JPS61270386A - Method for supplying copper ion to copper sulfate plating bath - Google Patents
Method for supplying copper ion to copper sulfate plating bathInfo
- Publication number
- JPS61270386A JPS61270386A JP11263785A JP11263785A JPS61270386A JP S61270386 A JPS61270386 A JP S61270386A JP 11263785 A JP11263785 A JP 11263785A JP 11263785 A JP11263785 A JP 11263785A JP S61270386 A JPS61270386 A JP S61270386A
- Authority
- JP
- Japan
- Prior art keywords
- copper
- copper sulfate
- plating
- plating bath
- bath
- 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.)
- Granted
Links
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- Electroplating And Plating Baths Therefor (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、硫酸銅めっき浴への銅イオン補給方法に関す
る。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for replenishing copper ions to a copper sulfate plating bath.
銅めっきは、銅が空気中で変色し易いので、防食用や装
飾用とし単独で利用されることは殆どないが、銅がニッ
ケル等の金属に対して良好な密着性を有することから、
中間めっき用として広く利用さている。また、銅めっき
は、浸炭防止用として利用されることもある。Copper plating is rarely used alone for corrosion protection or decoration because copper easily discolors in the air, but copper plating has good adhesion to metals such as nickel.
Widely used for intermediate plating. Copper plating is also sometimes used to prevent carburization.
かかる銅めっきを行う場合、硫酸銅めっき浴が古くから
用いられているが、該硫酸銅めっき浴を用いて長尺鋼帯
等の長尺帯状波めっき材に連続的に銅めっきを施す場合
は、硫酸銅(Cu S Oa ・5 H2O):15
0〜250g/6、硫酸(HZ SC2):50〜75
g//!の基本浴組成からなる硫酸銅めっき浴を用意し
、該めっき浴中にアノードとなる電極を浸漬し、該電極
の近傍を、コンダクタ−ロールにて給電されてカソード
となる長尺帯状波めっき材をして連続通過せしめ、電解
による電着を利用して該長尺帯状波めっき材の表面に銅
皮膜を形成する。When performing such copper plating, a copper sulfate plating bath has been used for a long time, but when copper plating is continuously applied to a long strip wave plated material such as a long steel strip using the copper sulfate plating bath, , copper sulfate (Cu SOa ・5 H2O): 15
0-250g/6, sulfuric acid (HZ SC2): 50-75
g//! A copper sulfate plating bath having a basic bath composition of The copper film is formed on the surface of the long band wave plated material using electrolytic electrodeposition.
ところで、上述の硫酸銅めっき浴へ銅イオンをいかに補
給するかについて言及するに、従来は銅電極を溶解電極
として用い、該銅電極を溶解させて銅イオンを補給する
のが通常であった。By the way, regarding how to replenish copper ions to the above-mentioned copper sulfate plating bath, it has conventionally been usual to use a copper electrode as a dissolving electrode and to melt the copper electrode to replenish copper ions.
具体例を挙げれば、第4図に示す如きめっき設備、即ち
、めっきタンク(41)内に貯留した硫酸銅めっき浴(
L)内にジンクロール(42)を浸漬し、該ジンクロー
ル(42)によって硫酸銅めっき浴(L)内へ案内され
る長尺帯状波めっき材(S)(該長尺帯状波めっき材(
S)は矢符にて示す如く鉛直方向へ送給される)を挾ん
で平行に並ぶように銅電極(43)・・(43)を吊支
した設備が用いられ、該銅電極(43)・・(43)を
溶解させることにより銅イオンを硫酸銅めっき浴(L)
中へ補給していた。なお、第4図中、(44) (44
)は長尺帯状波めっき材(S)へ給電するためのコンダ
クタ−ロールである。To give a specific example, the plating equipment as shown in FIG. 4, that is, the copper sulfate plating bath (41) stored in the plating tank (41)
Zinc roll (42) is immersed in L), and the long band wave plating material (S) is guided into the copper sulfate plating bath (L) by the zinc roll (42).
S) is fed in the vertical direction as shown by the arrow mark)) is used, and equipment is used in which copper electrodes (43) are suspended so as to be lined up in parallel. ...(43) to remove copper ions from copper sulfate plating bath (L)
They were resupplying inside. In addition, (44) (44
) is a conductor roll for supplying power to the long strip wave plated material (S).
