JP2004269977A - Insoluble anode for plating - Google Patents
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Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は印刷用ロールの銅めっき、プリント配線基盤のスルホール銅めっき、電解銅箔等の硫酸銅めっき浴からの銅めっき、装飾用光沢ニッケルめっき、半光沢ニッケルめっきなどのニッケルめっき、Ｎｉ−Ｗ、Ｎｉ−Ｐ、Ｎｉ−Ｆｅ、Ｓｎ−Ｐｂ、Ｓｎ−Ａｇなどの各種合金めっき技術に関するものである。
【０００２】
【従来の技術】
従来のニッケルめっき、Ｓｎめっきなどの水溶液からの電気めっきプロセスにおいて、めっき液中の金属イオンや水素イオン濃度を制御するため、めっき槽内にカチオン交換膜でめっき液から隔てた陽極室を設置し、この中に黒鉛、フェライト、鉛などからなる不溶性陽極、Ｐｔ被覆あるいは酸化物を塗布したチタン性陽極を装入してめっきすることが提案され、使われ始めている。
【０００３】
これらの陽極室は、塩化ビニル材、ＰＰ材、アクリル材、ＦＲＰなどで作製され、陽極室材料の強度を確保するため板厚１ｃｍ程度以上の材料を用い、また、壁面の一部にカチオン交換膜などのイオン交換膜を取り付けるため、陽極室の大きさはめっき槽内で大きな容積を占める。また、陽極室重量が大きくなり、陽極室のめっき槽からの取り付け、取り外しが容易ではない。さらに、イオン交換膜をこれら樹脂製の陽極室に取り付ける際に、取り付け具を締め付け過ぎると樹脂に亀裂が生じて破壊されることから、陽極室材とイオン交換膜接合部からの液漏れを起こさないようにしっかり固定することも容易ではない。
【０００４】
【発明が解決しようとする課題】
以上のように、従来のプラスチックスを使った陽極室では陽極室の容積が過大になり、また、重量も大きいため取り扱いが面倒であった。更に陽極室からの液漏れ、あるいはめっき液の陽極室への液漏れが生じ易かった。このことはめっき作業において大きな問題となっていた。
【０００５】
【課題を解決するための手段】
本発明者らは、上記問題を解決するために鋭意検討した結果、新規な不溶性陽極を見出し、本発明を完成するに至った。
【０００６】
すなわち、本発明は、陰極である被めっき材が浸せきされためっき液から、カチオン交換膜で隔てられた陽極室において、該陽極室の材質が本質的にチタンからなり、かつ該陽極室内壁面の全部または一部に白金、白金−酸化イリジウム、酸化イリジウムから選ばれる少なくとも一つを被覆してなる陽極室一体型めっき用不溶性陽極である。
【０００７】
陽極室構造材は本質的にチタニウムからなる。従って、主成分がチタニウムであれば、他の金属が従属的に含まれた合金であってよいが、純粋なチタニウムが好ましい。陽極室構造材の厚さはめっき装置全体のスケールにもよるが、１〜５ｍｍの金属チタニウム板であってよい。
【０００８】
陽極室の側壁の一部は壁が取り払われているか又は多数の穴が空けられており、当該箇所にカチオン交換膜が取り付けられ、めっき液側と陽極室内部が分離される。通常、陽極室に取り付けられたカチオン交換膜の存在する面をめっき対象物と向かい合うように陽極室を配置するのがイオンの移動の観点から好ましい。
【０００９】
陽極室内壁面の全部または一部被覆される白金、白金−酸化イリジウムまたは酸化イリジウムはそれぞれ単独で皮膜を形成していてもよいし、成分が混ざり合った複合皮膜であってもよい。また、種々の目的に合わせ、陽極室内壁面を区画し、区分ごとに異なる皮膜を形成してもよい。酸化イリジウムが好ましい。
【００１０】
陽極室内壁面を部分的に被覆する場合は、カチオン交換膜の対抗面であることが好ましい。ここで「対抗面」とは、カチオン交換膜が取り付けられている壁のいわゆる対面にある陽極室内壁面を意味するものとする（側面図１−１参照）。
また、当該対抗面は陽極室内部に向かって突出しているのがカチオン交換膜までの距離が短くなる点で好ましい。ここで、「突出」とは、不溶性陽極部分が対抗面である本来の陽極室壁位置からカチオン交換膜面側に向かって相対的に近接している状態を意味するものとする（側面図１−２参照）。
【００１１】
一方、別法として、上記カチオン交換膜が装着される陽極室開口部が網状に成型加工されている場合は、当該網状部分の全部または一部に被覆することが可能である。
【００１２】
カチオン交換膜は特に限定されるものではなく、めっき液の種類、めっき方法等に応じて種々選定することができる。めっき液についても特に限定はないが、銅めっきをする場合には硫酸銅水溶液を好ましく使用することができる。陰極には被めっき材が装着される。
【００１３】
【発明の実施の形態】
本発明の陽極室模式図を図１に例示具体的に示す。陽極室（１）は金属チタニウム材からなり、その内壁面の全部または一部が白金、白金−酸化イリジウム、酸化イリジウムから選ばれる少なくとも一つで被覆してなるものである。被覆は陽極室組立て後に該当する内壁面にこれら白金等を塗布・焼付けしてもよく、また組立て前の部品に予め塗布・焼付けしてもよい。更には、加工前の板金に塗布・焼付けしておいてもよい。
【００１４】
カチオン交換膜（２）はこれら不溶性陽極が施された壁の対面にある壁か（側面図１−１、１−２）、あるいは不溶性陽極が施された壁と同じ壁の外壁側（側面図２）に取り付けることができる。
【００１５】
カチオン交換膜を、不溶性陽極が施された壁の対面の壁（側面図１−１、１−２）に取り付ける場合は、不溶性陽極は板状チタン、パンチングチタンやメッシュ状チタンの採用が可能である。板状チタンを採用する場合は陽極室内壁面に直接被覆することができ、一方パンチングチタンやメッシュ状チタンを採用する場合は別途作製した陽極板を陽極室内壁面に溶接やボルト締め等により固定してもよい（側面図１−１）。
