JP2000345381A - Electrolytic copper foil manufacturing method, electrolytic copper foil, copper-covered laminate substrate, and printed circuit board - Google Patents
Electrolytic copper foil manufacturing method, electrolytic copper foil, copper-covered laminate substrate, and printed circuit boardInfo
- Publication number
- JP2000345381A JP2000345381A JP11161644A JP16164499A JP2000345381A JP 2000345381 A JP2000345381 A JP 2000345381A JP 11161644 A JP11161644 A JP 11161644A JP 16164499 A JP16164499 A JP 16164499A JP 2000345381 A JP2000345381 A JP 2000345381A
- Authority
- JP
- Japan
- Prior art keywords
- copper foil
- electrolytic
- electrolytic solution
- electrolytic copper
- copper
- 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
Abstract
Description
【０００１】[0001]
【発明の技術分野】本発明は、電解銅箔の製造方法に関
する。さらに詳しくは、電解銅箔製造時に、電解液中に
含まれるＰｂイオンによるＰｂ微粉の析出を抑制する電
解銅箔の製造方法、および該方法で得られた電解銅箔、
該電解銅箔を用いて製造された銅張り積層板および該電
解銅箔を用いて製造されたプリント配線板に関する。The present invention relates to a method for producing an electrolytic copper foil. More specifically, during the production of an electrolytic copper foil, a method for producing an electrolytic copper foil that suppresses the precipitation of Pb fine powder due to Pb ions contained in an electrolytic solution, and an electrolytic copper foil obtained by the method,
The present invention relates to a copper-clad laminate manufactured using the electrolytic copper foil and a printed wiring board manufactured using the electrolytic copper foil.
【０００２】[0002]
【発明の技術的背景】従来、電解銅箔は、Ｔｉ製の円筒
型ドラムを陰極とし、不溶性の陽極と対峙させて、硫酸
銅などの電解液の電解を行い、円筒型ドラム表面に銅を
電着させることによって連続的に銅箔を製造している。
特に、近年、電子機器の小型化、高密度化されるのに伴
い、使用されるプリント配線板の回路幅、回路間隔は年
々細線化しており、それにともなって使用される銅箔
も、表面の粗度が低いものが要望されている。BACKGROUND OF THE INVENTION Conventionally, an electrolytic copper foil is formed by using a cylindrical drum made of Ti as a cathode, facing an insoluble anode, and electrolyzing an electrolytic solution such as copper sulfate to deposit copper on the surface of the cylindrical drum. Copper foil is manufactured continuously by electrodeposition.
In particular, in recent years, as electronic devices have become smaller and more dense, circuit widths and circuit intervals of printed wiring boards used have become thinner year by year. What has low roughness is demanded.
【０００３】このような表面の粗度が低い銅箔を製造す
る際には、通常、塩素濃度が０．１〜５．０ｍｇ／Ｌの
硫酸銅電解液浴が使用されている。しかしながら、この
ような低塩素濃度の電解液を使用して、電解銅箔を製造
する際には、電解液中に不純物としてＰｂが含まれてい
ると、電解時にデンドライド状のＰｂ微粉が発生し、電
解銅箔中に共析することがあった。Ｐｂ微粉は大きさが
１〜５０μｍの範囲にあり、特に５〜２０μｍの範囲に
あり、電解後の銅箔表面近くに多く共析している。な
お、「共析」とは浮遊している微粉が、電解によって析
出した銅中に取り込まれることをいう。[0003] In producing such a copper foil having a low surface roughness, a copper sulfate electrolyte bath having a chlorine concentration of 0.1 to 5.0 mg / L is usually used. However, when producing an electrolytic copper foil using such an electrolytic solution having a low chlorine concentration, if Pb is contained as an impurity in the electrolytic solution, fine dendritic Pb powder is generated during electrolysis. And eutectoid in the electrolytic copper foil. The Pb fine powder has a size in the range of 1 to 50 µm, particularly in the range of 5 to 20 µm, and is eutectoid near the copper foil surface after electrolysis. Note that “eutectoid” means that floating fine powder is taken into copper precipitated by electrolysis.
【０００４】このようなＰｂ微粉が含まれた銅箔を使用
して、プリント配線板にたとえば線幅５０μｍ／線間５
０μｍのファイン回路を形成すると、Ｐｂ微粉によっ
て、回路が断線したり、回路の短絡が生じるなどの問題
を引き起こすことがあった。しかも得られた電解銅箔
は、プリント配線板に必要な特性を具備させるための表
面処理が施され、たとえば限界電流密度以上の電流で電
解銅箔表面に粗化処理を施した後、ＺnやＮiメッキ、ク
ロメート処理、シランカップリング剤処理などの防錆処
理が施される。このため、銅箔中にＰｂ微粉があって
も、検出することが極めて難しいという問題があった。[0004] Using a copper foil containing such Pb fine powder, a printed wiring board has, for example, a line width of 50 μm / line gap of 5 μm.
When a fine circuit of 0 μm is formed, Pb fine powder may cause problems such as disconnection of the circuit or short circuit of the circuit. Moreover, the obtained electrolytic copper foil is subjected to a surface treatment for providing the required characteristics to the printed wiring board. For example, after performing a roughening treatment on the surface of the electrolytic copper foil with a current higher than the limit current density, Zn or Rust prevention treatment such as Ni plating, chromate treatment, and silane coupling agent treatment is performed. For this reason, there is a problem that even if there is Pb fine powder in the copper foil, it is extremely difficult to detect it.
【０００５】なお、特開平6-146051号公報、特開平6-14
6052号公報には、鉛合金を陽極として使用して金属箔の
電析を行う際に、電解液に炭酸ストロンチウムを添加す
ることによって、硫酸鉛などの鉛成分を共沈させて濾過
して除去することが記載されている。しかしながら、こ
の特開平6-146051号公報、特開平6-146052号公報には、
炭酸ストロンチウムを添加することは、電解液中のＰｂ
濃度が高い場合に有効な方法であるものの、電解液中の
Ｐｂ濃度が低くなると、鉛の共沈物を濾過できず、Ｐｂ
イオンは電解銅箔中に取り込まれてしまうと記載されて
おり、特に、本発明のように低塩素濃度の電解液におけ
る鉛の除去方法について何ら開示されていない。Incidentally, Japanese Patent Application Laid-Open Nos. Hei 6-46051 and 6-14
No. 6052 discloses that when depositing a metal foil using a lead alloy as an anode, by adding strontium carbonate to the electrolyte, a lead component such as lead sulfate is coprecipitated and removed by filtration. Is described. However, JP-A-6-46051 and JP-A-6-46052 disclose,
The addition of strontium carbonate can reduce the amount of Pb in the electrolyte.
