JP3352081B2 - Printed circuit board copper plating equipment - Google Patents
Printed circuit board copper plating equipmentInfo
- Publication number
- JP3352081B2 JP3352081B2 JP2001025521A JP2001025521A JP3352081B2 JP 3352081 B2 JP3352081 B2 JP 3352081B2 JP 2001025521 A JP2001025521 A JP 2001025521A JP 2001025521 A JP2001025521 A JP 2001025521A JP 3352081 B2 JP3352081 B2 JP 3352081B2
- Authority
- JP
- Japan
- Prior art keywords
- printed circuit
- anode
- plating
- copper
- circuit board
- 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、プリント基板の銅
めっき装置に関し、特に電解槽内でめっき液を適正に流
動させつつ電解処理を施すことによって、プリント基板
の表面については勿論のこと、スルホール内についても
均一なめっきを可能ならしめようとするものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a copper plating apparatus for a printed circuit board, and more particularly, to an electroplating treatment while appropriately flowing a plating solution in an electrolytic bath, so that not only the surface of the printed circuit board but also the through hole can be formed. It is intended to make uniform plating possible even inside.
【０００２】[0002]
【従来の技術】プリント基板において、多層板のスルホ
ールめっきは、内層回路と表裏両面回路とを接続させる
ために行うもので、必要な部分に貫通孔すなわちスルホ
ールを形成し、そのスルホールの内面に銅めっきを施し
て両回路部分を接続するようにしている。通常のめっき
工程としては、最初にスルホール内の絶縁材料の表面を
パラジウム含有浴で活性処理し、ついで無電解銅めっき
により銅の薄膜を析出させて導電性を付与したのち、電
解処理により銅めっきを行うことが一般的である。2. Description of the Related Art In a printed circuit board, through-hole plating of a multilayer board is performed to connect an inner layer circuit and a circuit on both front and back sides. A through-hole, that is, a through-hole is formed at a necessary portion, and copper is formed on an inner surface of the through-hole. The two circuit parts are connected by plating. In the normal plating process, the surface of the insulating material in the through hole is first activated with a palladium-containing bath, then a thin film of copper is deposited by electroless copper plating to impart conductivity, and then the copper plating is performed by electrolytic treatment. It is common to do
【０００３】ここに、電解銅めっきは、エッチングを均
一に行うだけでなく、直径が 0.1mm以下のスルホール内
に均一にめっきを施す必要があることから、極めて厳し
い管理が要求されている。すなわち、直径：0.1 mm以下
のスルホール内に均一にめっき液が入り込むように付き
まわりが良好であること、銅めっきが適度の硬さを有す
ること、ヒビ割れ等が生じないことおよび光沢を有しヤ
ケ等が起こらないこと等である。従って、上記したよう
な種々の要求を満足させるために、通常、有機性添加剤
をめっき浴中に含有させている。Here, electrolytic copper plating requires not only uniform etching but also uniform plating in a through hole having a diameter of 0.1 mm or less, so that extremely strict control is required. That is, it has good adherence so that the plating solution can uniformly enter the through hole having a diameter of 0.1 mm or less, that the copper plating has an appropriate hardness, that it does not crack, and that it has luster . This is because burns do not occur. Therefore, in order to satisfy the various requirements as described above, an organic additive is usually contained in the plating bath.
【０００４】しかしながら、かような添加剤はいずれ
も、陽分極によって酸化分解し易いという問題があり、
またかかる添加剤の分解は陽極の平衡電位が高いほど生
じ易い。従って、従来の銅めっき法では、陽極として銅
または銅合金等の可溶性陽極を使用し、平衡電位を下げ
ることによって添加剤の分解防止を図っている。[0004] However, all of these additives have a problem that they are easily oxidatively decomposed by positive polarization.
The decomposition of the additive is more likely to occur as the equilibrium potential of the anode increases. Therefore, in the conventional copper plating method, a soluble anode such as copper or a copper alloy is used as the anode, and the decomposition of the additive is prevented by lowering the equilibrium potential.
【０００５】すなわち、陽極として銅や銅合金等の可溶
性電極を使用した場合の陽極（Cu→Cu2＋2e）の平衡電
位は 0.236Ｖと極めて低いのに対し、不溶性電極を使用
した場合の陽極反応は通常、酸素発生反応(2OH- ＋2e→
１/2O2＋H2O)を伴うため、その平衡電位は 1.229Ｖ（pH
＝０）となり、１Ｖ近く高くなる。That is, the anode (Cu → Cu 2 + 2e) has an extremely low equilibrium potential of 0.236 V when a soluble electrode such as copper or copper alloy is used as the anode, whereas the anode reaction when an insoluble electrode is used is used. usually, oxygen evolution reaction (2OH - + 2e →
1/2 O 2 + H 2 O), its equilibrium potential is 1.229 V (pH
= 0), which is nearly 1V higher.
【０００６】しかしながら、陽極が純銅の溶解電極の場
合は、このように低い電位においても添加剤の分解が生
じるため、常時補給して一定濃度に保持する必要があ
る。従って、可溶性電極の定めとして、めっき量と溶解
電極のアンバランスおよび電解浴中における銅イオンの
濃度変化を抑制するために、溶解電極を交換するなど電
解液や電極の煩雑な保守管理が必要という問題がある。However, when the anode is a pure copper dissolving electrode, the additive is decomposed even at such a low potential, so it is necessary to constantly supply and maintain a constant concentration. Therefore, in order to determine the soluble electrode, in order to suppress the imbalance between the plating amount and the dissolving electrode and the change in the concentration of copper ions in the electrolytic bath, it is necessary to perform complicated maintenance of the electrolytic solution and the electrode such as replacing the dissolving electrode. There's a problem.
