JPH0631461B2 - Method for manufacturing electrolytic copper foil - Google Patents
Method for manufacturing electrolytic copper foilInfo
- Publication number
- JPH0631461B2 JPH0631461B2 JP14698587A JP14698587A JPH0631461B2 JP H0631461 B2 JPH0631461 B2 JP H0631461B2 JP 14698587 A JP14698587 A JP 14698587A JP 14698587 A JP14698587 A JP 14698587A JP H0631461 B2 JPH0631461 B2 JP H0631461B2
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- Prior art keywords
- copper foil
- copper
- ppm
- electrolytic copper
- electrolytic
- 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.)
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- Electroplating Methods And Accessories (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は電解銅箔の製造方法に関し、さらに詳しくは、
硫酸銅と硫酸を主成分とする酸性銅メッキ浴に３種類の
添加剤を配合して、電解処理を行うことにより、特に多
層プリント配線板に好適な品質を具備する電解銅箔を製
造する方法に関する。The present invention relates to a method for producing an electrolytic copper foil, and more specifically,
A method for producing an electrolytic copper foil having suitable quality especially for a multilayer printed wiring board by mixing three kinds of additives in an acidic copper plating bath containing copper sulfate and sulfuric acid as main components and performing electrolytic treatment Regarding
近年、電子機器等に使用される銅張積層板の需要増加は
著しく、技術的には高密度化、高多層化傾向へ移行しつ
つある。In recent years, the demand for copper-clad laminates used in electronic devices and the like has increased remarkably, and technically there is a trend toward higher densities and higher multilayers.
特に多層プリント配線板はコンピューター等に広く使用
され、その品質は信頼性の高いものが要求され、これに
用いられるプリント回路用銅箔も、それに適した特性を
有するものが要望されている。In particular, a multilayer printed wiring board is widely used in computers and the like, and its quality is required to be highly reliable, and the copper foil for printed circuits used therein is also required to have characteristics suitable for it.
例えば、銅箔自体のもつ物理的特性の中に、抗張力、伸
び、あらさ、硬さ等があげられるが、多層プリント配線
板に使用される銅箔に必要とされる特性として、加熱時
（１８０℃雰囲気）における伸び率の優れたものが望ま
れる。その理由は、銅箔を内層回路として使用し、基
材、例えば、エポキシ樹脂含浸ガラス基材と積層する場
合、形成させた銅箔の内層回路が半田処理などの熱スト
レスを受けると、銅箔回路と樹脂の熱膨張率の差により
銅箔自身に亀裂を生じたり、ややもすると破断したりす
る致命的な事故が発生し、品質の信頼性を損なうことと
なるからである。For example, among the physical properties of the copper foil itself, there are tensile strength, elongation, roughness, hardness, etc., but the properties required for a copper foil used for a multilayer printed wiring board are that when heated (180 A material having an excellent elongation rate in a (° C atmosphere) is desired. The reason is that when copper foil is used as an inner layer circuit and is laminated with a substrate, for example, an epoxy resin-impregnated glass substrate, when the inner layer circuit of the formed copper foil receives thermal stress such as soldering, the copper foil This is because the copper foil itself may crack due to the difference in the coefficient of thermal expansion between the circuit and the resin, or even if it breaks a little, a fatal accident will occur and the reliability of the quality will be impaired.
そのような実情からＩＰＣ規格のＩＰＣ−ＣＦ−１５０
Ｅクラス４の要求特性には、常態（２３℃）抗張力14.6
kg/mm2以上、同伸び率３％以上、加熱時（１８０℃雰囲
気）においては、抗張力10.55kg/mm2以上、同伸び率４
％以上（何れも換算値）と規定されている。From such circumstances, the IPC standard IPC-CF-150
E class 4 required properties are normal (23 ℃) tensile strength 14.6
kg / mm 2 or more, same elongation 3% or more, tensile strength at heating (at 180 ° C atmosphere) 10.55 kg / mm 2 or more, same elongation 4
% Or more (both are converted values).
