明の重要な構成要素であるカチオン交換
膜隔膜は、陽極室壁に、カチオン交換膜ならばどのよう
なものでもよいが、めっき液から隔離するように被覆装
着して使用される。このようにすれば、Cu2+イオンとH+
イオンだけがこの膜を通じて、めっき液中に供給され
る。そのようなカチオン交換膜としては耐熱性と耐酸化
性を有するものが好ましく、最も好ましくは含フッ素ポ
リマーカチオン交換膜である。そのような好適な１例と
しては、パーフルオロスルフォン酸基を有するポリマ
ー、商標名ナフィオン(Nafionデュポン社製)が挙げられ
る。なお、陰極室内めっき液は公知の銅めっき液であっ
てよい。所望により硫酸を添加した硫酸銅水溶液であ
る。めっき操作前の陽極室内の液も公知のものであって
よい。具体的には硫酸、硫酸銅水溶液又は硫酸と硫酸銅
水溶液であってよい。As one of the copper anodes installed in the anode chamber, not only conventional phosphorus-containing copper, but also electrolytic copper and oxygen-free copper which cannot be used conventionally can be used.
Examples of the other insoluble anode include an oxide electrode obtained by baking platinum, titanium, ferrite, graphite, lead peroxide, or RuO 2 or OsO 2 on a titanium plate. The cation-exchange membrane diaphragm, which is an important component of the present invention, may be any cation-exchange membrane as long as it is a cation-exchange membrane, but it is used by being coated and attached so as to be isolated from the plating solution. By doing this, Cu 2+ ions and H +
Only ions are supplied into the plating solution through this film. As such a cation exchange membrane, one having heat resistance and oxidation resistance is preferable, and a fluoropolymer cation exchange membrane is most preferable. One such preferable example is a polymer having a perfluorosulfonic acid group, trade name Nafion (manufactured by Nafion DuPont). The cathode chamber plating solution may be a known copper plating solution. It is a copper sulfate aqueous solution to which sulfuric acid is added if desired. The liquid in the anode chamber before the plating operation may be a known one. Specifically, it may be sulfuric acid, an aqueous solution of copper sulfate, or an aqueous solution of sulfuric acid and copper sulfate.
【００１１】本発明に従って陽極室内銅陽極と不溶性陽
極とを併設すれば、陽極室内において銅陽極から生成す
るCu+イオンが不溶性陽極から発生する酸素によって酸
化されるので、不均化反応による銅或いは亜酸化銅微粒
子の発生が抑制される。また、陽極室で生成するCu++イ
オンと水素イオンのみが選択的にカチオン交換膜を通し
てめっき液に補給されて、陽極スライムがたとえ発生し
ても前記イオン交換膜で物理的に遮蔽されるので、めっ
き液を汚染することがなく、従ってめっき皮膜のざらつ
き、ピット発生が回避されるので、良質の銅めっき皮膜
が安定的に得られる。銅陽極として含リン銅を使用して
も、不溶性陽極を併用するので黒いヘドロ状の膜が形成
されないし、めっき液の必須成分である塩化物イオンは
カチオン交換膜で遮蔽されて銅陽極に接触することがな
いので、不動態化の可能性も全くなくなる。If a copper anode and an insoluble anode are provided side by side according to the present invention, Cu + ions generated from the copper anode in the anode chamber are oxidized by oxygen generated from the insoluble anode. Generation of cuprous oxide fine particles is suppressed. Further, only Cu ++ ions and hydrogen ions generated in the anode chamber are selectively replenished to the plating solution through the cation exchange membrane, and even if anode slime occurs, it is physically shielded by the ion exchange membrane. Since the plating solution is not contaminated and the plating film is not roughened or pits are generated, a good quality copper plating film can be stably obtained. Even if phosphorus-containing copper is used as the copper anode, a black sludge-like film is not formed because the insoluble anode is also used, and chloride ions, which are an essential component of the plating solution, are shielded by the cation exchange membrane and contact the copper anode. Since there is nothing to do, there is no possibility of passivation.