【０００７】この点、通常の銅めっきでは、上記の問題
を解消するために、含リン銅ボールアノードをチタンバ
スケット（ケース）に入れ、電解浴中に吊るした状態で
電解を行うめっき法が採用されている。しかしながら、
上記のめっき法では、可溶性陽極の銅ボールの表面にブ
ラックフィルムが形成され、添加剤と銅陽極の接触度が
増大するため、添加剤の分解および銅の過剰溶出が抑制
できないだけでなく、スラッジが生成するなど、その保
守作業にも大きな問題を残していた。In this regard, in ordinary copper plating, in order to solve the above-mentioned problem, a plating method in which a phosphorus-containing copper ball anode is placed in a titanium basket (case) and electrolyzed while suspended in an electrolytic bath is adopted. Have been. However,
In the above plating method, a black film is formed on the surface of the copper ball of the soluble anode, and the degree of contact between the additive and the copper anode increases, so that not only decomposition of the additive and excessive elution of copper cannot be suppressed, but also sludge Generated a major problem in its maintenance work.
【０００８】ところで、上記の問題を克服する方法とし
て、陽極として不溶性白金族電極を使用すると共に、電
解液中の銅イオンは、電解槽とは別に設けた溶解槽から
供給する方法が提案されている。しかしながら、この方
法では、チタンケース陽極を使用した場合の問題は解消
されるものの、添加剤が分解し易いという問題は依然と
して残っており、また前記したスルホールめっきのよう
な特殊な条件下でも安定な添加剤はまだ開発されていな
いこともあって、この方法は工業的に採用されるまでに
は至っていない。As a method for overcoming the above-mentioned problem, a method has been proposed in which an insoluble platinum group electrode is used as an anode and copper ions in an electrolytic solution are supplied from a dissolving tank provided separately from the electrolytic tank. I have. However, in this method, although the problem in the case of using the titanium case anode is solved, the problem that the additive is easily decomposed still remains, and the method is stable even under special conditions such as the above-described through-hole plating. This method has not yet reached industrial adoption, as additives have not yet been developed.
【０００９】[0009]
【発明が解決しようとする課題】本発明は、上記したよ
うな現状に鑑み開発されたもので、スルホールめっきの
ような特殊なめっき処理においても均一めっきを実現し
て高品質の被めっき材を得ることができる、プリント基
板の銅めっき装置を提案することを目的とする。SUMMARY OF THE INVENTION The present invention has been developed in view of the above situation, and realizes uniform plating even in a special plating process such as through-hole plating to produce a high quality plated material. An object of the present invention is to propose a copper plating apparatus for a printed circuit board, which can be obtained.
【００１０】[0010]
【課題を解決するための手段】さて、発明者らは、上記
の目的を達成すべく鋭意研究を重ねた結果、均一めっき
を実現するためには、被めっき材であるプリント基板の
表面に常に新しいめっき液を供給すること、すなわちプ
リント基板の表面において常にめっき液を更新流動させ
ることが、所期した目的を達成する上で極めて有効であ
ることの知見を得た。また、添加剤の分解を防止するた
めには、陽極として、チタン系基材上に白金族金属酸化
物を被覆した不溶性電極を用いることが有効であること
も併せて見出した。さらに、電極に対する給電方式とし
ては、めっき液中で給電を行う液中給電式とすること
が、めっき効率を向上させる上で有効であることも見出
した。本発明は、上記の知見に立脚するものである。Means for Solving the Problems Now, the inventors of the present invention have conducted intensive studies to achieve the above-mentioned object. As a result, in order to realize uniform plating, the surface of a printed board, which is a material to be plated, is always provided. It has been found that supplying a new plating solution, that is, constantly renewing the plating solution on the surface of the printed circuit board is extremely effective in achieving the intended purpose. In addition, they have found that it is effective to use an insoluble electrode in which a platinum-based metal oxide is coated on a titanium-based substrate as an anode in order to prevent the decomposition of the additive. Furthermore, it has been found that an in-solution power supply system in which power is supplied in a plating solution is effective in improving plating efficiency. The present invention is based on the above findings.
【００１１】[0011]
【００１２】[0012]
【００１３】[0013]
【００１４】すなわち、本発明の要旨構成は次のとおり
である。 １ ．電解槽内に対向して配置した給電ブスバーにそれぞ
れ、不溶性電極からなる陽極とプリント基板用被めっき
材の陰極を掛止し、銅イオン、塩基性炭酸銅および有機
性添加剤を含有する電解液中にて電解処理を行うことに
よって、陰極であるプリント基板用被めっき材の表面お
よびスルホール内に銅めっきを施すめっき装置におい
て、陽極である不溶性電極板に多数の貫通孔を設けると
共に、該不溶性電極板の背面側において、該貫通孔に対
応する位置に噴射ノズルを配置しためっき液の噴流用受
槽箱を設置し、この噴流用受槽箱内にパイプを介して電
解槽中のめっき液を強制的に循環供給することにより、
不溶性電極板の貫通孔を通して、該不溶性電極板から被
めっき材であるプリント基板に向かう均一なめっき液の
噴流を形成させることを特徴とするプリント基板の銅め
っき装置。 That is, the gist of the present invention is as follows.
It is. 1 . An anode comprising an insoluble electrode and a cathode of a material to be plated for a printed circuit board are respectively hooked to a power supply bus bar opposed to the inside of the electrolytic cell, and an electrolytic solution containing copper ions, basic copper carbonate and an organic additive. In a plating apparatus for performing copper plating on the surface of a plated material for a printed board and a through hole in a plating apparatus by performing an electrolytic treatment in the inside, a large number of through holes are provided in an insoluble electrode plate as an anode, and the insoluble On the back side of the electrode plate, a plating liquid jet receiving tank box in which an injection nozzle is disposed at a position corresponding to the through hole is installed, and the plating liquid in the electrolytic cell is forcibly forced through a pipe in the jet liquid receiving box. Circulating supply
Through the through-holes of the insoluble electrode plates, copper plating apparatus of the printed circuit board, characterized in that to form a jet of uniform plating solution toward the printed circuit board is a material to be plated from the insoluble electrode plates.
【００１５】２．上記１において、噴射ノズルを、不溶性電極板に対
して固定配置としたことを特徴とするプリント基板の銅
めっき装置。 ３ ．上記１または２において、陽極が、チタン系基材上
に白金族金属酸化物を被覆した貫通孔付き不溶性白金族
電極であることを特徴とするプリント基板の銅めっき装
置。４．上記２または３において、噴射ノズルの材質が、チ
タン系基材上に白金族金属酸化物を被覆したものである
ことを特徴とするプリント基板の銅めっき装置。 [0015] 2. In the above item 1, the injection nozzle is connected to the insoluble electrode plate.