この場合、不溶性陽極部分はカチオン交換膜側に突出させることができる。例えば、不溶性陽極部分を桁状に別途取り付けて当該部分を陽極室の壁面から浮かせたり、また、陽極室の壁自体を内部に向けて凸状に加工して変形させてもよい（側面図１−２）。
陽極室の壁のうち、カチオン交換膜で覆われる部分は壁が取り払われているか又は多数の穴が空けられ、イオン交換膜を介して特定物質（イオン）の膜内外の移動を可能としている。
【００１６】
カチオン交換膜を不溶性陽極が施された壁と同じ壁の外壁側（側面図２）に取り付ける場合は、不溶性陽極が施された壁には開口部として網状に多数の穴が空けられている。当該穴の空けられた壁はパンチングチタンやメッシュ状チタンの構造であるのがよい。これらの形状は陽極室の壁をそのまま加工したり、また別途作製した部材を陽極室と溶接やボルト締めにより固定（４）することで得ることができる。
【００１７】
不溶性陽極は白金、白金−酸化イリジウムまたは酸化イリジウムにより被覆されてよい。中でも酸化イリジウムを主成分として被覆した陽極は酸素発生に触媒活性があり、かつ耐久性が優れている点で好ましい。
【００１８】
カチオン交換膜（２）は金網やメッシュのついたチタン製のフレーム（３）で陽極室外面からねじ（４）などで固定して取り付けることができる。カチオン交換膜としてはデュポン社製のナフィオン、旭硝子製のセレミオンやトクヤマ製のネオセプタ等の使用が可能である。
【００１９】
電源からのブスバーと接続するための取り付け治具は、チタン製で陽極室の大きさ、通電量に応じて接合数を決め、陽極室に溶接してよい。陽極室は酸水溶液で満たされており、中でも希硫酸、リン酸などの酸水溶液を好ましく使用することができる。
【００２０】
【作用】
図２には、硫酸銅めっき液中と硫酸中での金属チタニウムの電流電位曲線、および希硫酸中での酸化イリジウムを被覆したチタニウム電極の電流電位曲線が示されている。金属チタニウムでは１．６Ｖまで陽分極しても１０μＡ／ｃｍ２以下の不働態化電流が認められるのみであるのに対し、酸化イリジウム電極上では激しく酸素発生を伴い５００ｍＡ／ｃｍ２に達する電流が認められる。従って、金属チタニウムは水溶液中での電解による酸素発生に対して極めて大きな過電圧を持ち、めっき液中で不働態化しており、これを陽極室構造材として用いてもこの上での陽極反応は起こらず、陽極室構造材の面上に施された酸化物皮膜あるいは白金皮膜上でのみ陽極反応が起こる。
【００２１】
次に実施の一例を示す。本発明はこれに限定されるものではない。
【実施例１】
高さ１５ｃｍ、幅５ｃｍ、陽極室厚さ２ｃｍ、陽極室容量１２５ｍｌのカチオン交換膜を取り付けたチタニウム製不溶性陽極固着型陽極室を作製し、これを耐熱塩ビ製の槽容量２リットルのめっき槽（高さ１５ｃｍ、幅１０ｃｍ、長さ１６ｃｍ）に装着した。陽極室の構造材は厚さ１ｍｍのチタン板とした。カチオン交換膜（旭硝子製セレミオン）は、面積０．３ｄｍ２とし、陽極室内の壁面（カチオン交換膜の対抗面側）に酸化イリジウムを塗布・焼き付けして陽極材料とした。酸化イリジウム被覆面積は０．３ｄｍ２とした。
めっき槽には光沢銅めっき液を満たし、陽極室には５％硫酸を満たして、ハルセル板（真鍮板１０ｃｍ×６ｃｍ、厚さ０．５ｍｍ）に銅めっきを行った。液組成を表１に示す。めっきを行うと、陽極室内の酸化物電極表面上でのみ酸素発生反応が起こり、めっきも良好な光沢銅めっきが得られた。
【００２２】
【表１】
【発明の効果】
本発明による陽極室一体型めっき用不溶性陽極をめっき処理に使用した場合、陽極反応である酸素発生反応は陽極室内に施された不溶性陽極上でのみ起こり、従来の樹脂製陽極室内に不溶性陽極を装入した場合と同様な機能を有するものである。また、硫酸銅めっき、ニッケルめっきなど多くのめっき液に適用が可能であり、陽極室および陽極構造がコンパクトかつ軽量となることから、作業性の改善や陽極液の液漏れを効果的に防止でき、その結果経済的メリットが大きい。
【図面の簡単な説明】
【図１】陽極室一体型めっき用不溶性陽極の構造を示した図である。
【図２】金属チタンと酸化イリジウムの電流電位曲線を示した図である。
【符号の説明】
１ 陽極室
２ イオン交換膜
３ 抑えフレーム
４ 抑えねじ
５ 不溶性陽極
６ 不溶性陽極固定具[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to copper plating of a printing roll, through-hole copper plating of a printed wiring board, copper plating from a copper sulfate plating bath such as electrolytic copper foil, bright nickel plating for decoration, nickel plating such as semi-bright nickel plating, Ni-W , Ni-P, Ni-Fe, Sn-Pb, Sn-Ag and the like.
[0002]
[Prior art]