Although this method is effective when the concentration is high, when the Pb concentration in the electrolytic solution is low, the lead co-precipitate cannot be filtered, and Pb
It is described that ions are incorporated into the electrolytic copper foil, and in particular, there is no disclosure of a method for removing lead from an electrolytic solution having a low chlorine concentration as in the present invention.
【０００６】このような事情を鑑み、本発明者らは鋭意
検討した結果、電解液として、Ｃｌイオンを０．１〜
５．０ｍｇ／Ｌの量で含むものを使用する際に、電解液
に、炭酸ストロンチウムを、電解液中に含まれるＰｂイ
オンの量に対して８〜１００(g/Pb-g)の量で添加するこ
とによって、電解液中に含まれている不純物中のＰｂイ
オンを、極めて少量にまで、効果的に減らすことがで
き、これにより、電解時にＰｂ微粉の共析が少ない電解
銅箔が得られることを見出し、本発明を完成するに至っ
た。In view of such circumstances, the inventors of the present invention have conducted intensive studies and as a result, have found that Cl ions can be used as an electrolytic solution in an amount of 0.1 to 0.1%.
When using an electrolyte containing 5.0 mg / L, strontium carbonate is used in the electrolyte in an amount of 8 to 100 (g / Pb-g) based on the amount of Pb ions contained in the electrolyte. By the addition, Pb ions in impurities contained in the electrolytic solution can be effectively reduced to a very small amount, whereby an electrolytic copper foil with less eutectoid Pb fine powder during electrolysis can be obtained. And found that the present invention was completed.
【０００７】[0007]
【発明の目的】本発明は上記のような従来技術に伴う問
題点を解決するためのものであって、低塩素イオン濃度
電解液を用いて電解銅箔を製造する際に、電解銅箔中に
共析するＰｂ微粉を効果的に低減しうる電解銅箔の製造
方法、および該方法によって得られた電解銅箔、さらに
該電解銅箔から製造された銅張り積層板およびプリント
配線板を提供することを目的としている。SUMMARY OF THE INVENTION The object of the present invention is to solve the problems associated with the prior art as described above, and when producing an electrolytic copper foil using a low chloride ion concentration electrolytic solution, the electrolytic copper foil Provided is a method for producing an electrolytic copper foil capable of effectively reducing Pb fine powder that is eutectoid to copper, an electrolytic copper foil obtained by the method, and a copper-clad laminate and a printed wiring board produced from the electrolytic copper foil. It is intended to be.
【０００８】[0008]
【発明の概要】本発明に係る電解銅箔の製造方法は、硫
酸銅を含む電解液を用いて、電解銅箔を製造するに際し
て、電解液として、Ｃｌイオンを０．１〜５．０ｍｇ／
Ｌの量で含むものを使用し、かつ、電解液に、炭酸スト
ロンチウムを、電解液中に含まれるＰｂイオンの量に対
して８〜１００(g/Pb-g)の量で添加し、電解液中に含ま
れるＰｂイオンを除去して電解銅箔を形成することを特
徴としている。SUMMARY OF THE INVENTION According to the method for producing an electrolytic copper foil according to the present invention, when producing an electrolytic copper foil using an electrolytic solution containing copper sulfate, 0.1 to 5.0 mg / Cl is used as an electrolytic solution.
L, and adding strontium carbonate to the electrolytic solution in an amount of 8 to 100 (g / Pb-g) with respect to the amount of Pb ions contained in the electrolytic solution. It is characterized in that Pb ions contained in the solution are removed to form an electrolytic copper foil.
【０００９】また、本発明に係る電解銅箔は、上記方法
によって製造されるものであり、Ｐｂ微粉を含んでいな
い。さらにまた、本発明に係る銅張り積層板およびプリ
ント配線板はこのような電解銅箔を用いて製造されるも
のである。The electrolytic copper foil according to the present invention is produced by the above method and does not contain Pb fine powder. Furthermore, the copper-clad laminate and the printed wiring board according to the present invention are manufactured using such electrolytic copper foil.
【００１０】[0010]
【発明の具体的説明】以下、本発明に係る電解銅箔の製
造方法、電解銅箔、銅張り積層板およびプリント配線板
について具体的に説明する。 ［電解銅箔の製造方法］本発明に係る電解銅箔の製造方
法は、硫酸銅を含む電解液を用いて、電解銅箔を製造す
るに際して、電解液として、Ｃｌイオンを０．１〜５．
０ｍｇ／Ｌの量で含むものを使用し、かつ、電解液に、
炭酸ストロンチウムを、電解液中に含まれるＰｂイオン
の量に対して８〜１００(g/Pb-g)の量で添加し、電解液
中に含まれるＰｂイオンを除去して電解銅箔を形成する
ことを特徴とするものである。DETAILED DESCRIPTION OF THE INVENTION Hereinafter, a method for producing an electrolytic copper foil, an electrolytic copper foil, a copper-clad laminate, and a printed wiring board according to the present invention will be specifically described. [Method of Manufacturing Electrodeposited Copper Foil] In the method of manufacturing an electrolytic copper foil according to the present invention, when an electrolytic copper foil is manufactured using an electrolytic solution containing copper sulfate, Cl ions are used as an electrolytic solution in an amount of 0.1 to 5%. .
Use the one containing 0 mg / L, and in the electrolyte,
Strontium carbonate is added in an amount of 8 to 100 (g / Pb-g) based on the amount of Pb ions contained in the electrolytic solution, and the Pb ions contained in the electrolytic solution are removed to form an electrolytic copper foil. It is characterized by doing.
【００１１】このような製造方法では、たとえば、図１
に示されるような製造装置が使用される。図１は本発明
に係る電解銅箔の製造方法で使用される製造装置の一例
を示すものである。参照数字１は陰極ドラムが回転可能
に配置された電解槽、２は尾液槽、３は銅原料溶解槽、
４は補給液貯槽、５は添加剤槽、６は濾過機、７は巻き
取りドラム、８は銅原料である。また図中、Ｐは定量ポ
ンプを示している。In such a manufacturing method, for example, FIG.