Printed circuit board characterized by fixed arrangement
Plating equipment. 3 . The copper plating apparatus for printed circuit boards according to 1 or 2, wherein the anode is an insoluble platinum group electrode with a through hole obtained by coating a platinum base metal oxide on a titanium-based substrate. 4. In the above item 2 or 3, the material of the injection nozzle is
A platinum-based metal oxide coated on a tan-based substrate
A copper plating apparatus for printed circuit boards.
【００１６】５．上記１〜４のいずれかにおいて、陽極
側の給電ブスバーをめっき液中に浸漬させ、給電方式を
液中給電式としたことを特徴とするプリント基板の銅め
っき装置。 5 . In any one of the above items 1 to 4, a copper plating apparatus for printed circuit boards, wherein the power supply bus bar on the anode side is immersed in a plating solution, and the power supply method is a submerged power supply type.
【００１７】６．上記１〜５のいずれかにおいて、陽極
と陰極の極間距離を調整するためのスライド機構を備え
ることを特徴とするプリント基板の銅めっき装置。 6 . In any one of the above items 1 to 5, a copper plating apparatus for a printed circuit board, comprising a slide mechanism for adjusting a distance between the anode and the cathode.
【００１８】[0018]
【発明の実施の形態】以下、本発明を具体的に説明す
る。図１に、本発明の実施に用いて好適な銅めっき装置
を模式で示し、図中番号１は電解槽、２は給電ブスバ
ー、３は陽極、４は陰極、そして５がめっき浴である。
また、６は陽極用給電ブスバー２-1の固定治具、７はモ
ータやシリンダーからなるを可とする陽極用給電ブスバ
ー２-1のスライド機構であり、このスライド機構７を駆
動することによって、陽極３を陽極用給電ブスバー２-1
ごと、陰極４に対し、自由に進退移動させることができ
る仕組みになっている。さらに、この例で、陽極用給電
ブスバー２-1の先端部はめっき浴中に浸漬されていて、
陽極３はこの陽極用給電ブスバー２-1とめっき浴中で接
続されている。すなわち、陽極３に対する給電はめっき
浴中で行われるいわゆる液中給電方式になっている。BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below. FIG. 1 schematically shows a copper plating apparatus suitable for carrying out the present invention. In the figure, reference numeral 1 denotes an electrolytic cell, 2 denotes a power supply bus bar, 3 denotes an anode, 4 denotes a cathode, and 5 denotes a plating bath.
Reference numeral 6 denotes a fixture for the anode power supply bus bar 2-1. Reference numeral 7 denotes a slide mechanism of the anode power supply bus bar 2-1 which can be formed of a motor or a cylinder. By driving the slide mechanism 7, Anode 3 is used to feed the anode busbar 2-1
And the cathode 4 can be freely moved forward and backward. Furthermore, in this example, the tip of the anode power supply bus bar 2-1 is immersed in a plating bath,
The anode 3 is connected to the anode power supply bus bar 2-1 in a plating bath. That is, the power supply to the anode 3 is a so-called submerged power supply method performed in a plating bath.
【００１９】また、陰極４は、被めっき材すなわち銅め
っきを施すべきプリント基板であり、この被めっき材４
は、合成樹脂上に銅箔を薄く被覆し、所定位置に多数の
スルホールが施工された複合板である。この被めっき材
４は、電気めっきに先立ち、それを円滑に行うために、
その表面に無電解銅めっきにより薄い銅めっき層を形成
しておくことが好ましい。また、かかる被めっき材は、
通常、 340mm×510mm 程度の板で、一度の操業で多数処
理できるように、上下、左右方向に並べ、一枚の大きな
平板状とし所定の治具で電解槽内に設置される。The cathode 4 is a material to be plated, that is, a printed board to be plated with copper.
Is a composite plate in which copper foil is thinly coated on a synthetic resin and a large number of through holes are formed at predetermined positions. Prior to electroplating, the material 4 to be plated is
It is preferable to form a thin copper plating layer on the surface by electroless copper plating. In addition, such a material to be plated
Usually, a plate of about 340 mm x 510 mm is arranged in the vertical and horizontal directions so that a large number of sheets can be processed in one operation, is formed into a single large flat plate, and is installed in the electrolytic cell with a predetermined jig.
【００２０】さて、本発明では、上記の被めっき材４の
表面に常時、新しいめっき液を供給するために、図２に
示すように、陽極板３に多数の貫通孔８を均等に設ける
と共に、その背面から被めっき材４に向けてめっき液を
多孔噴流として噴射し、被めっき材４の全面にめっき液
をソフトに衝突させる仕組みになっている。ここに、上
記したような多孔噴流を生じさせるために、本発明で
は、陽極板３に設けた多数の貫通孔８に対応する位置に
噴射ノズル９を配置しためっき液の噴流用受槽箱10を設
置し、この噴流用受槽箱内にパイプ11を介して電解槽中
のめっき液をポンプ（図示省略）によって強制的に循環
供給するものとする。In the present invention, in order to constantly supply a new plating solution to the surface of the material 4 to be plated, as shown in FIG. The plating solution is jetted from the back surface of the plating material 4 toward the plating material 4 as a porous jet, and the plating solution softly collides with the entire surface of the plating material 4. Here, in order to generate the above-described porous jet, in the present invention, a plating solution jet receiving tank box 10 in which jet nozzles 9 are arranged at positions corresponding to the large number of through holes 8 provided in the anode plate 3 is provided. The plating solution in the electrolytic cell is forcibly circulated and supplied by a pump (not shown) through the pipe 11 into the jet receiving tank box.