かかる設備を用いて銅めっきを行う場合、銅電極(43
)・・(43)を上方へ又は水平方向へ移動させること
が容易であるので、溶解電極たる銅電極(43)・・(
43)の交換を簡単に行えるという利点があるが、ジン
クロール(42)の軸受部からの硫酸銅めっき浴(L)
の漏れが問題となる。また、長尺帯状波めっき材(S)
を硫酸銅めっき浴(L)内にて送給方向を転換させると
いう送給方法は、長尺帯状波めっき材(S)が複雑な径
路を辿ることとなって通根性が悪いという問題がある。When performing copper plating using such equipment, a copper electrode (43
)...(43) can be easily moved upward or horizontally, so the copper electrode (43) serving as the melting electrode...(
43) has the advantage of being easy to replace, but the copper sulfate plating bath (L) from the bearing part of the zinc roll (42)
leakage becomes a problem. In addition, long strip wave plated material (S)
The feeding method in which the feeding direction is changed in the copper sulfate plating bath (L) has the problem that the long band wave plated material (S) follows a complicated path, resulting in poor rootability. .
そこで、かかる問題を解消するために、第1図(縦断面
図)及び第2図(第1図のn−n線による横断面図)に
示す如(長尺帯状波めっき材(S)を水平方向へ送給す
るめっき設備が考えられている。即ち、めっきタンク(
11)内に充満させた硫酸銅めっき浴(L)をその上層
部から溢出させ、該硫酸銅めっき浴(L)の上層部へ、
コンダクタ−ロール(12) (12)から給電されて
カソードとなる長尺帯状波めっき材(S)を水平方向へ
送給し、該長尺帯状波めっき材(S)の上下に平行に並
ぶようにカソードとなる電極(13) (14)を水平
配置した設備が用いられている。なお、めっきタンク(
11)から溢出した硫酸銅めっき浴(L)は貯蔵タンク
(16)にて全量回収され、該貯蔵タンク(16)に付
設されたポンプ(15)にてめっきタンク(11)へ循
環供給されるようになっている。Therefore, in order to solve this problem, as shown in Fig. 1 (longitudinal cross-sectional view) and Fig. 2 (cross-sectional view taken along line nn in Fig. 1), we developed a long band-shaped wave plated material (S). A plating equipment that feeds horizontally is being considered.In other words, a plating tank (
11) The copper sulfate plating bath (L) filled in the interior overflows from the upper layer thereof to the upper layer of the copper sulfate plating bath (L),
Electricity is supplied from the conductor roll (12) (12) to feed the long band wave plated material (S) which becomes the cathode in the horizontal direction so that the long band wave plated material (S) is lined up and down in parallel. Equipment in which electrodes (13) and (14) serving as cathodes are arranged horizontally is used. In addition, the plating tank (
The copper sulfate plating bath (L) overflowing from 11) is collected in its entirety in a storage tank (16), and is circulated and supplied to the plating tank (11) by a pump (15) attached to the storage tank (16). It looks like this.
かかるめっき設備を用い、電極(13) (14)とし
て溶解電極を用いる場合は、硫酸銅めっき浴(L)の漏
れがなくなり、長尺帯状波めっき材(S)の通根性が改
善されるが、長尺帯状波めっき材(S)の下方に水平配
置される電極(14)の交換作業が極めて厄介な作業と
なる。即ち、該電極(14)を交換するには、長尺帯状
波めっき材(S)の送給を停止し、該長尺帯状波めっき
材(S)が電極(14)の上方に存在しない状態にした
上で該電極(14)を交換する必要があり、生産性を低
下させる要因ともなる。When such plating equipment is used and dissolving electrodes are used as the electrodes (13) and (14), leakage of the copper sulfate plating bath (L) is eliminated and the root permeability of the long strip wave plated material (S) is improved. The work of replacing the electrode (14) horizontally arranged below the long band wave plated material (S) becomes extremely troublesome work. That is, in order to replace the electrode (14), the feeding of the long strip wave plating material (S) is stopped, and the state in which the long strip wave plating material (S) is not present above the electrode (14) is changed. It is necessary to replace the electrode (14) after the electrode (14) has been replaced, which also causes a decrease in productivity.
しかも、陰極効率及び陽極効率の関係から硫酸銅めっき
浴(L)中の銅イオン濃度が変化し易く、そのコントロ
ールが極めて難しいという問題がある上、硫酸を絶えず
補給する必要もある。Moreover, there is a problem that the copper ion concentration in the copper sulfate plating bath (L) tends to change due to the relationship between cathode efficiency and anode efficiency, and it is extremely difficult to control it, and it is also necessary to constantly replenish sulfuric acid.
そこで、電極(13) (14)としてチタンを主成分
とする基材の表面に2μm程度の白金めっき層を形成し
たものや貴金属の酸化物を焼き付けた不溶解電極を用い
、上述した如き溶解電極を用いた場合の問題を解決する
ことが検討されている。Therefore, as the electrodes (13) and (14), we used an insoluble electrode with a platinum plating layer of about 2 μm formed on the surface of a base material mainly composed of titanium, or an insoluble electrode with a noble metal oxide baked on, and the dissolving electrode as described above. It is being considered to solve the problem when using .