【００１２】[0012]
【発明の実施の形態】以下、本発明の具体的実施態様を
添付図面ならびに実施例によって説明する。本発明によ
るめっき装置の１例を示す概略断面図において、めっき
用電解槽１は陰極室３と陽極室４とに区画されており、
両者を隔てているのは交換膜５（好ましくはフッ素ポリ
マー系カチオン交換膜）である。電解槽１には硫酸銅め
っき液２が装填されており、陰極室３には陰極としての
被めっき物31が挿入されており、陽極室４内には銅陽極
41と不溶性陽極42が並行して併設されている。カチオン
交換膜５は陽極室４の、陰極室に対向する壁に取着され
ている。陽極室４内にはめっき液と同じ主成分の液43、
すなわち硫酸銅および／または硫酸が含まれている。陽
極室４には、液の撹拌を行うための（ないしスライムの
溶解のための）撹拌手段９例えば機械的撹拌器又は液循
環ポンプそして陰極室3において自体公知の手段に従っ
た空気攪拌器を設置することが好ましい。そのようにす
れば、Cu +イオンの酸化及びスライムの溶解が陽極室で
円滑に行なわれる。銅陽極41と不溶性陽極42は電流調節
装置８によってめっき工程において両者の電流配分比を
調節する。図面番号７は直流電源である。カチオン交換
膜５は何回か使用後新品と交換可能であり、止め具で壁
に脱着可能に固定されている。BEST MODE FOR CARRYING OUT THE INVENTION Specific embodiments of the present invention will be described below.
The description will be made with reference to the accompanying drawings and examples. According to the invention
In a schematic sectional view showing an example of a plating device
The electrolytic cell 1 is divided into a cathode chamber 3 and an anode chamber 4,
Separating the two is an exchange membrane 5 (preferably fluorine poly
Mer-based cation exchange membrane). Copper sulphate is used in the electrolytic cell 1.
The plating solution 2 is loaded and the cathode chamber 3 serves as a cathode.
The object to be plated 31 is inserted, and the copper anode is placed in the anode chamber 4.
41 and insoluble anode 42 are installed side by side in parallel. Cation
The exchange membrane 5 is attached to the wall of the anode chamber 4 facing the cathode chamber.
ing. In the anode chamber 4, a liquid 43 having the same main component as the plating liquid,
That is, it contains copper sulfate and / or sulfuric acid. Sun
The polar chamber 4 has a (or slime) for stirring the liquid.
Stirring means 9 (for dissolution), eg mechanical stirrer or liquid circulation
In the ring pump and in the cathode chamber 3 follow the means known per se
It is preferable to install an air stirrer. Do that
If Cu +Oxidation of ions and dissolution of slime in the anode chamber
It is done smoothly. Copper anode 41 and insoluble anode 42 regulate current
The current distribution ratio between the two in the plating process by the device 8
Adjust. Drawing number 7 is a DC power supply. Cation exchange
Membrane 5 can be replaced with a new one after several uses, with fasteners on the wall
It is fixed to be removable.
【００１３】実施例１
下記表１のめっき液を用いて、陰極としてプリント配線
板を用いる以外は実施例２と同様のめっき装置、めっき
条件でめっきを行った。両陽極への電流配分比を95：５
とすることにより30時間めっき後のめっき液組成を測定
した結果、硫酸銅濃度は74.4 g/l、硫酸濃度は203.5 g/
lであった。従って銅濃度は実質的に維持されたことが
分かる。また陽極室内には陽極スライムは見られず、ピ
ットやざらつきのない良好な銅めっき皮膜が得られた。Example 1 Using the plating solutions shown in Table 1 below, plating was performed under the same plating apparatus and plating conditions as in Example 2 except that a printed wiring board was used as the cathode. The current distribution ratio to both anodes is 95: 5
As a result of measuring the plating solution composition after plating for 30 hours, the copper sulfate concentration was 74.4 g / l and the sulfuric acid concentration was 203.5 g / l.
It was l. Therefore, it can be seen that the copper concentration was substantially maintained. No anode slime was found in the anode chamber, and a good copper plating film without pits or roughness was obtained.