A manufacturing apparatus as shown in FIG. FIG. 1 shows an example of a manufacturing apparatus used in the method for manufacturing an electrolytic copper foil according to the present invention. Reference numeral 1 is an electrolytic cell in which a cathode drum is rotatably arranged, 2 is a tail liquid tank, 3 is a copper raw material dissolving tank,
4 is a replenisher tank, 5 is an additive tank, 6 is a filter, 7 is a take-up drum, and 8 is a copper raw material. In the figure, P indicates a metering pump.
【００１２】図１に示す製造装置では、電解液が供給さ
れる電解槽中１で、円筒状の陰極ドラム（図１中、１
a）と、該陰極ドラムに沿ってほぼ一定の距離に保たれ
て配置される電解用陽極（図１中、１b）との間に、硫
酸銅を含む電解液を流し、銅が電析するような量の電圧
を印加し、回転する陰極ドラム周囲に銅を電着させるよ
うになっている。所定の厚さになった銅箔は、連続的に
剥離され、巻き取りロール７によって巻き取られる。陰
極ドラム１aおよび電解用陽極１bの間に供給され、電析
により銅イオンが減少した電解液（本明細書では尾液と
いうこともある）は、オーバーフローして連続的に尾液
槽２に戻される。尾液は、尾液槽２から銅原料溶解槽３
に送液される。該溶解槽３内では、銅原料８から供給さ
れた銅原料と尾液とを接触させて銅を溶解し、銅イオン
の補充が行われる。銅溶解が終了した電解液は補給液貯
槽４に送液される。補給液貯槽４には炭酸ストロンチウ
ムが添加剤槽５より添加されたのち、濾過機６によっ
て、生成した液中の固形物（沈殿物）を除去したのち、
電解液の補給液として、電解槽１に供給される。In the manufacturing apparatus shown in FIG. 1, a cylindrical cathode drum (1 in FIG. 1) is provided in an electrolytic cell 1 to which an electrolytic solution is supplied.
An electrolytic solution containing copper sulfate flows between a) and an anode for electrolysis (1b in FIG. 1) which is arranged at a substantially constant distance along the cathode drum, and copper is deposited. By applying such a voltage, copper is electrodeposited around the rotating cathode drum. The copper foil having a predetermined thickness is continuously peeled off and wound up by a winding roll 7. The electrolytic solution (also referred to as a tail solution in this specification) supplied between the cathode drum 1a and the anode for electrolysis 1b and having reduced copper ions by electrodeposition overflows and is continuously returned to the tail solution tank 2. It is. The tail liquid is supplied from the tail liquid tank 2 to the copper raw material dissolving tank 3.
Liquid. In the dissolving tank 3, the copper raw material supplied from the copper raw material 8 is brought into contact with the tail liquid to dissolve the copper and replenish the copper ions. The electrolytic solution in which copper dissolution has been completed is sent to the replenishing solution storage tank 4. After strontium carbonate is added from the additive tank 5 to the replenishing liquid storage tank 4, solids (sediment) in the generated liquid are removed by the filter 6.
The electrolytic solution is supplied to the electrolytic cell 1 as a replenisher.
【００１３】本発明に係る製造方法で得られる電解銅箔
は、通常、陰極ドラム面側がシャイニー面（光沢面）と
なり、電着面側がマット面（粗面）となる。本発明で使
用される電解液は、塩素イオン濃度が０．１〜５．０ｍ
ｇ／Ｌの範囲にあり、かつ硫酸銅を含み、電解銅箔製造
用に使用されるものであれば、特に制限なく使用するこ
とができる。The electrolytic copper foil obtained by the production method according to the present invention usually has a shiny surface (glossy surface) on the cathode drum surface side and a matte surface (rough surface) on the electrodeposition surface side. The electrolyte used in the present invention has a chloride ion concentration of 0.1 to 5.0 m.
It can be used without particular limitation as long as it is in the range of g / L, contains copper sulfate, and is used for producing an electrolytic copper foil.
【００１４】通常、電解液中の銅濃度は、３０〜１００
g/Lの範囲にあり、硫酸濃度が５０〜３００g/Lの範囲に
あることが好ましい。上記のような電解液には、通常１
〜３０ｍｇ／Ｌ程度のＰｂ成分（主にＰｂイオン）が不
純物として含まれている。このＰｂ成分は、次に示すよ
うなところから混入してくる。たとえば、銅原料として
溶解する銅くず原料には不純物としてＰｂ成分が多く含
まれており、この他に同じく銅原料の硫酸銅中にも含ま
れる。また、銅箔製造装置の配管や各槽の内張りなどに
含まれているＰｂが溶出することによっても、電解液中
に含まれるようになる。Usually, the concentration of copper in the electrolyte is 30 to 100.
g / L, and the sulfuric acid concentration is preferably in the range of 50 to 300 g / L. The above-mentioned electrolyte usually contains 1
About 30 mg / L of Pb components (mainly Pb ions) are contained as impurities. This Pb component is mixed in from the following places. For example, a copper scrap material dissolved as a copper material contains a large amount of Pb component as an impurity, and is also contained in copper sulfate as a copper material. In addition, the elution of Pb contained in the piping of the copper foil production apparatus and the lining of each tank also causes the Pb to be contained in the electrolytic solution.
【００１５】本発明では、以上のような電解液に、炭酸
ストロンチウムを添加して、Ｐｂ成分（Ｐｂイオン）を
除去する。炭酸ストロンチウムの添加量は、電解液中に
含まれるＰｂイオンの量に対して、８〜１００g/Pb-g、
好ましくは１０〜７０g/Pb-gの範囲にあることが好まし
い。このような範囲で、炭酸ストロンチウムを添加する
と、Ｐｂイオンを効率よく除去することができる。な
お、炭酸ストロンチウムの量が８g/Pb-gより少ない場合
は、炭酸ストロンチウムを添加する効果が充分ではな
く、また炭酸ストロンチウムの量を１００g/Pb-gより多
くしても、それ以上の効果は期待できない。In the present invention, strontium carbonate is added to the above-mentioned electrolytic solution to remove Pb components (Pb ions). The amount of strontium carbonate added is 8 to 100 g / Pb-g, based on the amount of Pb ions contained in the electrolytic solution.
Preferably, it is in the range of 10 to 70 g / Pb-g. By adding strontium carbonate in such a range, Pb ions can be efficiently removed. When the amount of strontium carbonate is less than 8 g / Pb-g, the effect of adding strontium carbonate is not sufficient, and even if the amount of strontium carbonate is more than 100 g / Pb-g, the further effect is not obtained. Can't expect.