然るに、電極(13) (14)を溶解させることによ
り銅イオンを硫酸銅めっき浴(L)中へ補給する方法を
採らない場合には、硫酸銅めっき浴(L)中への銅イオ
ン補給方法を新たに考えなければならないが、これまで
、その適切な補給方法は創案されていない。However, if the method of replenishing copper ions into the copper sulfate plating bath (L) by dissolving the electrodes (13) (14) is not adopted, there is a method of replenishing copper ions into the copper sulfate plating bath (L). It is necessary to think about this in a new way, but to date, no suitable method of replenishment has been devised.
本発明は、かかる事情に鑑みてなされたものであり、硫
酸銅めっき浴(L)中への銅イオン補給方法を新たに創
案し、電極(13) (14)の不熔解化を図るもので
ある。The present invention has been made in view of the above circumstances, and aims to make the electrodes (13) and (14) insoluble by devising a new method for replenishing copper ions into the copper sulfate plating bath (L). be.
本発明に係る硫酸銅めっき浴の銅イオン補給方法は、酸
化&Pl(CaO)と硫酸ipJ (Cu S 04
・5H20)とを併用補給する点に特徴を有している。The method for replenishing copper ions in a copper sulfate plating bath according to the present invention includes oxidation &Pl (CaO) and sulfuric acid ipJ (Cu S 04
・5H20) is unique in that it can be supplied in combination with
なお、酸化銅と硫M銅とを併用補給することとしたのは
、酸化銅のみを補給することとすれば、コストが高くな
る上、従来通り硫酸の補給が必要となるからであり、ま
た硫酸銅のみを補給することとすれば、硫酸銅めっき浴
中の硫酸濃度が上昇して浴バランスがくずれるからであ
る。The reason why we decided to replenish copper oxide and copper sulfate in combination was that if we were to replenish only copper oxide, the cost would be high and we would need to replenish sulfuric acid as usual. This is because if only copper sulfate is supplied, the sulfuric acid concentration in the copper sulfate plating bath will increase and the bath balance will be disrupted.
かかる銅イオン補給方法を採用し、長尺鋼帯等の長尺帯
状波めっき材に連続的に銅めっきを施す場合は、溶解電
極を用いなくとも硫酸銅めっき浴中へ銅イオンが適正に
補給され、長尺帯状波めっき材に適正な銅めっきが施さ
れる。When such a copper ion replenishment method is adopted and continuous copper plating is applied to a long strip wave plated material such as a long steel strip, copper ions can be appropriately replenished into the copper sulfate plating bath without using a dissolving electrode. Then, appropriate copper plating is applied to the long strip wave plated material.
しかも、電極は不溶解電極となるので、該電極を絶えず
交換する必要がなくなり、電極交換のために長尺帯状波
めっき材の送給を停止する必要がなくなる。Moreover, since the electrode becomes an insoluble electrode, there is no need to constantly replace the electrode, and there is no need to stop feeding the long strip wave plating material for electrode replacement.
〔実施例)
第1図及び第2図に示す設備を用い、めっきタンク(I
I)内に充満させた硫酸銅めっき浴(L)をその上層部
から溢出させると共に溢出した硫酸銅めっき浴(L)は
貯蔵タンク(16)にて全量回収した上でポンプ(15
)にてめっきタンク(11)へ循環させ、該めっきタン
ク(11)内の硫酸銅めっき浴(Lの上層部に水平配置
された電極(13) (14)の間へ長尺帯状波めっき
材(S)を水平方向へ送給することにより、咳長尺帯状
被めっき材(S)に銅めっきを施した。[Example] Using the equipment shown in Figures 1 and 2, a plating tank (I
The copper sulfate plating bath (L) filled in the tank I) is allowed to overflow from its upper layer, and the overflowing copper sulfate plating bath (L) is collected in its entirety in a storage tank (16) and then transferred to a pump (15).
) to the plating tank (11), and the long strip wave plating material is passed between the electrodes (13) and (14) horizontally arranged on the upper layer of the copper sulfate plating bath (L) in the plating tank (11). By feeding (S) in the horizontal direction, copper plating was applied to the long strip-shaped material to be plated (S).
硫酸銅めっき浴(L)は、所期の浴組成が硫酸銅:20
0g/β、硫酸:50g/lのものを用い、該硫酸銅め
っき浴(L)へは、酸化銅と硫酸銅とを夫々3:1 (
重量比)の割合にて補給した。The intended bath composition of the copper sulfate plating bath (L) is copper sulfate: 20
0 g/β, sulfuric acid: 50 g/l, and copper oxide and copper sulfate were added to the copper sulfate plating bath (L) at a ratio of 3:1 (
It was replenished at a ratio of (weight ratio).