また一方では、多層プリント配線板の高密度化に伴って
狭小回路となれば、当然のことながら銅箔の粗面側は均
一性を有する凹凸のある形状、即ち具体的には、あらさ
を形づくる一つ一つの凹凸が電子顕微鏡（ＳＥＭ）で観
察した場合（倍率１０００倍、傾斜角度４５°）、それ
ぞれに円錐形を有していることが、銅箔の剥離強度等を
高める上で実用上有利とされている。On the other hand, if the circuit becomes narrower as the density of the multilayer printed wiring board increases, it is natural that the rough surface of the copper foil has an uneven shape with uniformity, that is, concretely, the roughness is formed. When each unevenness is observed with an electron microscope (SEM) (magnification: 1000 times, tilt angle: 45 °), each has a conical shape in order to increase the peel strength of the copper foil, etc. It is regarded as an advantage.
さて、電解銅箔の製造方法は、主として銅イオンを含む
酸性銅メッキ浴を用いて、限界電流密度を超えない範囲
において陰極面上に銅の薄膜を形成させる第１工程と、
ついで形成銅薄膜（銅箔）を陰極面上から剥離し、該銅
箔の粗面側を限界電流密度を超える範囲とそれ以下の範
囲を併用して電解処理を施し、該粗面側に樹脂基材との
剥離強度を向上させる目的で、いわゆるアンカー効果を
十分発揮させるため樹枝状もしくは粒状の銅を電着させ
る第２工程と、さらに耐熱性、耐薬品性等の特性を高め
るため、例えば、クロメート処理、キレート剤処理、亜
鉛等の金属を被着させる等の表面処理を施す第３工程と
を経て製造されている。Now, the manufacturing method of the electrolytic copper foil, by using an acidic copper plating bath mainly containing copper ions, a first step of forming a copper thin film on the cathode surface in a range not exceeding the limiting current density,
Then, the formed copper thin film (copper foil) is peeled off from the cathode surface, and the rough surface side of the copper foil is subjected to an electrolytic treatment by using a range exceeding the limiting current density and a range below it together, and the resin is applied to the rough surface side. For the purpose of improving the peeling strength from the base material, a second step of electrodepositing dendritic or granular copper in order to sufficiently exert the so-called anchor effect, and to further enhance the characteristics such as heat resistance and chemical resistance, for example, , A chromate treatment, a chelating agent treatment, and a third step of performing a surface treatment such as depositing a metal such as zinc.
従って、特に多層プリント配線板に必要とされる前記し
た特性の向上をはかるためには、まず第１工程で形成さ
れる銅箔の製造条件を考慮し管理することが重要であ
る。Therefore, in order to improve the above-mentioned characteristics particularly required for the multilayer printed wiring board, it is important to consider and control the manufacturing conditions of the copper foil formed in the first step.
この第１工程で形成される銅箔は従来、銅イオンを含む
酸性銅メッキ浴を用いて電解処理して得られるが、この
とき、好ましい特性を得るため一般的には何らかの特定
な添加剤をメッキ浴に配合させる。例えば、ゼラチン、
にかわ等を添加することにより目的に応じた特性を具え
た銅箔が得られる。そのため、これまでにいくつかの提
案がなされている。一例を挙げると、特公昭４９−３１
４１４号公報には、硫酸銅３００ｇ／、硫酸１００ｇ
／からなる酸性銅メッキ液中にピロリン酸0.2ｇ／
とポリエチレングリコール0.4ｇ／等を添加した電解
液を用いて銅箔を製造する方法が開示されている。この
方法により得られた銅箔は靱性、耐熱性に優れているも
のの、満足するものは得られていない。The copper foil formed in the first step is conventionally obtained by electrolytic treatment using an acidic copper plating bath containing copper ions. At this time, generally, some specific additive is added to obtain preferable characteristics. Add to plating bath. For example, gelatin,
By adding glue or the like, a copper foil having characteristics suitable for the purpose can be obtained. Therefore, some proposals have been made so far. For example, Japanese Examined Patent Publication Sho-49-31
No. 414 discloses copper sulfate 300 g / and sulfuric acid 100 g.
0.2g of pyrophosphoric acid in acidic copper plating solution consisting of /
And a method for producing a copper foil by using an electrolytic solution containing 0.4 g / polyethylene glycol and the like. The copper foil obtained by this method has excellent toughness and heat resistance, but no satisfactory one has been obtained.