【００２１】かくして、噴流用受槽箱10に対し、パイプ
11を介してめっき液を強制的に供給すると、めっき液は
ノズル９から各貫通孔８を通って被めっき材４に向かっ
て均一に噴射され、被めっき材４に対しソフトに衝突す
ることになる。従って、被めっき材４の表面では、めっ
き液が常に更新される、換言すれば、銅イオンが常に補
給されている状態に維持される。[0021] Thus, the pipe 10 is
When the plating solution is forcibly supplied through 11, the plating solution is uniformly sprayed from the nozzle 9 through each through hole 8 toward the material to be plated 4 and collides with the material to be plated 4 softly. Become. Therefore, on the surface of the material 4 to be plated, the plating solution is constantly renewed, in other words, the state where the copper ions are constantly supplied is maintained.
【００２２】本発明では、上記のようにして、被めっき
材の表面に常に十分な銅イオンを送り込むことができ、
また同時に陰極側で発生するガスを効果的に除去するこ
とができるので、被処理材であるプリント基板の表面に
ついては勿論のこと、スルホール内についても均一なめ
っきを施すことができるのである。In the present invention, as described above, sufficient copper ions can always be sent to the surface of the material to be plated.
At the same time, since the gas generated on the cathode side can be effectively removed, uniform plating can be applied not only on the surface of the printed circuit board to be processed, but also in the through holes.
【００２３】なお、図２(c) では、陽極板３に開口した
貫通孔８に対して、噴射ノズル９を非接触状態で配置し
た場合について示したが、この点については図３に示す
ように、貫通孔８と噴射ノズル９を適切に位置合わせし
た状態で固定することもでき、このようにすることによ
り、噴射ノズル９からのめっき液の噴射速度をより正確
に制御することができる。さらに、この場合、噴射ノズ
ル９として、陽極板３と同様、チタン系基材上に白金族
金属酸化物を被覆したものを用いれば、この噴射ノズル
９も陽極として機能するので、めっき効率の一層の向上
を図ることができる。FIG. 2 (c) shows a case where the injection nozzle 9 is arranged in a non-contact state with respect to the through hole 8 opened in the anode plate 3, but this point is as shown in FIG. In addition, the through-hole 8 and the injection nozzle 9 can be fixed in a state where they are properly aligned, and thus, the injection speed of the plating solution from the injection nozzle 9 can be more accurately controlled. Further, in this case, as in the case of the anode plate 3, if a titanium-based substrate coated with a platinum group metal oxide is used as the injection nozzle 9, the injection nozzle 9 also functions as an anode, so that the plating efficiency is further improved. Can be improved.
【００２４】ここに、陽極に設ける貫通孔の直径は 1.0
〜20mm程度、またその個数は１m2当たり26〜46個程度と
することが好ましい。さらに、孔の配置は千鳥状とし、
その間隔は 100〜200 mmピッチ程度とするのがとりわけ
有利である。また、かかるかかる貫通孔を通して陰極側
に噴射するめっき液の噴射速度は、プリント基板に達し
た時の流速が0.05〜2.0m/s好ましくは 0.2〜0.5m/s程度
となる速度とすることが好適である。Here, the diameter of the through hole provided in the anode is 1.0
Preferably, the number is about 20 to about 20 mm, and the number thereof is about 26 to 46 per 1 m 2 . Furthermore, the arrangement of the holes is staggered,
It is particularly advantageous that the spacing is on the order of 100 to 200 mm pitch. Further, the spraying speed of the plating solution sprayed to the cathode side through such a through hole may be a speed at which the flow velocity when reaching the printed circuit board is 0.05 to 2.0 m / s, preferably about 0.2 to 0.5 m / s. It is suitable.
【００２５】さらに、本発明では、陽極３として、白金
族金属酸化物をチタン基体に被覆させた不溶性電極を用
いることが好ましい。というのは、この不溶性電極は、
可溶性電極に比べると、陽極電位（酸素発生電位）は高
いけれども、白金族金属を基材に被覆した電極や鉛電極
と比較すると陽極電位が 500〜700 mV低いために、添加
剤の分解を有効に防止することができるからである。こ
こに、白金族金属酸化物としては、例えば酸化パラジウ
ムや酸化イリジュウム、酸化ルテニウム等が有利に適合
する。なお、不溶性電極を使用した場合には、銅源中の
塩素濃度が問題となるが、上記した酸化パラジウム処理
の白金族金属酸化物は、塩素を分解して、かような弊害
を解消する作用もある。また、上記した酸化パラジウム
による塩素の分解を促進し、かつ酸化パラジウムの消耗
を軽減するために、陽極を取り囲んでイオン交換膜やア
ノード隔膜を設置することは一層有利である。Further, in the present invention, it is preferable to use, as the anode 3, an insoluble electrode in which a platinum base metal oxide is coated on a titanium substrate. Because this insoluble electrode is
Although the anode potential (oxygen generation potential) is higher than soluble electrodes, the decomposition of additives is effective because the anode potential is 500-700 mV lower than electrodes coated with platinum group metals or lead electrodes This is because it can be prevented. Here, as the platinum group metal oxide, for example, palladium oxide, iridium oxide, ruthenium oxide and the like are advantageously suited. Note that when an insoluble electrode is used, the chlorine concentration in the copper source becomes a problem, but the above-mentioned platinum group metal oxide of the palladium oxide treatment decomposes chlorine to eliminate such an adverse effect. There is also. In order to promote the decomposition of chlorine by palladium oxide and reduce the consumption of palladium oxide, it is more advantageous to provide an ion exchange membrane or an anode diaphragm surrounding the anode.
【００２６】さらに、陽極を電解槽内に設置するには、
図１に示したように、給電ブスバー２をめっき液中に浸
漬させ、この液中式ブスバーに陽極３を直接吊り下げ
て、給電方式を液中給電式とすることが、陽極−陰極間
の電流密度ひいてはめっき効率を向上せる上で好まし
い。Further, to install the anode in the electrolytic cell,
As shown in FIG. 1, the power supply bus bar 2 is immersed in a plating solution, and the anode 3 is directly hung from the submerged bus bar to make the power supply system a submerged power supply system. It is preferable from the viewpoint of improving the density and hence the plating efficiency.