【００１４】[0014]
【表１】 硫酸銅 硫酸 添加剤 塩素イオン めっき液組成 80 g/l 200 g/l 適量 50 ppm 陽極室組成 200 g/l 20 g/l ― ― [Table 1] Copper sulfate Sulfuric acid Additive Chloride Plating solution composition 80 g / l 200 g / l Suitable amount 50 ppm Anode chamber composition 200 g / l 20 g / l ― ―
【００１５】実施例２
めっき用電解槽１を含フッ素ポリマー系カチオン交換膜
（商標名ナフィオン）５で500mlの陽極室４と1000mlの
陰極室３とに分割して、陰極室には下記表２の硫酸銅め
っき液を、陽極室には硫酸酸性にした硫酸銅溶液を満た
した。陰極にはめっき素地として0.5dm2の銅板を、陽極
室内には表面積80cm2の電気銅および白金被覆したチタ
ン金網を設置し、槽電流１Aで約30時間めっきを行っ
た。両陽極への、電流配分比を97：3、95：5および90：
10に変えて、めっき槽内の銅濃度と硫酸銅濃度の変化を
調べたところ、表２の結果が得られた。これからは、銅
濃度は不溶性陽極への電流配分が大きいと減少するが、
この例では97：3の場合にほぼ一定に維持されたことが
分かる。陽極室内にはいずれの電流配分比でも陽極スラ
イムの形成は見られず、ピットやざらつきのない美麗な
銅めっき皮膜が得られた。Example 2 An electrolytic bath 1 for plating was divided into a 500 ml anode chamber 4 and a 1000 ml cathode chamber 3 with a fluorinated polymer cation exchange membrane (Nafion) 5 and the cathode chamber shown in Table 2 below was used. The copper sulfate plating solution of 1 was filled in the anode chamber with a copper sulfate solution acidified with sulfuric acid. A 0.5 dm 2 copper plate as a plating base was installed in the cathode, and an electrolytic copper and platinum-coated titanium wire net having a surface area of 80 cm 2 was installed in the anode chamber, and plating was performed at a tank current of 1 A for about 30 hours. Current distribution ratio to both anodes 97: 3, 95: 5 and 90:
When changing to 10, the changes in the copper concentration and the copper sulfate concentration in the plating tank were examined, and the results shown in Table 2 were obtained. From now on, the copper concentration decreases as the current distribution to the insoluble anode increases, but
In this example, it can be seen that it was maintained almost constant in the case of 97: 3. No formation of anode slime was observed in any of the current distribution ratios in the anode chamber, and a beautiful copper plating film without pits or roughness was obtained.
【００１６】[0016]
【表２】 [Table 2]
【００１７】[0017]
【表３】 [Table 3]
【００１８】実施例３
グラビア印刷用シリンダーの銅めっきを、慣用条件下で
（温度40℃、電流密度10A/dm2）、実施例１と同様の装
置と方法によって表４に示す浴を用いて連続50時間行っ
た。陽極室の電流配分比は電気銅90：白金極10であっ
た。50時間めっき後のめっき液組成は硫酸銅228.6 g/
l、硫酸62.5 g/lであり、銅濃度が維持されたことが分
かる。得られためっき皮膜はピット、ざらつきがなく、
光沢のよいものであった。Example 3 Copper plating of a gravure printing cylinder was carried out under the conventional conditions (temperature 40 ° C., current density 10 A / dm 2 ), using the same apparatus and method as in Example 1 and using the baths shown in Table 4. It was carried out continuously for 50 hours. The current distribution ratio in the anode chamber was electrolytic copper 90: platinum electrode 10. The plating solution composition after plating for 50 hours is copper sulfate 228.6 g /
1 and sulfuric acid 62.5 g / l, showing that the copper concentration was maintained. The obtained plating film has no pits and roughness,
It was glossy.
【００１９】[0019]
【表４】 硫酸銅 硫酸 添加剤 塩素イオン めっき液組成 240 g/l 60 g/l 適量 50 ppm 陽極室組成 300 g/l 15 g/l ― ―[Table 4] Copper sulfate Sulfuric acid additive Chloride plating solution composition 240 g / l 60 g / l Appropriate amount 50 ppm Anode chamber composition 300 g / l 15 g / l ― ―
【００２０】実施例４
陽極として電気銅と白金極を併用し、下記のめっき液を
使用して、両者の電流配分比を1.9Aと0.1A(95：5)に選
んで、表５のめっき条件下でめっきを行った。比較例と
して従来法の陽極として電気銅をポリプロピレン製アノ
ードバッグで被覆したものを用いて、同じめっき液とめ
っき条件下で比較実験を行った。めっき液組成
硫酸銅 220 g/l
硫酸 60 g/l
添加剤 適量
塩素イオン 50 ppm
従来法では２時間のめっきで、得られためっき皮膜はざ
らついて、殆ど無光沢であった。またアノードバッグ中
には多量の銅のスライムがあり、めっき槽の中にも浮遊
していた。対照的に、本発明の方法では、10時間のめっ
きでも光沢があり、ピットやざらつきは見られなかっ
た。そして陽極室のスライムは完全に溶解しており浮遊
物はなかった。Example 4
Use electrolytic copper and platinum electrode together as the anode, and use the following plating solution
Used to select the current distribution ratio of both to 1.9A and 0.1A (95: 5).