また、特開昭６１−５２３８７号公報には、硫酸酸性銅
メッキ液にトリイソプロパノールアミンを添加して、高
温加熱時の伸び率が優れた電解銅箔の製造方法が開示さ
れている。しかし、この方法により得られる銅箔は高温
加熱時の伸び率が優れ、しかも、粗面側は微細粗面とな
るが、その形状は不定形であり、均一性を欠き、剥離強
度等を高めるための配慮が不十分であるという難点があ
る。Further, Japanese Patent Application Laid-Open No. 61-52387 discloses a method for producing an electrolytic copper foil having an excellent elongation rate when heated at high temperature by adding triisopropanolamine to a sulfuric acid copper plating solution. However, the copper foil obtained by this method has an excellent elongation rate when heated at high temperature, and the rough surface side becomes a fine rough surface, but its shape is irregular, lacks uniformity, and enhances peel strength and the like. However, there is a problem that the consideration is insufficient.
本発明は基材と組み合わせて、特に、多層プリント配線
板としたときに、加熱時の伸び率が優れていることによ
り内層回路としての使用に十分耐えられ、なおかつ、粗
面側を形成する凹凸が円錐形を有し、しかもそれらが均
一性を保つことにより、剥離強度等の品質が高められる
という双方の利点を併せもつ電解銅箔を製造する方法を
提供することを目的とする。INDUSTRIAL APPLICABILITY The present invention, in combination with a base material, has excellent elongation at the time of heating, particularly when it is used as a multilayer printed wiring board, and thus is sufficiently durable to be used as an inner layer circuit, and has unevenness forming a rough surface side. It is an object of the present invention to provide a method for producing an electrolytic copper foil which has the advantages of having a conical shape and maintaining the uniformity thereof, and that both qualities such as peel strength can be improved.
本発明は硫酸銅と硫酸を主成分とする酸性銅メッキ浴を
用いて電解銅箔を製造するにあたり、該メッキ浴に、ヒ
ドロキシアルキルアミン、塩素イオン、およびゼラチン
を添加して電解処理を行うことを特徴とする電解銅箔の
製造方法に関する。In the present invention, when an electrolytic copper foil is produced using an acidic copper plating bath containing copper sulfate and sulfuric acid as a main component, a hydroxyalkylamine, chlorine ion, and gelatin are added to the plating bath for electrolytic treatment. And a method for producing an electrolytic copper foil.
以下、本発明を詳細に説明する。Hereinafter, the present invention will be described in detail.
本発明に用いるメッキ浴は、硫酸銅と硫酸を主成分とす
る酸性銅メッキ浴であり、硫酸銅（ＣｕＳｏ４・５Ｈ２
Ｏ）の濃度は、１００〜４００ｇ／の範囲とすること
が好ましい。濃度が１００ｇ／未満の場合は、高電流
密度で生産性を高める場合、水素ガスの発生を伴ういわ
ゆるヤケメッキとなり、銅箔自体の特性、例えば、抗張
力、伸び率等の品質が低下し、また、濃度が４００ｇ／
を超える場合は、タンク、配管等の装置や、機器類に
硫酸銅が再結晶しやすくなる。一方、硫酸（Ｈ２Ｓ
Ｏ４）の濃度は５０〜１５０ｇ／の範囲が好ましい。
濃度が５０ｇ／未満の場合は浴電圧の上昇を伴い、製
造原価が増大し、１５０ｇ／を超える場合は、電解装
置、とりわけ、陽極側の鉛電極、陰極側のチタンドラム
の腐食が大となる。Plating baths used in the present invention is an acidic copper plating bath composed mainly of copper sulfate and sulfuric acid, copper sulfate (CuSo 4 · 5H 2
The concentration of O) is preferably in the range of 100 to 400 g /. When the concentration is less than 100 g /, when the productivity is increased with a high current density, so-called burn plating is accompanied by the generation of hydrogen gas, and the characteristics of the copper foil itself, for example, the tensile strength, elongation and other qualities are degraded, and Concentration is 400g /
If it exceeds, the copper sulfate is likely to be recrystallized in devices such as tanks and pipes and devices. On the other hand, sulfuric acid (H 2 S
The concentration of O 4 ) is preferably in the range of 50 to 150 g /.
When the concentration is less than 50 g /, the manufacturing cost increases with the increase of the bath voltage, and when it exceeds 150 g /, the electrolytic device, especially the lead electrode on the anode side and the titanium drum on the cathode side are greatly corroded. .