【００２７】さらに、プリント基板用被めっき材の光沢
やレべリングバランスを均一にするためには、銅イオン
濃度、塩素イオン濃度、浴の導電性および陰極電流密度
等を適正に調整することが重要であるが、このうち陰極
電流密度を制御するには、陽極と陰極の極間距離を調整
することが好適である。従って、例えば、図１に示した
ように、陽極３を陰極４に対して自在に接近・離隔移動
できるようなスライド機構７を備えることが、レべリン
グバランスのより優れた均一めっきを行う上で有効であ
る。Furthermore, in order to make the luster and leveling balance of the material to be plated for a printed board uniform, it is necessary to appropriately adjust the copper ion concentration, the chloride ion concentration, the conductivity of the bath and the cathode current density. It is important to adjust the distance between the anode and the cathode to control the cathode current density. Therefore, for example, as shown in FIG. 1, the provision of the slide mechanism 7 that can freely move the anode 3 toward and away from the cathode 4 is necessary for performing uniform plating with more excellent leveling balance. Is effective in
【００２８】なお、本発明において、電解槽は、従来の
可溶性陽極を使用してきた槽を転用して何ら問題ない。
具体的には、可溶性陽極を不溶性陽極と交換し、また銅
イオンを外部から供給する手段を付加すれば良い。使用
する電解液は、銅イオン、塩基性炭酸銅および有機性添
加剤を含むものとする。また、光沢剤としては、有機性
光沢材を使用する。In the present invention, there is no problem in diverting a conventional electrolytic cell using a soluble anode.
Specifically, the soluble anode may be replaced with an insoluble anode, and a means for externally supplying copper ions may be added. The electrolyte used should contain copper ions, basic copper carbonate and organic additives. As the brightener, an organic brightener is used.
【００２９】また、電流濃度、印加電圧、電流密度およ
び液温度等の電解条件は、従来の可溶性陽極を使用した
場合と同じで良く、たとえば電流濃度は 0.5〜8.0 A/リッ
トル、印加電圧は 2.5〜6.0 Ｖ、陽極電流密度は１〜12 A
/dm2、陰極電流密度は 1.0〜8.0 A/dm2 、液温は20〜35
℃程度とすることが好ましい。The electrolysis conditions such as current concentration, applied voltage, current density and liquid temperature may be the same as those when a conventional soluble anode is used. For example, the current concentration is 0.5 to 8.0 A / liter and the applied voltage is 2.5 6.0V, anode current density 1-12A
/ dm 2 , cathode current density 1.0 ~ 8.0 A / dm 2 , liquid temperature 20 ~ 35
It is preferable that the temperature be about ° C.
【００３０】さらに、銅イオンの供給は、電解槽とは別
な槽（溶解槽）において、電解液に適宜銅化合物や塩基
性炭酸銅を溶解し、この溶解槽と電解槽とを循環させ
て、被めっき材にめっきされて減少した分の銅イオンを
補充し、電解槽の銅イオン濃度が一定に維持されるよう
にする。かくして、本発明によれば、表面およびスルホ
ール内に均一厚みの銅めっき層が形成された複合板を製
造することができ、後工程の洗浄処理ののち、プリント
基板製造工程に供給されるのである。Further, copper ions are supplied by appropriately dissolving a copper compound or basic copper carbonate in the electrolytic solution in a tank (dissolving tank) separate from the electrolytic tank, and circulating the dissolving tank and the electrolytic tank. In addition, the amount of copper ions reduced by plating on the material to be plated is replenished so that the concentration of copper ions in the electrolytic cell is kept constant. Thus, according to the present invention, it is possible to manufacture a composite board having a copper plating layer having a uniform thickness formed on the surface and in the through-hole, and after cleaning processing in a later step, is supplied to a printed circuit board manufacturing step. .
【００３１】なお、図１では、陰極である被めっき材４
の両面側に陽極３を配置して、被めっき材４の両面に同
時にめっきを施す場合について説明したが、本発明は、
これだけに限るものではなく、被めっき材４の片面のみ
にめっきする場合については勿論、図４に示すように、
二列で連続移動する被めっき材４に対して連続的にめっ
きを施す場合についても、同様にして適用することがで
きる。すなわち、図４は、陰極である被めっき材４を二
列とし、かつ紙面の垂直方向に連続して移動させる間に
銅めっきを施す場合について図解したものであるが、本
発明は、かような場合にも、好適に適用することができ
るのである。In FIG. 1, the material to be plated 4 which is a cathode is shown.
The case where the anodes 3 are arranged on both sides of the substrate and the both surfaces of the material to be plated 4 are plated simultaneously has been described.
However, the present invention is not limited to this. For example, when plating only on one side of the material 4 to be plated, as shown in FIG.
The same applies to the case where plating is continuously performed on the workpiece 4 that moves continuously in two rows. That is, FIG. 4 illustrates the case where the plated material 4 serving as the cathode is formed in two rows and copper plating is performed while continuously moving in the vertical direction of the paper surface. In such a case, it can be suitably applied.
【００３２】[0032]
【実施例】以下、本発明の実施例について説明するが、
この実施例は本発明を限定するものではない。図１に示
したような銅めっき装置を用い、工業的規模にて実装銅
めっきを行った。この際、電解槽の構成は次のとおりと
した。 １) 陰極 化学銅めっき処理後の積層板にスルホール穴開け施工を
施した、長さ：510 mm, 高さ：340 mm, 厚さ：1.6 mmの
基板寸法になるプリント基板計６枚を、板状専用治具
（カソードラック）により左右二列で一枚の平板状陰極
が形成されるようにセットし、カソードバーに吊り下げ
た。この時、基板の外周にエッジによるめっき厚異常が
発生することを避けるため、端部側にチャンネル状にＰ
ＶＣの枠を取り付け、窓枠状にダミー電極として銅板を
設置した。全陰極面積は2.1 m2であった。Hereinafter, embodiments of the present invention will be described.