【００１６】炭酸ストロンチウムを添加した電解液は、
そのまま電解液として使用することもできるが、図１に
示されるように炭酸ストロンチウム添加後の電解液を濾
過し、反応生成物を除去しておくことが望ましい。濾過
機としては、公知のものを使用することが可能であり、
具体的には、メンブランフィルター、カートリッジフィ
ルター、ウルトラフィルターなどが使用される。The electrolyte containing strontium carbonate is:
Although the electrolyte solution can be used as it is, it is desirable to filter the electrolyte solution after adding strontium carbonate to remove reaction products as shown in FIG. As the filter, it is possible to use a known filter,
Specifically, a membrane filter, a cartridge filter, an ultra filter, or the like is used.
【００１７】炭酸ストロンチウムを添加することによっ
て、電解液中に含まれるＰｂの量は、通常、２mg/L以下
に低減される。本発明のように０．１〜５．０ｍｇ／Ｌ
の低塩素イオン濃度の電解液に、特定量の炭酸ストロン
チウムを添加することによって、電解液中のＰｂイオン
の量を低減できる理由は、酸性の電解液中でＰｂ成分が
炭酸ストロンチウムと優先的に反応し、鉛−ストロンチ
ウム複合物の沈殿を生じ、これにより電解液中のＰｂイ
オンが除去されるものと考えられる。[0017] By adding strontium carbonate, the amount of Pb contained in the electrolyte is usually reduced to 2 mg / L or less. 0.1 to 5.0 mg / L as in the present invention
The reason that the amount of Pb ions in the electrolyte can be reduced by adding a specific amount of strontium carbonate to the electrolyte having a low chloride ion concentration is that the Pb component preferentially takes place over strontium carbonate in an acidic electrolyte. It is believed that the reaction caused precipitation of the lead-strontium composite, thereby removing Pb ions in the electrolyte.
【００１８】このようにＰｂイオンが除去された電解液
を用いて電解を行うと、Ｐｂ微粉を含まない電解銅箔が
製造できる。なお、特開平6-146051号公報、特開平6-14
6052号公報には、鉛濃度の少ない電解液に、炭酸ストロ
ンチウムを添加しても、微小な硫酸鉛のフロックを生じ
るのみで、充分に濾過して除去できない旨が記載されて
いる。しかしながら、本発明のように、塩素イオン濃度
が０．１〜５．０ｍｇ／Ｌの電解液を使用する場合に
は、添加する炭酸ストロンチウムの量を、電解液中に含
まれるＰｂイオンに対して８〜１００(g/Pb-g)の量とす
れば、鉛−ストロンチウム複合物の沈殿物が生じ、しか
もこの沈殿物は、濾過などの方法によって除去できるの
であり、このことは、本発明者らによる新たな知見であ
る。When electrolysis is performed using the electrolytic solution from which Pb ions have been removed, an electrolytic copper foil containing no Pb fine powder can be produced. Incidentally, JP-A-6-46051, JP-A-6-14
No. 6052 describes that even if strontium carbonate is added to an electrolyte solution having a low lead concentration, only fine flocs of lead sulfate are generated and cannot be sufficiently removed by filtration. However, when an electrolytic solution having a chloride ion concentration of 0.1 to 5.0 mg / L is used as in the present invention, the amount of strontium carbonate to be added is changed with respect to the amount of Pb ions contained in the electrolytic solution. When the amount is 8 to 100 (g / Pb-g), a precipitate of the lead-strontium complex is generated, and the precipitate can be removed by a method such as filtration. These are new findings by the authors.
【００１９】また、本発明で使用する電解液には、必要
に応じて公知の添加剤が添加されていてもよい。添加剤
としては、たとえばブドウ糖、チオ尿素、グリシン、ポ
リ塩化ビニル、ポリエチレングリコール、トリエタノー
ルアミン、ヒドラジン、酢酸ビニルなどが挙げられる。
また、ニカワ、ゼラチンなどを添加剤として使用するこ
ともできる。Further, known additives may be added to the electrolytic solution used in the present invention, if necessary. Examples of the additives include glucose, thiourea, glycine, polyvinyl chloride, polyethylene glycol, triethanolamine, hydrazine, and vinyl acetate.
Also, glue, gelatin and the like can be used as additives.
【００２０】なお、この硫酸銅を含む電解液を使用し
て、電解する場合、電解液の液温は、３０〜８０℃の範
囲にあることが望ましく、また電流密度は８〜１００Ａ
／ｄｍ 2の範囲あることが好ましい。このような本発明
に係る方法によって得られたＰｂ微粉を含まない電解銅
箔を使用して銅張り積層板およびプリント配線板を製造
することができる。The electrolytic solution containing copper sulfate was used.
When performing electrolysis, the temperature of the electrolytic solution is in the range of 30 to 80 ° C.
And a current density of 8 to 100 A
/ Dm TwoIs preferably within the range. The present invention as described above
Copper containing no Pb fine powder obtained by the method according to the present invention
Manufacture copper-clad laminates and printed wiring boards using foil
can do.
【００２１】電解銅箔を、銅張り積層板およびプリント
配線板の形成用銅箔として使用する場合、必要に応じ
て、電解銅箔のマット面（粗面）側上に、粒子状の銅電
着物層が形成される。この粒子状の銅電着物層を形成す
る処理を「コブ付け処理」あるいは「粗化処理」とい
う。このコブ付け処理は、マット面（粗面）側を電極に
対向させて配置させ、銅イオンを含む電解液を電解して
行われ、通常、ヤケメッキおよびカブセメッキからな
る。When the electrolytic copper foil is used as a copper foil for forming a copper-clad laminate and a printed wiring board, if necessary, a particulate copper electrode may be provided on the matte (rough) side of the electrolytic copper foil. A kimono layer is formed. The process of forming the particulate copper electrodeposit layer is referred to as “bumping” or “roughening”. This bumping treatment is performed by arranging the mat surface (rough surface) side to face the electrode and electrolyzing an electrolytic solution containing copper ions, and usually comprises burnt plating and curb plating.