さて、このメッキ浴に前記の添加剤を配合させるが、本
発明においては、ヒドロキシアルキルアミン、塩素イオ
ン、およびゼラチンの３種類の添加剤を併用する。Now, the above-mentioned additives are mixed in this plating bath, but in the present invention, three kinds of additives of hydroxyalkylamine, chloride ion, and gelatin are used together.
添加剤のそれぞれの作用について説明すると、まず、ヒ
ドロキシアルキルアミンは、加熱時の伸び率を増大させ
るために有効な必須成分である。その添加濃度は0.5〜
１５ppmの範囲が好ましい。濃度が0.5ppm未満の場合、
または、濃度が１５ppmを超える場合においては、いず
れも加熱時の伸び率の効果が減少する傾向にある。そし
て、この濃度の特に好ましい範囲は１〜１０ppmであ
る。Explaining each action of the additive, first, the hydroxyalkylamine is an essential component effective for increasing the elongation percentage upon heating. The addition concentration is 0.5 ~
A range of 15 ppm is preferred. If the concentration is less than 0.5 ppm,
Alternatively, when the concentration exceeds 15 ppm, the effect of the elongation percentage upon heating tends to decrease. The particularly preferable range of this concentration is 1 to 10 ppm.
本発明において用いられるヒドロキシアルキルアミンと
しては、トリエタノールアミン、トリイソプロバノール
アミン等のトリヒドロキシアルキアルアミン、Ｎ−ｎ−
ブチルジエタノールアミン等のジヒドロキシアルキアル
アミン、２−ジメチルアミノエタノール等のモノヒドロ
キシアルキルアミンを挙げることができる。Examples of hydroxyalkylamines used in the present invention include trihydroxyalkylamines such as triethanolamine and triisopropanolamine, Nn-
Examples thereof include dihydroxyalkylamines such as butyldiethanolamine and monohydroxyalkylamines such as 2-dimethylaminoethanol.
また、塩素イオンは、銅の結晶を大きくさせる効果と、
その形状を円錐形にするために有効な必須成分である。
その添加濃度は１〜３０ppmの範囲が好ましい。濃度は
１ppm未満の場合は、上記する効果は十分には得られ
ず、３０ppmを超える場合は、その効果は飽和域に達
し、むしろ、陰極ドラム等を腐食させる原因となること
がある。そしてこの濃度の特に好ましい範囲は５〜１５
ppmである。塩素イオンの供給源としては、特に制限は
されないが、通常塩酸、塩化ナトリウム、塩化カリウ
ム、塩化銅等が用いられる。In addition, chlorine ions have the effect of enlarging copper crystals,
It is an essential component that is effective for making the shape a cone.
The added concentration is preferably in the range of 1 to 30 ppm. If the concentration is less than 1 ppm, the above effect is not sufficiently obtained, and if the concentration exceeds 30 ppm, the effect reaches the saturation region, which may rather cause corrosion of the cathode drum and the like. And a particularly preferable range of this concentration is 5 to 15.
ppm. The supply source of chlorine ions is not particularly limited, but usually hydrochloric acid, sodium chloride, potassium chloride, copper chloride or the like is used.
一方、ゼラチンは銅の結晶成長を抑止させ、均一化させ
る効果がある。その添加濃度は0.1〜５ppmの範囲が好ま
しい。濃度が0.1ppm未満の場合は、上記効果が減少し、
５ppmを超える場合は伸び率が低下する。そして、この
濃度の特に好ましい範囲は0.5〜２ppmである。On the other hand, gelatin has the effect of suppressing the crystal growth of copper and making it uniform. The added concentration is preferably in the range of 0.1 to 5 ppm. If the concentration is less than 0.1 ppm, the above effects will decrease,
If it exceeds 5 ppm, the elongation will decrease. The particularly preferable range of this concentration is 0.5 to 2 ppm.
上記の３種類の添加剤を添加することにより、加熱時の
伸び率が優れ、なおかつ、粗面側の銅の結晶を円錐形に
形成することができ、しかもその均一性を保つことがで
きる。By adding the above-mentioned three kinds of additives, the elongation at the time of heating is excellent, the copper crystal on the rough surface side can be formed into a conical shape, and the uniformity can be maintained.