This example does not limit the invention. Using a copper plating apparatus as shown in FIG. 1, mounting copper plating was performed on an industrial scale. At this time, the configuration of the electrolytic cell was as follows. 1) Cathode A total of six printed circuit boards with a board size of length: 510 mm, height: 340 mm, and thickness: 1.6 mm, were subjected to through-hole drilling on the laminated board after chemical copper plating. The plate was set so that one flat cathode was formed in two rows on the left and right sides by a jig (cathode rack) dedicated to the shape, and hung on a cathode bar. At this time, in order to avoid the occurrence of abnormal plating thickness due to the edge on the outer periphery of the substrate, a channel-like P
A VC frame was attached, and a copper plate was installed as a dummy electrode in a window frame shape. All cathode area was 2.1 m 2.
【００３３】２) 陽極 長さ：700 mm, 高さ：1100mm, 厚さ：３mmのチタン板基
材の表面に酸化イリジウム、酸化ルテニウム系のコーテ
ングを施して陽極とした。また、この陽極全体をイオン
交換膜とポリプロピレン膜（アノード隔膜）で覆った。
給電部として、裏面に液中給電用チタン治具をボルト締
め付けとし、アノードブスバーに吊り下げた。なお、か
かる陽極は、陰極の両面に対して給電するため二枚用意
した。2) Anode An iridium oxide-ruthenium oxide-based coating was applied to the surface of a titanium plate base material having a length of 700 mm, a height of 1100 mm and a thickness of 3 mm to form an anode. The entire anode was covered with an ion exchange membrane and a polypropylene membrane (anode diaphragm).
As a power supply unit, a titanium jig for submerged power supply was bolted to the back surface, and was suspended from the anode bus bar. In addition, two such anodes were prepared to supply power to both surfaces of the cathode.
【００３４】３) 電解槽 有効容積が長さ：1800mm×高さ：1500mm×幅：600 mm＝
1.62m3の電解槽を使用し、カソードロッカーは連続運動
機構とし、底部にはエアーバブリング用散気管を設置し
た。また、槽外のフィルターおよび銅イオン供給塔との
連続循環方式とした。3) Electrolytic tank Effective volume is length: 1800 mm x height: 1500 mm x width: 600 mm =
Using the electrolytic cell of 1.62M 3, cathode rocker is a continuous motion mechanism, the bottom was placed a sparge tube for air bubbling. Further, a continuous circulation system with a filter outside the tank and a copper ion supply tower was used.
【００３５】４) 銅イオン供給塔 上部に塩基性炭酸銅を連続的に投入できるホッパーを設
置した円筒と、その内部に撹拌装置を組み込み、積算電
流計に連動させて、落下用下部より塩基性炭酸銅を溶解
槽に導入し、溶解後の上澄み液をオーバーフローさせ、
フィルター通過後、電解槽に投入した。4) Copper ion supply tower A cylinder equipped with a hopper on the top of which a basic copper carbonate can be continuously charged, and a stirrer incorporated in the inside of the tower, and linked with an integrating ammeter to make a basic Copper carbonate is introduced into the dissolution tank, and the supernatant liquid after dissolution is allowed to overflow,
After passing through the filter, it was charged into the electrolytic cell.
【００３６】前処理後、無電解銅めっき処理により 0.5
μm 厚の銅めっきを施した基板を固定したカソード用治
具（ラック）を、電解槽の所定位置に垂直に吊り下げ、
エアバブリングを行いながらカソードロッカーを作動さ
せ、銅イオンを供給しつつ、電解処理を開始した。電
流：600 Ａで陰極電流密度が 2.5 A/dm2の条件で48分間
電解処理を行った。この時、塩基性炭酸銅の溶解速度
は、銅析出の電流効率を95％と仮定して算出すると、表
面１D/m2＝2.5(A)×0.22×48(min) ×95(%) ＝25μm と
なる。また、めっき液の噴射速度は、プリント基板に達
した時の流速が 0.3m/s 程度となるように調整した。光
沢剤としては、日本メルテックス株式会社製の不溶性電
極専用光沢材を2.2ml/minの割合で注入した。After the pretreatment, 0.5% by electroless copper plating.
A cathode jig (rack) to which a μm-thick copper-plated substrate is fixed is suspended vertically at a predetermined position in the electrolytic cell.
The cathode locker was operated while performing air bubbling, and the electrolytic treatment was started while supplying copper ions. The electrolytic treatment was performed at a current of 600 A and a cathode current density of 2.5 A / dm 2 for 48 minutes. At this time, the dissolution rate of the basic copper carbonate is calculated assuming that the current efficiency of copper deposition is 95%, and the surface 1D / m 2 = 2.5 (A) × 0.22 × 48 (min) × 95 (%) = 25 μm. The spray speed of the plating solution was adjusted so that the flow velocity upon reaching the printed circuit board was about 0.3 m / s. As a brightener, a brightener for insoluble electrodes manufactured by Nippon Meltex Co., Ltd. was injected at a rate of 2.2 ml / min.
【００３７】上記の電解処理に際して、めっき浴中の銅
イオンの濃度変化はほとんど見られなかった。電気めっ
き後の基板は、光沢ある正常な外観を示し、銅めっき厚
さは25μm でほぼ均一な厚さであった。また、かくして
得られた銅めっき板について、破壊検査により、スルホ
ール部の付きまわり性およびコーナークラックの発生の
有無について調べたが、問題は全くなかった。さらに、
引張強度、伸びおよび硬度も正常であり、またエッチン
グ性、はんだ濡れ性、熱サイクルおよび熱干渉試験につ
いても何ら異常がなく、めっき品質はプリント基板とし
て十分満足できるものであった。During the above-mentioned electrolytic treatment, almost no change in the concentration of copper ions in the plating bath was observed. The substrate after electroplating exhibited a glossy and normal appearance, and the copper plating thickness was 25 μm and was almost uniform. Further, the copper plated sheet thus obtained was examined by a destructive inspection for the throwing power of the through-hole portion and the occurrence of corner cracks, but there was no problem at all. further,
The tensile strength, elongation and hardness were normal, and there was no abnormality in the etching property, solder wettability, thermal cycle and thermal interference test, and the plating quality was sufficiently satisfactory as a printed circuit board.