Then, plating was performed under the plating conditions shown in Table 5. Comparative example
Then, as the anode of the conventional method, electrolytic copper was used as an anode made of polypropylene.
The same plating solution should be
A comparative experiment was conducted under the same conditions.Plating solution composition
Copper sulfate 220 g / l
Sulfuric acid 60 g / l
Additive amount
Chloride ion 50 ppm
With the conventional method, the plating film obtained by plating for 2 hours
It was dull and almost matte. Also in the anode bag
Has a large amount of copper slime and floats in the plating tank
Was. In contrast, the method of the present invention uses 10 hours of plating.
Glossy, no pits or roughness
It was And the slime in the anode chamber is completely dissolved and floats
There was nothing.
【００２１】[0021]
【表５】 [Table 5]
【００２２】実施例５
陽極室の銅陽極として含リン銅を用いる以外は、実施例
２と全く同様の条件でめっきを行った。銅めっき皮膜は
良好な光沢を有し、ピットやざらつきは全くなかった。
また陽極室のスライムも認められなかった。Example 5 Plating was performed under exactly the same conditions as in Example 2 except that phosphorus-containing copper was used as the copper anode in the anode chamber. The copper plating film had good luster and had no pits or roughness.
Also, no slime was observed in the anode chamber.
【００２３】実施例６
陽極室の銅陽極として、無酸素銅を用いる以外は、実施
例２と全く同様の条件にてめっきを行った。その結果、
陽極スライムは認められず、めっき皮膜の外観も良好で
あった。Example 6 Plating was performed under exactly the same conditions as in Example 2 except that oxygen free copper was used as the copper anode in the anode chamber. as a result,
No anode slime was observed, and the appearance of the plating film was good.
【００２４】[0024]
【発明の効果】本発明のめっき装置ならびに方法によれ
ば、陽極として銅陽極と不溶性陽極を併用するとともに
カチオン交換膜で陽極室をめっき液(陰極室)から隔離す
ることによって、陽極スライムの形成が阻止されるのみ
ならず、凹凸形状の被めっき物の隅々にまで均質にめっ
きされて、ピットやざらつきの全くない、優れためっき
皮膜が得られる。従ってスルーホールや半導体などの精
密部品のめっきに対し特に好適である。また、めっき液
がカチオン交換膜で遮蔽されて銅陽極に接触しないの
で、塩化物イオンに起因する陽極の不動態化も全く起こ
らないし、さらには、めっき添加剤たとえば光沢剤の消
耗も大幅に削減されるので、使用量が少なくてすみ経済
的である。なによりスライムやヘドロなどの廃棄物、廃
液などを出さないので処理のための手間やコストのみな
らず、環境に対する負荷も大幅に軽減することができ
る。According to the plating apparatus and method of the present invention, a copper anode and an insoluble anode are used together as an anode, and a cation exchange membrane separates the anode chamber from the plating solution (cathode chamber) to form an anode slime. Not only is prevented, but also every corner of the uneven object to be plated is uniformly plated, and an excellent plating film having no pits or roughness is obtained. Therefore, it is particularly suitable for plating precision parts such as through holes and semiconductors. In addition, since the plating solution is shielded by the cation exchange membrane and does not come into contact with the copper anode, passivation of the anode due to chloride ions does not occur at all, and the consumption of plating additives such as brighteners is greatly reduced. Because it is used, it is economical because it consumes a small amount. Above all, it does not generate waste such as slime or sludge, waste liquid, etc., so that not only the labor and cost for the treatment but also the burden on the environment can be significantly reduced.
【００２５】[0025]
【図１】本発明のめっき装置の1例を示す概略正面断面
図である。FIG. 1 is a schematic front sectional view showing an example of a plating apparatus of the present invention.