上記の電解処理にあたっては、前記添加剤に加えて、ポ
リエチレングリコール等の他の有機添加剤を加えること
も可能である。In the above electrolytic treatment, other organic additives such as polyethylene glycol can be added in addition to the above additives.
また、電解処理における電解密度は、硫酸銅、および硫
酸の濃度、浴温、液流速等によって、それぞれ変動した
値を示すので、一概には決められないが、生産速度をも
考慮にいれて、好ましい範囲は、電流密度は１０〜３０
０Ａ／dm2、浴温は３５〜８０℃、流速は0.1〜５ｍ／秒
の範囲であり、この範囲のうちから適宜選択される。In addition, the electrolytic density in the electrolytic treatment shows a value that varies depending on the concentration of copper sulfate and sulfuric acid, the bath temperature, the liquid flow rate, etc., so it cannot be determined unconditionally, but considering the production rate, A preferable range is a current density of 10 to 30.
0 A / dm 2 , the bath temperature is 35 to 80 ° C., and the flow rate is 0.1 to 5 m / sec. The range is appropriately selected.
このようにして、得られた銅箔は、必要に応じて、前記
第２工程、第３工程の処理を経て、多層プリント配線板
に好適に使用できる銅箔とすることができる。In this way, the obtained copper foil can be processed into the second step and the third step, if necessary, to be a copper foil which can be suitably used for a multilayer printed wiring board.
以下、本発明を実施例に基づいて詳細に説明するが、本
発明はこれに限定されるものではない。Hereinafter, the present invention will be described in detail based on examples, but the present invention is not limited thereto.
実施例１ 硫酸銅２７０ｇ／、硫酸１００ｇ／を含む酸性銅メ
ッキ浴に添加剤としてトリエタノールアミン（試薬１級
ＪＩＳ Ｋ−８６６３）２ppm、塩素イオン（塩酸中の
塩素イオンとして）３ppm、およびゼラチン0.5ppmを添
加し電解液を作成した。Example 1 2 ppm of triethanolamine (reagent first grade JIS K-8663) as an additive, 3 ppm of chlorine ion (as chlorine ion in hydrochloric acid), and 0.5 of gelatin in an acidic copper plating bath containing 270 g / of copper sulfate and 100 g / of sulfuric acid. An electrolyte was prepared by adding ppm.
この電解液を試験用製箔装置（直径３５０mm、長さ３５
０mmのチタン製回転ドラムを陰極となし、該ドラムの下
方半分に近接させて半円型の純鉛陽極を対向配置させそ
の両極の間隙、即ち、極間距離を５mmとした）を用い、
上記のとおり調整された電解液を浴温４５℃に保持し、
両極の間を液流速0.2m/sで循環させた。This electrolyte was used in a test foil-making device (diameter 350 mm, length 35
A 0 mm titanium rotary drum is used as a cathode, and a semi-circular pure lead anode is arranged in close proximity to the lower half of the drum so that the gap between both electrodes, that is, the distance between the electrodes is 5 mm.
The electrolytic solution prepared as described above is kept at a bath temperature of 45 ° C.,
The liquid was circulated between both electrodes at a liquid flow rate of 0.2 m / s.
次に銅箔の厚みが３０μになるようにチタン製回転ドラ
ムを回転させ、電流密度３０Ａ／dm2で通電し、該陰極
上に銅を電解析出させ、これをはがし電解銅箔を製造し
た。Next, the titanium rotary drum was rotated so that the thickness of the copper foil was 30 μ, and current was applied at a current density of 30 A / dm 2 , copper was electrolytically deposited on the cathode, and this was peeled off to produce an electrolytic copper foil. .
この銅箔をサンプルとして、下記の特性について測定
し、その結果を一括して表に示す。Using this copper foil as a sample, the following characteristics were measured, and the results are collectively shown in the table.