また、電極(13) (14)としては、470龍X1
700HX IQmのチタンの表面に貴金属の酸化物を
焼成した層又は2μm白金めっき層を形成した不溶解電
極を2枚並べたものを用いた。In addition, as the electrodes (13) and (14), 470 Dragon
Two insoluble electrodes were used in which a layer of baked noble metal oxide or a 2 μm platinum plating layer was formed on the surface of titanium of 700 HX IQm.
而して、100日間にわたって連続操業を行った結果、
長尺帯状波めっき材(S)には適正な銅めっきが施され
、電極(13) (14)の交換も不要であった。As a result of continuous operation for 100 days,
Appropriate copper plating was applied to the long strip wave plated material (S), and there was no need to replace the electrodes (13) (14).
なお、硫酸銅めっき浴(L)へ補給する酸化銅の20℃
(・印)及び40℃(○印)における溶解度曲線を調査
した結果を第3図に示すが、常温より) も40℃に
加熱した場合の方が高い溶解度を示すことが分かる。従
って、通常30℃に硫酸銅めっき浴(L)を加熱して行
うめっき操業において、酸化銅は硫酸銅めっき浴(L)
によく解けて好都合であることが分かる。In addition, the temperature of copper oxide to be supplied to the copper sulfate plating bath (L) is 20°C.
Figure 3 shows the results of examining the solubility curves at (*) and 40°C (○), and it can be seen that the solubility is higher when heated to 40°C (than at room temperature). Therefore, in plating operations that are normally carried out by heating the copper sulfate plating bath (L) to 30°C, copper oxide is used in the copper sulfate plating bath (L).
It can be seen that it is convenient because it can be easily solved.
また、酸化銅の代わりに水酸化銅又は亜酸化銅を使用す
る方法も考えられる。Further, a method of using copper hydroxide or cuprous oxide instead of copper oxide is also considered.
(発明の効果〕
以上述べたように、本発明方法を用いることにより、電
極を溶解させて銅イオンを硫酸銅めっき浴中へ補給せず
とも適正に銅イオンを補給することができる。その結果
、電極は不溶解電極とすることができ、被めっき材を水
平方向へ送給する場合においても、電極交換のためにラ
インを停止する必要がなくなってライン停止による生産
性低下を防止することができる。(Effects of the Invention) As described above, by using the method of the present invention, copper ions can be appropriately replenished into the copper sulfate plating bath without dissolving the electrode and replenishing copper ions into the copper sulfate plating bath. The electrode can be an insoluble electrode, and even when the material to be plated is fed horizontally, there is no need to stop the line to replace the electrode, which prevents productivity loss due to line stoppage. can.
【図面の簡単な説明】
第1図は長尺帯状波めっき材を水平方向へ送給するめっ
き設備を模式的に示す縦断面図、第2図は第1図のn−
n線による横断面図、第3図は酸化銅の溶解度曲線を示
すグラフ、第4図は長尺帯状波めっき材を鉛直方向へ送
給するめっき設備を模式的に示す縦断面図である。
IL41:めっきタンク、13,14,43 :電極、
16:貯蔵タンク、42ニシンクロール、L:硫酸銅め
っき浴、S:長尺帯状波めっき材。[Brief explanation of the drawings] Fig. 1 is a vertical cross-sectional view schematically showing a plating equipment that feeds a long strip wave plating material in the horizontal direction, and Fig. 2 is a vertical cross-sectional view schematically showing the plating equipment that feeds long strip wave plating materials in the horizontal direction.
3 is a graph showing a solubility curve of copper oxide, and FIG. 4 is a longitudinal sectional view schematically showing a plating equipment that feeds a long band wave plating material in the vertical direction. IL41: Plating tank, 13, 14, 43: Electrode,
16: storage tank, 42 herring roll, L: copper sulfate plating bath, S: long strip wave plating material.
Claims (1)
る硫酸銅めっき浴への銅イオン補給方法。(1) A method for replenishing copper ions to a copper sulfate plating bath, which comprises replenishing copper oxide and copper sulfate in combination.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP11263785A JPH0243833B2 (en) | 1985-05-24 | 1985-05-24 | RYUSANDOMETSUKYOKUHENODOIONHOKYUHOHO |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP11263785A JPH0243833B2 (en) | 1985-05-24 | 1985-05-24 | RYUSANDOMETSUKYOKUHENODOIONHOKYUHOHO |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS61270386A true JPS61270386A (en) | 1986-11-29 |
JPH0243833B2 JPH0243833B2 (en) | 1990-10-01 |
Family
ID=14591709
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP11263785A Expired - Lifetime JPH0243833B2 (en) | 1985-05-24 | 1985-05-24 | RYUSANDOMETSUKYOKUHENODOIONHOKYUHOHO |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0243833B2 (en) |
-
1985
- 1985-05-24 JP JP11263785A patent/JPH0243833B2/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
JPH0243833B2 (en) | 1990-10-01 |
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