【００２２】ヤケメッキの一例としては、製造した電解
銅箔のマット面（粗面）側を電極に対向させて配置し、
以下の条件で電解液の電解を行うことができる。 銅濃度：５〜３０g/L 硫酸濃度：５０〜１５０g/L 液温：２０〜３０℃ 電流密度：２０〜４０A/dm2 時間：５〜１５秒 この電解条件により、ヤケメッキと呼ばれる樹枝状の銅
電着物層が、電解銅箔のマット面（粗面）側に形成され
る。As an example of burn plating, the matte surface (rough surface) of the produced electrolytic copper foil is arranged so as to face the electrode,
Electrolysis of the electrolytic solution can be performed under the following conditions. Copper concentration: 5 to 30 g / L Sulfuric acid concentration: 50 to 150 g / L Liquid temperature: 20 to 30 ° C Current density: 20 to 40 A / dm 2 hours: 5 to 15 seconds Under these electrolytic conditions, dendritic copper called burnt plating is obtained. An electrodeposit layer is formed on the matte (rough) side of the electrolytic copper foil.
【００２３】カブセメッキの一例としては、上記のヤケ
メッキ工程を施した電解銅箔の表面に、さらに以下の条
件で電解を行うことができる。 銅濃度：４０〜８０g/L 硫酸濃度：５０〜１５０g/L 液温：４５〜５５℃ 電流密度：２０〜４０A/dm2 時間：５〜１５秒 この電解条件により、前記樹枝状銅電着物層の上に、銅
の被覆層（カブセメッキと呼ばれる）が形成され、コブ
状の電着層が形成される。As an example of the fog plating, electrolysis can be further performed on the surface of the electrolytic copper foil that has been subjected to the burn plating step under the following conditions. Copper concentration: 40 to 80 g / L Sulfuric acid concentration: 50 to 150 g / L Liquid temperature: 45 to 55 ° C. Current density: 20 to 40 A / dm 2 hours: 5 to 15 seconds According to the electrolytic conditions, the dendritic copper electrodeposit layer is formed. A copper coating layer (referred to as "kabuse plating") is formed thereon, and a bump-like electrodeposition layer is formed.
【００２４】さらにこのようにカブセメッキが施された
表面は、必要に応じて、さらにヒゲメッキが行われても
よい。ヒゲメッキの一例としては、上記のカブセメッキ
を施した電解銅箔（プリント配線板用銅箔ということも
ある）の表面に、さらに以下の条件で電解を行うことが
できる。Further, the surface on which the cover plating has been performed as described above may be further subjected to a beard plating if necessary. As an example of the whisker plating, electrolysis can be further performed on the surface of the electrolytic copper foil (also sometimes referred to as a copper foil for a printed wiring board) on which the above-mentioned kabuse plating has been performed under the following conditions.
【００２５】 銅濃度：５〜３０g/L 硫酸濃度：３０〜６０g/L 液温：２０〜３０℃ 電流密度：１０〜４０A/dm2 時間：５〜１５秒 この電解条件により、前記銅の被覆層の上にヒゲ状の銅
層（ヒゲメッキと呼ばれる）が形成される。Copper concentration: 5 to 30 g / L Sulfuric acid concentration: 30 to 60 g / L Liquid temperature: 20 to 30 ° C. Current density: 10 to 40 A / dm 2 hours: 5 to 15 seconds Under the above electrolytic conditions, the copper is coated. A whisker-like copper layer (called whisker plating) is formed on the layer.
【００２６】このようなプリント配線板用銅箔には、通
常、防錆処理が施される。防錆処理としては、特に制限
されるものではなく、たとえば、亜鉛メッキ処理、錫メ
ッキ処理、クロメート処理などが挙げられる。亜鉛メッ
キ処理では、通常、硫酸亜鉛、ピロリン酸亜鉛などを含
む電解液を使用して行われる。また、クロメート処理
は、通常、無水クロム酸を０．２〜５g/Lの量で含み、
かつｐHが９〜１３の範囲にある電解液を、０．１〜３A
/dm2の電流密度で電気分解することによって行われる。
このときの電解時間は、１〜８秒であることが望まし
い。Such a copper foil for a printed wiring board is usually subjected to a rustproofing treatment. The rust prevention treatment is not particularly limited, and examples thereof include a zinc plating treatment, a tin plating treatment, and a chromate treatment. The galvanizing process is usually performed using an electrolytic solution containing zinc sulfate, zinc pyrophosphate, and the like. The chromate treatment usually contains chromic anhydride in an amount of 0.2 to 5 g / L,
And an electrolyte having a pH in the range of 9 to 13 is 0.1 to 3 A
It carried out by electrolysis at a current density of / dm 2.
The electrolysis time at this time is desirably 1 to 8 seconds.
【００２７】上記プリント配線板用銅箔では、さらに必
要に応じてシランカップリング剤で、表面処理されてい
てもよい。シランカップリング剤としては、具体的に
は、エポキシアルコキシシラン、アミノアルコキシシラ
ン、メタクリロキシアルコキシシラン、メルカプトアル
コキシシランなどのシランカップリング剤などが使用さ
れる。なお、このようなシランカップリング剤は、２種
以上混合して使用してもよい。The copper foil for a printed wiring board may be further surface-treated with a silane coupling agent, if necessary. Specific examples of the silane coupling agent include silane coupling agents such as epoxyalkoxysilane, aminoalkoxysilane, methacryloxyalkoxysilane, and mercaptoalkoxysilane. In addition, you may use these silane coupling agents in mixture of 2 or more types.
【００２８】シランカップリング剤は、ケイ素原子換算
で、０．１５〜２０ｍｇ／ｍ2、好ましくは０．３〜
２．０ｍｇ／ｍ2となるように塗布されていることが望
ましい。 ［銅張り積層板およびプリント配線板］上記方法で得ら
れた電解銅箔をプリント配線板用銅箔として、絶縁基材
と加熱圧着させることにより、電解銅箔と絶縁基材とか
ら形成された銅張り積層板が得られる。The silane coupling agent is 0.15 to 20 mg / m 2 in terms of silicon atom, preferably 0.3 to 20 mg / m 2 .
It is desirable that the coating be performed so as to be 2.0 mg / m 2 . [Copper-Clad Laminate and Printed Wiring Board] The electrolytic copper foil obtained by the above method was used as a copper foil for a printed wiring board, and was formed by press-bonding with an insulating base by heating and pressing. A copper clad laminate is obtained.