（１）抗張力(kg/mm2) Ａ．常温時（２３℃）における測定値 Ｂ．加熱時（１８０℃雰囲気）における測定値 （２）伸び率（％） Ａ．常温時（２３℃）における測定値 Ｂ．加熱時（１８０℃雰囲気）における測定値 （１），（２）いずれもＪＩＳ Ｚ−２２０１（金属材
料引張試験片）の５号試験片を作成し、ＪＩＳＺ−２２
４１（金属材料引張試験方法）を準用して測定した。(1) Tensile strength (kg / mm 2 ) A. Measured value at normal temperature (23 ° C.) B. Measured value during heating (at 180 ° C atmosphere) (2) Elongation (%) A. Measured value at normal temperature (23 ° C.) B. Measured values during heating (at 180 ° C. atmosphere) (1) and (2) For both JIS Z-2201 (metal material tensile test piece), No. 5 test piece was prepared, and JIS Z-22
41 (Metallic material tensile test method) was applied correspondingly.
（３）粗面側の凹凸の形状および均一性 走査型電子顕微鏡（ＳＥＭ）を用い、倍率１０００倍に
より粗面側の電析状態を観察した。(3) Concavo-convex shape and uniformity on rough surface side A scanning electron microscope (SEM) was used to observe the electrodeposited state on the rough surface side at a magnification of 1000 times.
表面の凹凸の形状は、円錐形、不定形のものが観察さ
れ、この中で円錐形のものは銅箔の剥離性（剥離強度）
が優れている。As for the shape of the surface irregularities, conical and irregular shapes are observed. Among them, the conical shape is the peelability of copper foil (peel strength).
Is excellent.
また、均一性については、○は凹凸の形状が円錐形であ
って、その底面の直径が５〜１０μｍのものが視野内の
凹凸のうちの６０％以上を占めることを意味し、×は前
記のような凹凸が４０％未満であることを意味する。Regarding the uniformity, ∘ means that the concavo-convex shape is conical, and the diameter of the bottom surface thereof is 5 to 10 μm occupies 60% or more of the concavity and convexity in the visual field, and x is the above. It means that such unevenness is less than 40%.
実施例２〜１１、比較例１〜７ メッキ浴濃度、添加剤の種類、添加剤濃度、電解条件を
表示のように変化させて実施例１と同様の製箔装置を用
い、各種の銅箔を製造した。Examples 2 to 11, Comparative Examples 1 to 7 Various copper foils were prepared by changing the plating bath concentration, the type of additive, the additive concentration, and the electrolysis conditions as shown, and using the same foil-making apparatus as in Example 1. Was manufactured.
これら各銅箔につき、実施例１と同様仕様で各特性を測
定しその結果を一括して表に示す。The characteristics of each of these copper foils were measured with the same specifications as in Example 1, and the results are collectively shown in the table.
本発明の方法により得られた電解銅箔は、表から明らか
なように加熱時の伸び率が優れており、なおかつ、粗面
側の電析状態の観察から形状が円錐形をしており、また
その均一性が優れている。他方、比較例においては、添
加剤が無添加状態のときは、銅箔自体にピンホール、銅
粒が発生しやすく、また、添加剤の種類が１種または２
種のときには、目的とする特性を同時に満足することは
できない。 The electrolytic copper foil obtained by the method of the present invention has excellent elongation upon heating as is clear from the table, and still has a conical shape from the observation of the electrodeposited state on the rough surface side, Moreover, its uniformity is excellent. On the other hand, in the comparative example, when the additive is not added, pinholes and copper particles are easily generated in the copper foil itself, and the type of the additive is 1 type or 2 types.
In the case of seeds, the desired characteristics cannot be satisfied at the same time.
本発明の方法により得られた電解銅箔は、加熱時の伸び
率と粗面側の表面状態に優れたものであり、この電解銅
箔は、特に多層プリント配線板に用いた場合、信頼性、
および剥離強度に優れた配線板が得られ、その工業的価
値は極めて大である。The electrolytic copper foil obtained by the method of the present invention is excellent in the elongation at heating and the surface condition on the rough surface side, and this electrolytic copper foil is particularly reliable when used in a multilayer printed wiring board. ,
Also, a wiring board excellent in peel strength can be obtained, and its industrial value is extremely large.
Claims (4)
浴を用いて電解銅箔を製造するにあたり、該メッキ浴
に、ヒドロキシアルキルアミン、塩素イオン、およびゼ
ラチンを添加して電解処理を行うことを特徴とする電解
銅箔の製造方法。1. When producing an electrolytic copper foil using an acidic copper plating bath containing copper sulfate and sulfuric acid as main components, a hydroxyalkylamine, chlorine ion, and gelatin are added to the plating bath for electrolytic treatment. A method for producing an electrolytic copper foil, which is characterized in that the method is performed.