【００３８】[0038]
【発明の効果】かくして、本発明によれば、プリント基
板のスルホールめっきのような特殊なめっき処理におい
ても均一で高品質の銅めっき材を得ることができ、プリ
ント基板のめっき方法として偉功を奏する。As described above, according to the present invention, a uniform and high-quality copper plating material can be obtained even in a special plating process such as through-hole plating of a printed circuit board, and it is very effective as a plating method for a printed circuit board. .
【図１】 本発明に従う銅めっき装置の模式図である。FIG. 1 is a schematic view of a copper plating apparatus according to the present invention.
【図２】 めっき液の多孔噴流を発生させる装置の説明
図である。FIG. 2 is an explanatory view of an apparatus for generating a porous jet of a plating solution.
【図３】 貫通孔に対して噴射ノズルを固定式とした場
合の説明図である。FIG. 3 is an explanatory diagram in a case where an injection nozzle is fixed to a through hole.
【図４】 本発明に従う銅めっき装置の別例の模式図で
ある。FIG. 4 is a schematic view of another example of the copper plating apparatus according to the present invention.
１ めっき槽 ２ 給電ブスバー ３ 陽極 ４ 陰極（被めっき材） ５ めっき浴 ６ 陽極用給電ブスバーの固定治具 ７ 陽極用給電ブスバーのスライド機構 ８ 貫通孔 ９ めっき液の噴射ノズル 10 噴流用受槽箱 11 めっき液供給用のパイプ DESCRIPTION OF SYMBOLS 1 Plating tank 2 Power supply bus bar 3 Anode 4 Cathode (material to be plated) 5 Plating bath 6 Fixing jig of power supply bus bar for anode 7 Slide mechanism of power supply bus bar for anode 8 Through hole 9 Injection nozzle for plating solution 10 Receiving tank box for jet flow 11 Pipe for supplying plating solution
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平４−362199（ＪＰ，Ａ) 特開 平５−13956（ＪＰ，Ａ) 特開 平10−121297（ＪＰ，Ａ) 特開 平11−61498（ＪＰ，Ａ) 特開 昭56−122198（ＪＰ，Ａ) 特開 昭59−112693（ＪＰ，Ａ) 特公 平６−73393（ＪＰ，Ｂ２) 特公 平７−48587（ＪＰ，Ｂ２) 特公 昭45−33828（ＪＰ，Ｂ１) 特公 昭58−16625（ＪＰ，Ｂ１) 特公 昭58−21840（ＪＰ，Ｂ１) 特許2510422（ＪＰ，Ｂ２) (58)調査した分野(Int.Cl.7，ＤＢ名) C25D 7/00 C25D 5/08 C25D 17/10 C25D 21/00 H05K 3/18 ──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-4-362199 (JP, A) JP-A-5-13956 (JP, A) JP-A-10-121297 (JP, A) JP-A-11- JP 61498 (JP, A) JP-A-56-122198 (JP, A) JP-A-59-112693 (JP, A) JP 6-73393 (JP, B2) JP 7-48587 (JP, B2) JP-B-45-33828 (JP, B1) JP-B-58-16625 (JP, B1) JP-B-58-21840 (JP, B1) Patent 2510422 (JP, B2) (58) Fields investigated (Int. Cl) . 7, DB name) C25D 7/00 C25D 5/08 C25D 17/10 C25D 21/00 H05K 3/18
Claims (6)
ーにそれぞれ、不溶性電極からなる陽極とプリント基板
用被めっき材の陰極を掛止し、銅イオン、塩基性炭酸銅
および有機性添加剤を含有する電解液中にて電解処理を
行うことによって、陰極であるプリント基板用被めっき
材の表面およびスルホール内に銅めっきを施すめっき装
置において、 陽極である不溶性電極板に多数の貫通孔を設けると共
に、該不溶性電極板の背面側において、該貫通孔に対応
する位置に噴射ノズルを配置しためっき液の噴流用受槽
箱を設置し、この噴流用受槽箱内にパイプを介して電解
槽中のめっき液を強制的に循環供給することにより、不
溶性電極板の貫通孔を通して、該不溶性電極板から被め
っき材であるプリント基板に向かう均一なめっき液の噴
流を形成させることを特徴とするプリント基板の銅めっ
き装置。An anode composed of an insoluble electrode and a cathode of a material to be plated for a printed circuit board are respectively hooked on a power supply bus bar opposed to the inside of an electrolytic cell, and copper ions, basic copper carbonate, and an organic additive are provided. In a plating apparatus that performs copper plating on the surface of the material to be plated for a printed board and a through hole by performing an electrolytic treatment in an electrolytic solution containing, a large number of through holes are formed in an insoluble electrode plate as an anode. At the same time, on the back side of the insoluble electrode plate, a plating solution jet tank having a jet nozzle disposed at a position corresponding to the through-hole is installed. by forcibly circulated and supplied to the plating solution, not
Through the through-hole of the soluble electrode plate, a copper plating apparatus of the printed circuit board, characterized in that to form a jet of uniform plating solution toward the printed circuit board is a material to be plated from the insoluble electrode plates.
性電極板に対して固定配置としたことを特徴とするプリ
ント基板の銅めっき装置。 2. The injection nozzle according to claim 1, wherein
Characterized in that it is fixed to the conductive electrode plate.
Copper plating equipment for printed circuit boards.
タン系基材上に白金族金属酸化物を被覆した貫通孔付き
不溶性白金族電極であることを特徴とするプリント基板
の銅めっき装置。3. The printed circuit board according to claim 1, wherein the anode is a through-hole insoluble platinum-group electrode with a platinum-based metal oxide coated on a titanium-based substrate. Copper plating equipment.
の材質が、チタン系基材上に白金族金属酸化物を被覆し
たものであることを特徴とするプリント基板の銅めっき
装置。 4. An injection nozzle according to claim 2, wherein
Is made of a platinum-based metal oxide coated on a titanium-based substrate.
Copper plating on printed circuit boards characterized by the following:
apparatus.
側の給電ブスバーをめっき液中に浸漬させ、給電方式を
液中給電式としたことを特徴とするプリント基板の銅め
っき装置。5. The copper plating apparatus for a printed circuit board according to claim 1, wherein the power supply bus bar on the anode side is immersed in a plating solution, and the power supply system is a submerged power supply system.