【００２９】絶縁基材としては、一般に電子機器用途と
して使用されている樹脂基材であればとくに限定されず
に使用できる。具体的には、紙−フェノール基材、紙−
エポキシ基材、ガラスエポキシ基材、ポリイミド基材な
どが挙げられる。次に、この銅張り積層板に、公知の方
法によりドライフィルムをラミネートし、所定のレジス
ト幅および回路間隔のパターンフィルムを用いてＵＶ露
光によって、パターンを形成し、公知の方法によってエ
ッチングを行うことによって、所望の配線パターンを有
するプリント配線板を得ることができる。なお、形成し
た回路パターンのエッチングは、市販の各種エッチング
液を用いて、公知の方法によって行うことができる。As the insulating base material, any resin base material generally used for electronic equipment can be used without any particular limitation. Specifically, paper-phenol base material, paper-
Epoxy base materials, glass epoxy base materials, polyimide base materials and the like can be mentioned. Next, a dry film is laminated on the copper-clad laminate by a known method, a pattern is formed by UV exposure using a pattern film having a predetermined resist width and a circuit interval, and etching is performed by a known method. Thereby, a printed wiring board having a desired wiring pattern can be obtained. The formed circuit pattern can be etched by a known method using various commercially available etching solutions.
【００３０】[0030]
【発明の効果】本発明のように塩素イオン濃度が０．１
〜５．０ｍｇ／Ｌの低塩素濃度の電解液に、特定の量の
炭酸ストロンチウムを添加することによって、電解液中
のＰｂイオンの量を極めて少なくすることが可能とな
り、製造設備や電解条件を変更することなく、Ｐｂ微粉
の偏在しない電解銅箔を製造することができる。しかも
製造された電解銅箔は、ファイン回路形成に適してい
る。According to the present invention, the chlorine ion concentration is 0.1%.
By adding a specific amount of strontium carbonate to an electrolytic solution having a low chlorine concentration of ~ 5.0 mg / L, the amount of Pb ions in the electrolytic solution can be extremely reduced. Without changing, it is possible to manufacture an electrolytic copper foil in which Pb fine powder is not unevenly distributed. Moreover, the manufactured electrolytic copper foil is suitable for forming a fine circuit.
【００３１】このような電解銅箔をプリント配線板用銅
箔として用いてプリント配線板を作製すると、たとえば
線幅５０μｍ／線間５０μｍのファイン回路を形成する
際に、Ｐｂ微粉によって、回路が断線したり、回路の短
絡が生じたりすることがなく、従来のプリント配線板用
銅箔と比較して信頼性が高いプリント配線板を作製する
ことができる。When a printed wiring board is manufactured by using such an electrolytic copper foil as a copper foil for a printed wiring board, for example, when a fine circuit having a line width of 50 μm / inter-line distance of 50 μm is formed, the circuit is broken by fine Pb powder. The printed wiring board can be manufactured with high reliability as compared with a conventional copper foil for a printed wiring board without causing a short circuit or a short circuit.
【００３２】[0032]
【実施例】以下、本発明を実施例により具体的に説明す
るが、本発明はこれらの実施例に何ら制限されるもので
はない。EXAMPLES Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples.
【００３３】[0033]
【実施例１】電解銅箔の作製 塩素イオンを３．０ｍｇ／Ｌで、銅イオンを８０g/L、
硫酸を２５０g/Lの濃度で含み、かつPbイオンを７．４m
g/Lの量で含む電解液に、炭酸ストロンチウムを、電解
液中に含まれる炭酸ストロンチウムの濃度が５００mg/L
（電解液中のＰｂイオンに対して６８g/Pb-g）となるよ
うに添加した。次いで、該電解液を濾過して、Ｐｂイオ
ンが除去された電解液を調製した。EXAMPLE 1 Preparation of Electrodeposited Copper Foil Chloride ion was 3.0 mg / L, copper ion was 80 g / L,
Contains sulfuric acid at a concentration of 250 g / L and contains Pb ions at 7.4 m
g / L in the electrolyte containing strontium carbonate, the concentration of strontium carbonate in the electrolyte is 500 mg / L
(68 g / Pb-g with respect to Pb ions in the electrolytic solution). Next, the electrolytic solution was filtered to prepare an electrolytic solution from which Pb ions had been removed.
【００３４】Ｐｂ除去後の電解液中のＰｂ濃度は、０．
２ｍｇ／Ｌ以下であった。得られたＰｂ除去後の電解液
を、連続的に、図１に示される電解槽１に供給し、５０
A/dm2の電圧を印加し、陰極ドラム１aに銅を電着させた
のち、得られた銅箔を、連続的に剥離して厚さ３５μｍ
の電解銅箔を作製した。Ｐｂ検出個数 得られた電解銅箔を１０cm×１０cmの大きさに切断した
のち、過硫酸アンモニウムを１００g/Lの濃度で含む化
学研磨液に浸漬して、銅箔を溶解させ、溶解液を０．２
μｍのメンブランフィルターで濾過した。濾紙上のＰｂ
残滓個数を光学顕微鏡により観察した。After the removal of Pb, the Pb concentration in the electrolytic solution is 0.1%.
It was 2 mg / L or less. The obtained electrolytic solution from which Pb has been removed is continuously supplied to the electrolytic cell 1 shown in FIG.
After applying a voltage of A / dm 2 to deposit copper on the cathode drum 1a, the obtained copper foil was continuously peeled off to a thickness of 35 μm.
Was produced. Pb detection number The obtained electrolytic copper foil was cut into a size of 10 cm × 10 cm, and then immersed in a chemical polishing solution containing ammonium persulfate at a concentration of 100 g / L to dissolve the copper foil. 2
The solution was filtered through a μm membrane filter. Pb on filter paper
The number of residues was observed with an optical microscope.
【００３５】以上の操作を５回繰り返し、５回分のＰｂ
残滓個数の合計をＰｂ検出個数とした。また得られた銅
箔の物性（面粗さ、抗張力、伸び率）を評価した。結果
を表１に示す。The above operation is repeated five times and Pb for five times
The total number of residues was determined as the number of detected Pb. The physical properties (surface roughness, tensile strength, elongation) of the obtained copper foil were evaluated. Table 1 shows the results.
【００３６】[0036]
【実施例２】実施例１において、炭酸ストロンチウム
を、電解液中に含まれる炭酸ストロンチウムの濃度が２
００mg/L（電解液中のＰｂイオンに対して２７g/Pb-g）
となるように添加した以外は、実施例１と同様にして電
解銅箔を作製した。得られた電解銅箔について、実施例
１と同様にしてＰｂ検出個数および銅箔物性を評価し
た。Example 2 In Example 1, strontium carbonate was replaced with strontium carbonate having a concentration of 2 in the electrolytic solution.