In conventional electroplating processes from aqueous solutions such as nickel plating and Sn plating, an anode chamber separated from the plating solution by a cation exchange membrane is installed in the plating tank to control the concentration of metal ions and hydrogen ions in the plating solution. It has been proposed that an insoluble anode made of graphite, ferrite, lead, or the like, and a titanium anode coated with Pt or an oxide are charged and plated.
[0003]
These anode chambers are made of a vinyl chloride material, a PP material, an acrylic material, FRP, or the like, and are made of a material having a thickness of about 1 cm or more to secure the strength of the anode chamber material. In order to mount an ion exchange membrane such as a membrane, the size of the anode chamber occupies a large volume in the plating tank. In addition, the weight of the anode chamber increases, and it is not easy to mount and remove the anode chamber from the plating tank. In addition, when the ion exchange membrane is attached to these resin anode chambers, if the attachment is overtightened, the resin will crack and break, causing liquid leakage from the anode chamber material and the ion exchange membrane junction. It is not easy to fix it firmly.
[0004]
[Problems to be solved by the invention]
As described above, in the conventional anode chamber using plastics, the volume of the anode chamber is excessively large and the weight is large, so that handling is troublesome. Further, liquid leakage from the anode chamber or liquid leakage of the plating solution to the anode chamber was likely to occur. This has been a major problem in the plating operation.
[0005]
[Means for Solving the Problems]
The present inventors have conducted intensive studies to solve the above problems, and as a result, have found a new insoluble anode, and have completed the present invention.
[0006]
That is, the present invention provides, in a plating solution in which a material to be plated, which is a cathode, is immersed, in an anode chamber separated by a cation exchange membrane, the material of the anode chamber consists essentially of titanium, and An insoluble anode for plating integrally with an anode chamber, which is entirely or partially coated with at least one selected from platinum, platinum-iridium oxide, and iridium oxide.
[0007]
The anode compartment structural material consists essentially of titanium. Therefore, if the main component is titanium, an alloy containing another metal depending may be used, but pure titanium is preferable. The thickness of the anode chamber structural material depends on the scale of the entire plating apparatus, but may be a metal titanium plate of 1 to 5 mm.