ルキルアミン0.5〜１５ppm、塩素イオン１〜３０ppmお
よびゼラチン0.1〜５ppmである特許請求の範囲第１項記
載の電解銅箔の製造方法。2. The method for producing an electrolytic copper foil according to claim 1, wherein the additive concentration in the plating bath is 0.5 to 15 ppm of hydroxyalkylamine, 1 to 30 ppm of chloride ion and 0.1 to 5 ppm of gelatin.
シアルキルアミンである特許請求の範囲第１項または第
２項記載の電解銅箔の製造方法。3. The method for producing an electrolytic copper foil according to claim 1, wherein the hydroxyalkylamine is trihydroxyalkylamine.
ノールアミンである特許請求の範囲第３項記載の電解銅
箔の製造方法。4. The method for producing an electrolytic copper foil according to claim 3, wherein the trihydroxyalkylamine is triethanolamine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14698587A JPH0631461B2 (en) | 1987-06-15 | 1987-06-15 | Method for manufacturing electrolytic copper foil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14698587A JPH0631461B2 (en) | 1987-06-15 | 1987-06-15 | Method for manufacturing electrolytic copper foil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63310989A JPS63310989A (en) | 1988-12-19 |
| JPH0631461B2 true JPH0631461B2 (en) | 1994-04-27 |
Family
ID=15420014
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14698587A Expired - Fee Related JPH0631461B2 (en) | 1987-06-15 | 1987-06-15 | Method for manufacturing electrolytic copper foil |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0631461B2 (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2706291B2 (en) * | 1989-01-12 | 1998-01-28 | 日鉱金属株式会社 | Painting support |
| US5181770A (en) * | 1989-04-19 | 1993-01-26 | Olin Corporation | Surface topography optimization through control of chloride concentration in electroformed copper foil |
| US5215645A (en) * | 1989-09-13 | 1993-06-01 | Gould Inc. | Electrodeposited foil with controlled properties for printed circuit board applications and procedures and electrolyte bath solutions for preparing the same |
| US5403465A (en) * | 1990-05-30 | 1995-04-04 | Gould Inc. | Electrodeposited copper foil and process for making same using electrolyte solutions having controlled additions of chloride ions and organic additives |
| DE69125573T2 (en) * | 1990-05-30 | 1997-07-17 | Gould Electronics Inc | ELECTROPLATED COPPER FILM AND THE PRODUCTION THEREOF USING ELECTROLYTIC SOLUTIONS WITH LOW CONCENTRATIONS OF CHLORINE IONS |
| US5431803A (en) * | 1990-05-30 | 1995-07-11 | Gould Electronics Inc. | Electrodeposited copper foil and process for making same |
| TW432124B (en) * | 1996-05-13 | 2001-05-01 | Mitsui Mining & Amp Smelting C | Electrolytic copper foil with high post heat tensile strength and its manufacturing method |
| JPH10330983A (en) | 1997-05-30 | 1998-12-15 | Fukuda Metal Foil & Powder Co Ltd | Electrolytic copper foil and its production |
| JP2001011685A (en) * | 1999-06-30 | 2001-01-16 | Mitsui Mining & Smelting Co Ltd | Electrolytic copper foil and its production |
| JP3250994B2 (en) * | 1999-12-28 | 2002-01-28 | 三井金属鉱業株式会社 | Electrolytic copper foil |
| JP2002053993A (en) * | 2000-08-04 | 2002-02-19 | Mitsui Mining & Smelting Co Ltd | Electrolytic copper foil, and method of manufacturing the same |
| CN1946879B (en) | 2005-01-25 | 2010-05-05 | 日矿金属株式会社 | Copper electrolysis solution containing compound having specific skeleton as additive, and electrolytic copper foil produced therefrom |
| JP6067910B1 (en) * | 2015-11-04 | 2017-01-25 | 古河電気工業株式会社 | Electrolytic copper foil and lithium ion secondary battery using the electrolytic copper foil |
-
1987
- 1987-06-15 JP JP14698587A patent/JPH0631461B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63310989A (en) | 1988-12-19 |
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