00mg / L (27g / Pb-g for Pb ion in electrolyte)
An electrolytic copper foil was produced in the same manner as in Example 1 except that the addition was performed so that About the obtained electrolytic copper foil, Pb detection number and the copper foil physical property were evaluated like Example 1. FIG.
【００３７】結果を表１に示す。The results are shown in Table 1.
【００３８】[0038]
【実施例３】実施例１において、炭酸ストロンチウム
を、電解液中に含まれる炭酸ストロンチウムの濃度が１
００mg/L（電解液中のＰｂイオンに対して１４g/Pb-g）
となるように添加した以外は、実施例１と同様にして電
解銅箔を作製した。得られた電解銅箔について、実施例
１と同様にしてＰｂ検出個数および銅箔物性を評価し
た。Example 3 In Example 1, strontium carbonate was replaced with strontium carbonate having a concentration of 1 contained in the electrolytic solution.
00mg / L (14g / Pb-g based on Pb ion in electrolyte)
An electrolytic copper foil was produced in the same manner as in Example 1 except that the addition was performed so as to be as follows. About the obtained electrolytic copper foil, Pb detection number and the copper foil physical property were evaluated like Example 1. FIG.
【００３９】結果を表１に示す。Table 1 shows the results.
【００４０】[0040]
【比較例１】実施例１において、炭酸ストロンチウム
を、電解液中に含まれる炭酸ストロンチウムの濃度が５
０mg/L（電解液中のＰｂイオンに対して７g/Pb-g）とな
るように添加した以外は、実施例１と同様にして電解銅
箔を作製した。得られた電解銅箔について、実施例１と
同様にしてＰｂ検出個数および銅箔物性を評価した。Comparative Example 1 In Example 1, strontium carbonate was replaced with strontium carbonate having a concentration of 5 in the electrolytic solution.
An electrolytic copper foil was prepared in the same manner as in Example 1 except that the addition was performed so as to be 0 mg / L (7 g / Pb-g with respect to Pb ions in the electrolytic solution). About the obtained electrolytic copper foil, Pb detection number and the copper foil physical property were evaluated like Example 1. FIG.
【００４１】結果を表１に示す。Table 1 shows the results.
【００４２】[0042]
【比較例２】実施例１において、炭酸ストロンチウムを
添加せずに、実施例１と同様にして電解銅箔を作製し
た。得られた電解銅箔について、実施例１と同様にして
Ｐｂ検出個数および銅箔物性を評価した。Comparative Example 2 An electrolytic copper foil was produced in the same manner as in Example 1 except that strontium carbonate was not added. About the obtained electrolytic copper foil, Pb detection number and the copper foil physical property were evaluated like Example 1. FIG.
【００４３】結果を表１に示す。Table 1 shows the results.
【００４４】[0044]
【表１】 [Table 1]
【００４５】表１から明らかなように、炭酸ストロンチ
ウムを添加することによって、得られる電解銅箔に含ま
れるＰｂ微粉の量を極めて少なくできることが判明し
た。しかも、得られた電解銅箔の銅箔特性は、従来の銅
箔と同程度のものであった。As is clear from Table 1, it was found that the amount of Pb fine powder contained in the obtained electrolytic copper foil can be extremely reduced by adding strontium carbonate. Moreover, the copper foil characteristics of the obtained electrolytic copper foil were comparable to those of conventional copper foil.
【図１】 本発明に係る電解銅箔の製造方法にて使用さ
れる製造装置の一例を示す図である。FIG. 1 is a diagram showing an example of a manufacturing apparatus used in a method for manufacturing an electrolytic copper foil according to the present invention.
１……電解槽 １a……陰極ドラム １b……電解用陽極 ２……尾液槽 ３……銅原料溶解槽 ４……補給液貯槽 ５……添加剤槽 ６……濾過機 ７……巻き取りロール ８……銅原料 DESCRIPTION OF SYMBOLS 1 ... Electrolysis tank 1a ... Cathode drum 1b ... Anode for electrolysis 2 ... Tail tank 3 ... Cu raw material dissolution tank 4 ... Supplementary liquid storage tank 5 ... Additive tank 6 ... Filter 7 ... Wound Take-up roll 8 Copper raw material
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4K024 AA09 AB01 AB02 AB19 BA09 BB11 BC02 CA02 DB03 DB04 GA16 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4K024 AA09 AB01 AB02 AB19 BA09 BB11 BC02 CA02 DB03 DB04 GA16
Claims (4)
製造するに際して、 電解液として、Ｃｌイオンを０．１〜５．０ｍｇ／Ｌの
量で含むものを使用し、かつ、電解液に、炭酸ストロン
チウムを、電解液中に含まれるＰｂイオンの量に対して
８〜１００(g/Pb-g)の量で添加し、電解液中に含まれる
Ｐｂイオンを除去して電解銅箔を形成することを特徴と
する電解銅箔の製造方法。When producing an electrolytic copper foil using an electrolytic solution containing copper sulfate, an electrolytic solution containing 0.1 to 5.0 mg / L of Cl ions is used as an electrolytic solution; To the electrolytic solution, strontium carbonate was added in an amount of 8 to 100 (g / Pb-g) with respect to the amount of Pb ions contained in the electrolytic solution, and the Pb ions contained in the electrolytic solution were removed to perform electrolysis. A method for producing an electrolytic copper foil, comprising forming a copper foil.
Ｐｂ微粉を含まない電解銅箔。2. An electrolytic copper foil containing no Pb fine powder, produced by the method according to claim 1.
れた銅張り積層板。3. A copper-clad laminate manufactured using the electrolytic copper foil according to claim 2.
れたプリント配線板。4. A printed wiring board manufactured using the electrolytic copper foil according to claim 2.