４ 陽極室 ４１ 銅陽極 ４２ 不溶性陽極 ５ カチオン交換膜 ８ 電流配分調節装置 4 Anode chamber 41 Copper anode 42 Insoluble anode 5 Cation exchange membrane 8 Current distribution controller
───────────────────────────────────────────────────── フロントページの続き (72)発明者 森河 務 大阪府和泉市あゆみ野２丁目７番１号 大阪府立産業技術総合研究所内 (72)発明者 中出 卓男 大阪府和泉市あゆみ野２丁目７番１号 大阪府立産業技術総合研究所内 (72)発明者 湯屋 進 大阪府豊中市長興寺北１丁目５番37号 有限会社ウイング内 (56)参考文献 特開 昭56−112500（ＪＰ，Ａ) 特開 昭51−140838（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C25D 17/00 C25D 7/00 C25D 17/10 C25D 21/12 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tsutomu Morikawa 2-7-1 Ayumino, Izumi City, Osaka Prefecture, Osaka Prefectural Industrial Technology Research Institute (72) Inventor Takuo Nakade 2-7-1, Ayumino, Izumi City, Osaka Prefecture No. within Osaka Prefectural Institute of Advanced Industrial Science and Technology (72) Inventor Susumu Yuya 1-537 Chokyoji Kita, Toyonaka City, Osaka Wing Co., Ltd. (56) Reference JP-A-56-112500 (JP, A) JP 51-140838 (JP, A) (58) Fields investigated (Int.Cl. 7 , DB name) C25D 17/00 C25D 7/00 C25D 17/10 C25D 21/12
Claims (8)
おいて、被めっき物である陰極と陽極室とを設置すると
ともに、陽極室内に銅陽極と不溶性陽極とを共に内部に
収納し、陽極室をめっき液から隔てるためにカチオン交
換膜を陽極室壁に取り付けてなる銅めっき中に陽極スラ
イムを実質的に発生しない電気銅めっき装置。1. A cathode tank and an anode chamber, which are objects to be plated, are installed in a plating tank filled with a copper sulfate plating solution, and a copper anode and an insoluble anode are both housed inside the anode chamber. anode slide the cation exchange membrane to separate from the plating solution in the copper plating becomes attached to the anode chamber wall
Electrolytic copper plating equipment that does not substantially generate im .
ある請求項１に記載の電気銅めっき装置。2. The electrolytic copper plating apparatus according to claim 1, wherein the cation exchange membrane is a fluorine-containing polymer.
なることを特徴とする請求項１又は２に記載の電気銅め
っき装置。3. The electrolytic copper plating apparatus according to claim 1, wherein the copper anode is made of electrolytic copper or oxygen free copper.
っき物を装入し、銅陽極と不溶性陽極とを内部に併設し
てなる陽極室を設置するとともに、前記陽極室をめっき
液から隔てるためのカチオン交換膜を陰極と対向する側
の陽極室壁に装着すること、ならびに両陽極への電流配
分比を、めっき液中の水素イオン濃度及び銅濃度を実質
的に一定に維持しうる値に調整しながら、めっきを行う
ことを特徴とする銅めっき中に陽極スライムを実質的に
発生しない銅めっき方法。4. A copper sulfate plating solution is charged with an object to be plated as a cathode, and an anode chamber is provided inside which a copper anode and an insoluble anode are provided side by side. A cation exchange membrane for separation is attached to the wall of the anode chamber on the side facing the cathode, and the current distribution ratio to both anodes can maintain the hydrogen ion concentration and the copper concentration in the plating solution substantially constant. The anodic slime is substantially removed during copper plating, which is characterized by performing plating while adjusting the value.
Copper plating method that does not occur .
銅を使用することを特徴とする請求項４に記載の銅めっ
き方法。5. The copper plating method according to claim 4, wherein electrolytic copper or oxygen-free copper is used as the copper anode.
とを併用するとともに、両陽極への電流配分比を99〜9
０：1〜10の範囲内に調整しながらめっきを行うことを
特徴とする請求項４に記載の銅めっき方法。6. An electrolytic copper anode and a platinum anode are used together as the anode, and the current distribution ratio to both anodes is 99 to 9.
The copper plating method according to claim 4, wherein the plating is performed while adjusting the thickness within the range of 0: 1 to 10.
収納し、かつ室壁の全部又は一部がカチオン交換膜から
なる銅めっき中に陽極スライムを実質的に発生しない陽
極室。7. A positive electrode, wherein both a copper anode and an insoluble anode are housed inside a chamber, and the anode slime is not substantially generated during copper plating in which the chamber wall is wholly or partially composed of a cation exchange membrane. > Polar room.
チオン交換膜である請求項４〜６に記載の銅めっき方
法.8. The copper plating method according to claim 4, wherein the cation exchange membrane is a fluoropolymer cation exchange membrane.
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| JP6653799B2 (en) * | 2017-07-31 | 2020-02-26 | メルテックス株式会社 | Anode for electrolytic copper plating and electrolytic copper plating apparatus using the same |
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