[0008]
A part of the side wall of the anode chamber has a wall removed or a large number of holes formed therein. A cation exchange membrane is attached to the portion, and the plating solution side and the inside of the anode chamber are separated. Usually, it is preferable to dispose the anode chamber so that the surface on which the cation exchange membrane attached to the anode chamber is present faces the plating object from the viewpoint of ion movement.
[0009]
Platinum, platinum-iridium oxide or iridium oxide, which covers all or part of the inner wall surface of the anode chamber, may form a film alone, or may be a composite film in which components are mixed. Further, the wall surface of the anode chamber may be partitioned according to various purposes, and a different coating may be formed for each section. Iridium oxide is preferred.
[0010]
In the case where the wall surface of the anode chamber is partially covered, it is preferable to face the cation exchange membrane. Here, the term "opposite surface" means the wall surface of the anode chamber that is the so-called opposite surface of the wall to which the cation exchange membrane is attached (see side view 1-1).
Further, it is preferable that the opposing surface protrudes toward the inside of the anode chamber in that the distance to the cation exchange membrane is reduced. Here, "projection" means a state where the insoluble anode portion is relatively close to the cation exchange membrane surface side from the original anode chamber wall position which is the opposing surface (side view 1). -2).
[0011]
On the other hand, as another method, when the opening of the anode chamber to which the cation exchange membrane is mounted is formed in a net shape, it is possible to cover all or a part of the net portion.
[0012]
The cation exchange membrane is not particularly limited, and can be variously selected according to the type of plating solution, plating method, and the like. There is no particular limitation on the plating solution, but in the case of copper plating, an aqueous solution of copper sulfate can be preferably used. A material to be plated is mounted on the cathode.
[0013]
BEST MODE FOR CARRYING OUT THE INVENTION
A schematic diagram of the anode chamber of the present invention is specifically shown in FIG. The anode chamber (1) is made of a metallic titanium material, and the whole or a part of the inner wall surface is coated with at least one selected from platinum, platinum-iridium oxide, and iridium oxide. The coating may be applied and baked with platinum or the like on the corresponding inner wall surface after assembling the anode chamber, or may be applied and baked in advance on parts before assembling. Further, it may be applied and baked on a sheet metal before processing.
[0014]
The cation exchange membrane (2) is either a wall opposite to the wall provided with the insoluble anode (side view 1-1, 1-2) or an outer wall side of the same wall provided with the insoluble anode (side view). 2) Can be attached.
[0015]
When the cation exchange membrane is attached to the wall opposite to the wall provided with the insoluble anode (side view 1-1, 1-2), the insoluble anode may be titanium plate, punched titanium or mesh titanium. is there. When plate-like titanium is used, it can be directly coated on the wall of the anode chamber.On the other hand, when punching titanium or mesh-like titanium is used, an anode plate made separately is fixed to the wall of the anode chamber by welding or bolting. (Side view 1-1).
In this case, the insoluble anode portion can protrude toward the cation exchange membrane. For example, an insoluble anode portion may be separately attached in a girder shape and the portion may be floated from the wall surface of the anode chamber, or the wall itself of the anode chamber may be formed into a convex shape toward the inside and deformed (side view 1). -2).
The portion of the wall of the anode chamber that is covered with the cation exchange membrane has the wall removed or a large number of holes formed therein, so that a specific substance (ion) can move inside and outside the membrane via the ion exchange membrane.
[0016]
When the cation exchange membrane is mounted on the outer wall side (side view 2) of the same wall as the wall provided with the insoluble anode, a large number of holes are formed as openings in the wall provided with the insoluble anode. The perforated wall may have a structure of punched titanium or mesh titanium. These shapes can be obtained by processing the wall of the anode chamber as it is or by fixing (4) a separately prepared member to the anode chamber by welding or bolting.
[0017]
The insoluble anode may be coated with platinum, platinum-iridium oxide or iridium oxide. Among them, an anode coated with iridium oxide as a main component is preferable because it has catalytic activity for generating oxygen and has excellent durability.
[0018]
The cation exchange membrane (2) can be fixedly attached with screws (4) or the like from the outer surface of the anode chamber with a titanium frame (3) provided with a wire mesh or a mesh. As the cation exchange membrane, Nafion manufactured by DuPont, Selemion manufactured by Asahi Glass or Neosepta manufactured by Tokuyama can be used.
[0019]
The mounting jig for connecting to the bus bar from the power source may be made of titanium, and the number of joints may be determined according to the size of the anode chamber and the amount of current supplied, and may be welded to the anode chamber. The anode chamber is filled with an aqueous acid solution, and among them, an aqueous acid solution such as dilute sulfuric acid or phosphoric acid can be preferably used.