と陰極の極間距離を調整するためのスライド機構を備え
ることを特徴とするプリント基板の銅めっき装置。6. A copper plating apparatus for a printed circuit board according to claim 1, further comprising a slide mechanism for adjusting a distance between the anode and the cathode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001025521A JP3352081B2 (en) | 2001-02-01 | 2001-02-01 | Printed circuit board copper plating equipment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001025521A JP3352081B2 (en) | 2001-02-01 | 2001-02-01 | Printed circuit board copper plating equipment |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2002226993A JP2002226993A (en) | 2002-08-14 |
| JP3352081B2 true JP3352081B2 (en) | 2002-12-03 |
Family
ID=18890495
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001025521A Expired - Lifetime JP3352081B2 (en) | 2001-02-01 | 2001-02-01 | Printed circuit board copper plating equipment |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3352081B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20230066314A (en) * | 2021-11-05 | 2023-05-15 | 가부시키가이샤 에바라 세이사꾸쇼 | Plating device and manufacturing method of the plating device |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007169700A (en) * | 2005-12-21 | 2007-07-05 | Victor Co Of Japan Ltd | Copper electroplating method using insoluble anode |
| DE102007026633B4 (en) * | 2007-06-06 | 2009-04-02 | Atotech Deutschland Gmbh | Apparatus and method for the electrolytic treatment of plate-shaped goods |
| JP2009249659A (en) * | 2008-04-02 | 2009-10-29 | Nippon Mektron Ltd | Electroplating device and electroplating method |
| KR20100068737A (en) * | 2008-12-15 | 2010-06-24 | 삼성전기주식회사 | Shield plate and electroplating apparatus |
| KR101880601B1 (en) * | 2016-12-16 | 2018-08-17 | (주)포인텍 | Anode moving type electrolysis plating apparatus |
| JP6859150B2 (en) * | 2017-03-22 | 2021-04-14 | 株式会社荏原製作所 | How to determine the plating equipment and plating tank configuration |
| CN110753763A (en) | 2017-09-20 | 2020-02-04 | Almex Pe 株式会社 | Electrolytic processing assembly and surface processing device using same |
| KR102443193B1 (en) * | 2018-01-29 | 2022-09-13 | 어플라이드 머티어리얼스, 인코포레이티드 | Systems and Methods for Copper(I) Suppression in Electrochemical Vapor Deposition |
| KR102410794B1 (en) * | 2020-04-03 | 2022-06-20 | (주)포인텍 | High-quality plating apparatus |
| KR102410787B1 (en) * | 2020-04-03 | 2022-06-20 | (주)포인텍 | Electrolysis plating apparatus having moving type vertical anode |
| CN115058756A (en) * | 2022-06-08 | 2022-09-16 | 江阴微弧金属科技有限公司 | Energy-saving type double-flying-target oxidation tank suitable for oxidation process of 3C electronic products |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2510422B2 (en) | 1988-05-25 | 1996-06-26 | ペルメレック電極 株式会社 | Copper plating method for printed circuit boards |
-
2001
- 2001-02-01 JP JP2001025521A patent/JP3352081B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2510422B2 (en) | 1988-05-25 | 1996-06-26 | ペルメレック電極 株式会社 | Copper plating method for printed circuit boards |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20230066314A (en) * | 2021-11-05 | 2023-05-15 | 가부시키가이샤 에바라 세이사꾸쇼 | Plating device and manufacturing method of the plating device |
| KR102616448B1 (en) | 2021-11-05 | 2023-12-27 | 가부시키가이샤 에바라 세이사꾸쇼 | Plating device and method of manufacturing the plating device |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2002226993A (en) | 2002-08-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5417112B2 (en) | Method for electrolytic deposition of metal layers | |
| JP4221064B2 (en) | Electrodeposition method of copper layer | |
| US8801912B2 (en) | Continuous copper electroplating method | |
| US6835294B2 (en) | Electrolytic copper plating method | |
| US5049221A (en) | Process for producing a copper-clad laminate | |
| JP3352081B2 (en) | Printed circuit board copper plating equipment | |
| JPH08507106A (en) | Method and apparatus for electrolytic deposition of metal layers | |
| JP2005320631A (en) | Improved plating method | |
| US20060151328A1 (en) | Method of electroplating a workpiece having high-aspect ratio holes | |
| JP2006316328A (en) | Method for manufacturing two-layer flexible copper-clad laminate | |
| JPH0452296A (en) | Copper plating method | |
| US3769179A (en) | Copper plating process for printed circuits | |
| TWI683931B (en) | Anode for electrolytic copper plating and electrolytic copper plating device using the same | |
| JP2510422B2 (en) | Copper plating method for printed circuit boards | |
| JPH04362199A (en) | Electroplating device | |
| KR100558129B1 (en) | Method and apparatus for regulating the concentration of substances in electrolytes | |
| EP2606163B1 (en) | METHOD FOR THE ADJUSTMENT OF NICKEL CONTENT AND pH OF A PLATING SOLUTION | |
| KR100426159B1 (en) | Electrodeposition method of metal film and apparatus therefor | |
| US6527934B1 (en) | Method for electrolytic deposition of copper | |
| JPH0673393B2 (en) | Copper plating method for printed circuit boards | |
| JPH04284691A (en) | Electrically plating method for printed circuit board | |
| CN1643186A (en) | Conveyorized plating line and method for electrolytically metal plating a workpiece | |
| KR19980014624A (en) | Spray electroplating method | |
| JPH1060684A (en) | Spray electroplating method | |
| Niksa et al. | The Use of Insoluble, Mixed Metal Oxide Coated Titanium Anodes to Improve Quality and Decrease Plating Times for Circuit Boards |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| TRDD | Decision of grant or rejection written | ||
| R150 | Certificate of patent or registration of utility model |
Ref document number: 3352081 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20070920 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080920 Year of fee payment: 6 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090920 Year of fee payment: 7 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100920 Year of fee payment: 8 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100920 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110920 Year of fee payment: 9 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120920 Year of fee payment: 10 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130920 Year of fee payment: 11 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| EXPY | Cancellation because of completion of term |