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11161644A JP3046301B1 (en) | 1999-06-08 | 1999-06-08 | Method for producing electrolytic copper foil, electrolytic copper foil, copper-clad laminate and printed wiring board |
| MYPI20002559 MY124018A (en) | 1999-06-08 | 2000-06-07 | Manufacturing method of electrodeposited copper foil, electrodeposited copper foil, copper-clad laminate and printed wiring board |
| TW089111033A TWI229152B (en) | 1999-06-08 | 2000-06-07 | Manufacturing method of electrodeposited copper foil |
| US09/590,528 US6444112B1 (en) | 1999-06-08 | 2000-06-08 | Manufacturing method of electrodeposited copper foil |
| AT00304865T ATE343665T1 (en) | 1999-06-08 | 2000-06-08 | METHOD FOR PRODUCING ELECTROLYTICALLY DEPOSITED COPPER FOIL, ELECTROLYTICALLY DEPOSTED COPPER FOIL, COPPER CLADDED LAMINATE AND CIRCUIT BOARD |
| EP00304865A EP1059367B1 (en) | 1999-06-08 | 2000-06-08 | Manufacturing method of electrodeposited copper foil, electrodeposited copper foil, copper-clad laminate and printed wiring board |
| DE60031479T DE60031479T2 (en) | 1999-06-08 | 2000-06-08 | Process for producing electrodeposited copper foil, electrodeposited copper foil, copper-clad laminate and printed circuit board |
| CNB001181955A CN1163638C (en) | 1999-06-08 | 2000-06-08 | Electrodeposit copper foil and its mfg method, copper coated laminate and PC board |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11161644A JP3046301B1 (en) | 1999-06-08 | 1999-06-08 | Method for producing electrolytic copper foil, electrolytic copper foil, copper-clad laminate and printed wiring board |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP3046301B1 JP3046301B1 (en) | 2000-05-29 |
| JP2000345381A true JP2000345381A (en) | 2000-12-12 |
Family
ID=15739111
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11161644A Expired - Fee Related JP3046301B1 (en) | 1999-06-08 | 1999-06-08 | Method for producing electrolytic copper foil, electrolytic copper foil, copper-clad laminate and printed wiring board |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3046301B1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006052441A (en) * | 2004-08-11 | 2006-02-23 | Mitsui Mining & Smelting Co Ltd | Copper foil, manufacturing method therefor, and tab tape |
| US9297091B2 (en) | 2012-09-18 | 2016-03-29 | Sumitomo Electric Industries, Ltd. | Method for producing aluminum film and method for producing aluminum foil |
| JP2020515712A (en) * | 2017-03-08 | 2020-05-28 | ナノワイヤード ゲーエムベーハー | Device and method for providing large numbers of nanowires |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104294324B (en) * | 2014-09-18 | 2017-06-06 | 北京科技大学 | A kind of experimental provision and method for screening and optimizing electrolytic copper foil technique |
-
1999
- 1999-06-08 JP JP11161644A patent/JP3046301B1/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006052441A (en) * | 2004-08-11 | 2006-02-23 | Mitsui Mining & Smelting Co Ltd | Copper foil, manufacturing method therefor, and tab tape |
| JP4549774B2 (en) * | 2004-08-11 | 2010-09-22 | 三井金属鉱業株式会社 | Method for producing electrolytic copper foil |
| US9297091B2 (en) | 2012-09-18 | 2016-03-29 | Sumitomo Electric Industries, Ltd. | Method for producing aluminum film and method for producing aluminum foil |
| JP2020515712A (en) * | 2017-03-08 | 2020-05-28 | ナノワイヤード ゲーエムベーハー | Device and method for providing large numbers of nanowires |
| JP7304290B2 (en) | 2017-03-08 | 2023-07-06 | ナノワイヤード ゲーエムベーハー | Apparatus and method for providing a large number of nanowires |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3046301B1 (en) | 2000-05-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3370624B2 (en) | Electrolytic copper foil with carrier foil and copper-clad laminate using the electrolytic copper foil | |
| US5679230A (en) | Copper foil for printed circuit boards | |
| JP2005076091A (en) | Method of producing ultrathin copper foil with carrier, and ultrathin copper foil with carrier produced by the production method | |
| JPH0754183A (en) | Electrodeposited copper foil and production of electro- deposited copper foil by using electrolyte solution containing chloride ion and additive for controlling organic additive | |
| JP2007186797A (en) | Method for producing ultrathin copper foil with carrier, ultrathin copper foil produced by the production method, and printed circuit board, multilayer printed circuit board and wiring board for chip on film using the ultrathin copper foil | |
| JP4709575B2 (en) | Copper foil roughening treatment method and roughening treatment liquid | |
| JP3739929B2 (en) | Copper foil for printed wiring board and method for producing the same | |
| WO2001016402A1 (en) | Electrolytic copper foil with carrier foil and method for manufacturing the same and copper-clad laminate using the electrolytic copper foil with carrier foil | |
| JP2001089892A (en) | Electrolytic copper foil with carrier foil, its producing method and copper-covered laminated sheet using the electrolytic copper foil with carrier foil | |
| JP2000309898A (en) | Electrolytic copper foil with carrier foil, production of the electrolytic copper foil and copper laminated sheet using the electrolytic copper foil | |
| EP1133220B1 (en) | Copper foil with low profile bond enhancement | |
| US6902824B2 (en) | Copper foil and metal foil with carrier foil for printed wiring board, and semi-additive process for producing printed wiring board using the same | |
| JP3250994B2 (en) | Electrolytic copper foil | |
| US6444112B1 (en) | Manufacturing method of electrodeposited copper foil | |
| JPS61119699A (en) | System and method for producing foil of metal or metal alloy | |
| JP3676152B2 (en) | Electrolytic copper foil with carrier foil and method for producing the same | |
| WO1990012129A1 (en) | Treatment of metal foil | |
| EP0250195A2 (en) | Double matte finish copper foil | |
| JPH08222857A (en) | Copper foil and high-density multilayered printed circuit board using the foil for its internal-layer circuit | |
| JP2005288856A (en) | Electrolytic copper foil with carrier foil and method for manufacturing the same and copper-clad laminated sheet using electrolytic copper foil with carrier foil | |
| JP3046301B1 (en) | Method for producing electrolytic copper foil, electrolytic copper foil, copper-clad laminate and printed wiring board | |
| JPH09272994A (en) | Electrolytic copper foil for fine pattern | |
| JP3906347B2 (en) | Copper foil for printed circuit | |
| JP3812834B2 (en) | Electrolytic copper foil with carrier foil, method for producing the same, and copper-clad laminate using the electrolytic copper foil with carrier foil | |
| US6270648B1 (en) | Process and apparatus for the manufacture of high peel-strength copper foil useful in the manufacture of printed circuit boards, and laminates made with such foil |
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: 3046301 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080317 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090317 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100317 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100317 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110317 Year of fee payment: 11 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110317 Year of fee payment: 11 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120317 Year of fee payment: 12 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120317 Year of fee payment: 12 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130317 Year of fee payment: 13 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130317 Year of fee payment: 13 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140317 Year of fee payment: 14 |
|
| 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 |
|
| LAPS | Cancellation because of no payment of annual fees |