[0020]
[Action]
FIG. 2 shows a current potential curve of titanium metal in a copper sulfate plating solution and sulfuric acid, and a current potential curve of a titanium electrode coated with iridium oxide in dilute sulfuric acid. In the case of metallic titanium, even when the polarization is positively increased to 1.6 V, only a passivation current of 10 μA / cm 2 or less is observed. On the iridium oxide electrode, a current that reaches 500 mA / cm 2 accompanied by vigorous oxygen generation. Is recognized. Therefore, titanium metal has a very large overvoltage against oxygen generation due to electrolysis in an aqueous solution, and is passivated in the plating solution. Even when this is used as an anode chamber structural material, an anodic reaction occurs on this. However, the anodic reaction occurs only on the oxide film or the platinum film applied on the surface of the anode chamber structural material.
[0021]
Next, an example of the embodiment will be described. The present invention is not limited to this.
A titanium insoluble anode-fixed anode chamber having a cation exchange membrane having a height of 15 cm, a width of 5 cm, an anode chamber thickness of 2 cm, and an anode chamber capacity of 125 ml was prepared. (Height 15 cm,
The plating tank was filled with a bright copper plating solution, the anode chamber was filled with 5% sulfuric acid, and a Hull cell plate (
[0022]
[Table 1]
【The invention's effect】
When the insoluble anode for plating with the anode chamber integrated according to the present invention is used for plating, the oxygen generation reaction, which is the anode reaction, occurs only on the insoluble anode provided in the anode chamber, and the insoluble anode is placed in the conventional resin anode chamber. It has the same function as when it is inserted. In addition, it can be applied to many plating solutions such as copper sulfate plating and nickel plating, and the anode chamber and anode structure are compact and lightweight, so that workability can be improved and anolyte solution leakage can be effectively prevented. As a result, the economic benefits are great.
[Brief description of the drawings]
FIG. 1 is a diagram showing a structure of an insoluble anode for plating with an anode chamber integrated type.
FIG. 2 is a diagram showing current potential curves of titanium metal and iridium oxide.
[Explanation of symbols]
DESCRIPTION OF
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003063512A JP3928013B2 (en) | 2003-03-10 | 2003-03-10 | Insoluble anode for plating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003063512A JP3928013B2 (en) | 2003-03-10 | 2003-03-10 | Insoluble anode for plating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2004269977A true JP2004269977A (en) | 2004-09-30 |
| JP3928013B2 JP3928013B2 (en) | 2007-06-13 |
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| Application Number | Title | Priority Date | Filing Date |
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| JP2003063512A Expired - Lifetime JP3928013B2 (en) | 2003-03-10 | 2003-03-10 | Insoluble anode for plating |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007046092A (en) * | 2005-08-09 | 2007-02-22 | Hyomen Shori System:Kk | Apparatus and method for plating copper on sheet-shaped workpiece |
| JP2014510842A (en) * | 2011-04-14 | 2014-05-01 | ティーイーエル ネックス，インコーポレイテッド | Electrochemical deposition apparatus and replenishment apparatus |
| KR101415680B1 (en) | 2012-08-09 | 2014-07-04 | (주)포인텍 | Shield box and electrode plate for electrolysis plating apparatus |
| CN104562162A (en) * | 2013-10-21 | 2015-04-29 | 欣兴电子股份有限公司 | Diaphragm device |
| CN109735879A (en) * | 2019-03-11 | 2019-05-10 | 江阴安诺电极有限公司 | The preparation method of electrolytic copper foil anode plate |
-
2003
- 2003-03-10 JP JP2003063512A patent/JP3928013B2/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007046092A (en) * | 2005-08-09 | 2007-02-22 | Hyomen Shori System:Kk | Apparatus and method for plating copper on sheet-shaped workpiece |
| JP2014510842A (en) * | 2011-04-14 | 2014-05-01 | ティーイーエル ネックス，インコーポレイテッド | Electrochemical deposition apparatus and replenishment apparatus |
| KR101415680B1 (en) | 2012-08-09 | 2014-07-04 | (주)포인텍 | Shield box and electrode plate for electrolysis plating apparatus |
| CN104562162A (en) * | 2013-10-21 | 2015-04-29 | 欣兴电子股份有限公司 | Diaphragm device |
| CN104562162B (en) * | 2013-10-21 | 2018-03-23 | 欣兴电子股份有限公司 | Diaphragm apparatus |
| CN109735879A (en) * | 2019-03-11 | 2019-05-10 | 江阴安诺电极有限公司 | The preparation method of electrolytic copper foil anode plate |
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| JP3928013B2 (en) | 2007-06-13 |
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