JP2002105699A - Electrolytic copper foil for copper-clad laminate, and manufacturing method thereof - Google Patents
Electrolytic copper foil for copper-clad laminate, and manufacturing method thereofInfo
- Publication number
- JP2002105699A JP2002105699A JP2000302122A JP2000302122A JP2002105699A JP 2002105699 A JP2002105699 A JP 2002105699A JP 2000302122 A JP2000302122 A JP 2000302122A JP 2000302122 A JP2000302122 A JP 2000302122A JP 2002105699 A JP2002105699 A JP 2002105699A
- Authority
- JP
- Japan
- Prior art keywords
- copper foil
- electrolytic copper
- clad laminate
- electrolytic
- etching
- 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.)
- Pending
Links
Landscapes
- Laminated Bodies (AREA)
- Parts Printed On Printed Circuit Boards (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、フアィンピッチの
配線パターンを精密に形成できる銅張り積層板用電解銅
箔及びその製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrolytic copper foil for a copper-clad laminate capable of precisely forming a fine-pitch wiring pattern and a method for producing the same.
【０００２】[0002]
【従来の技術】プリント配線（回路）板に使用される銅
張り積層板用銅箔として、多くは電解銅箔が用いられ
る。一般に、この電解銅箔は回転するドラムに銅を電着
させ、該ドラム上に析出した銅析出物を剥離して連続的
に製造されているが、剥離した銅箔は、ドラムに接して
いた面が平坦な光沢面（Ｓ面）となり、その逆の面であ
る電解液側が粗面（Ｍ面）となる。そして、粗面は通常
多数の激しい凹凸を備えている。この電解銅箔がドラム
に析出する初期の段階の組織は、結晶粒径が小さくラン
ダムに配向しているが、析出が進行するにしたがって結
晶組織が析出方向に向かって方向性を生じ、かつ結晶粒
径も粗大化する。そして、従来の電解銅箔ではこのよう
な粗面の凹凸を利用して樹脂基板との接着強度を持たせ
ているが、さらに接着強度を向上させるために、上記の
凹凸にさらに銅の微粒子を付着させる粗化処理をするこ
とも行われている。この電解銅箔を銅張り積層板に使用
する場合は、通常ガラス・エポキシ樹脂基板等の片面又
は両面に、前記電解銅箔の粗面側を樹脂基板に向け、加
熱圧着又は接着剤を介して熱圧着して使用する。得られ
た銅張り積層板の銅箔はエッチングを行って配線パター
ンを形成している。2. Description of the Related Art As a copper foil for a copper-clad laminate used for a printed wiring (circuit) board, an electrolytic copper foil is often used. Generally, this electrolytic copper foil is manufactured continuously by electrodepositing copper on a rotating drum and peeling copper deposits deposited on the drum, but the peeled copper foil was in contact with the drum. The surface becomes a flat glossy surface (S surface), and the opposite surface, ie, the electrolyte side, becomes a rough surface (M surface). The rough surface usually has a number of severe irregularities. The structure of the initial stage in which the electrolytic copper foil is deposited on the drum has a small crystal grain size and is randomly oriented, but as the deposition proceeds, the crystal structure produces directionality in the direction of deposition, and The particle size also increases. And, in the conventional electrolytic copper foil, the adhesive strength to the resin substrate is given by utilizing such unevenness of the rough surface, but in order to further improve the adhesive strength, fine copper particles are further added to the unevenness. Roughening treatment for adhesion is also performed. When this electrolytic copper foil is used for a copper-clad laminate, usually on one or both surfaces of a glass epoxy resin substrate, the rough side of the electrolytic copper foil is directed to the resin substrate, and then heated and pressed or via an adhesive. Use by thermocompression bonding. The copper foil of the obtained copper clad laminate is etched to form a wiring pattern.
【０００３】近年、銅張り積層板にフアィンピッチの配
線パターンを形成する要求がある。エッチングでこのよ
うなフアィンピッチの配線パターンを形成する場合、従
来の電解銅箔を利用した銅張り積層板では、エッチング
の配線パターン断面が、図１に示すように、上底１が狭
く下底２が広がるという、台形状にエッチングされる現
象がおきた。同図１において、符号３は銅箔を符号４は
樹脂基板を示す。台形状の導電パターンの短絡を防止す
るためには、その間隔をより広くとる必要があるから、
微細なパターンは形成できなくなるという問題がある。
本来、理想的には、図２に示すように上底５と下底６が
整列し、ほぼ垂直になっているのが望ましいエッチング
パターン形状である。上記のような台形の配線パターン
は、切れが悪くフアィンピッチの配線パターンを形成す
ることができない。このエッチング不良の原因を究明す
ると、電解銅箔の粗面に原因があり、粗面の凹凸が激し
いほどエッチング時に残存するパターン部が裾を引き、
樹脂基板側に比べ上面が強くエッチングが進むことが分
かった。これをエッチングファクターで示すと次のよう
になる。すなわち、図３に示すように、銅箔の厚さａ
と、裾に幅広く過剰にエッチングされた部位の幅ｂに関
して、ａ／ｂ（エッチングファクター）が大きいほど、
フアィンピッチの配線パターンのエッチング性は良くな
る。In recent years, there has been a demand for forming a fine-pitch wiring pattern on a copper-clad laminate. In the case of forming such a fine pitch wiring pattern by etching, in a conventional copper-clad laminate using an electrolytic copper foil, the cross section of the wiring pattern of the etching is such that the upper base 1 is narrow and the lower base 2 is narrow as shown in FIG. The phenomenon of etching into a trapezoidal shape occurred. In FIG. 1, reference numeral 3 indicates a copper foil, and reference numeral 4 indicates a resin substrate. In order to prevent short-circuiting of the trapezoidal conductive pattern, it is necessary to make the interval wider,
There is a problem that a fine pattern cannot be formed.
Originally, ideally, it is a desirable etching pattern shape that the upper bottom 5 and the lower bottom 6 are aligned and almost vertical as shown in FIG. The trapezoidal wiring pattern as described above is poorly cut and cannot form a fine pitch wiring pattern. When investigating the cause of this etching failure, there is a cause on the rough surface of the electrolytic copper foil, and the pattern part remaining at the time of etching is pulled down as the roughness of the rough surface becomes severe,
It was found that etching progressed more strongly on the upper surface than on the resin substrate side. This is represented by the following etching factor. That is, as shown in FIG.
With respect to the width b of the over-etched portion widely on the skirt, the larger the a / b (etching factor),
The etching property of the fine pitch wiring pattern is improved.
【０００４】しかし、上記のような従来の電解銅箔の粗
面の凹凸は、製造工程において必然的に形成されるもの
で、むしろ樹脂基板との接着強度を向上させる意味から
推奨されていたものである。したがって、電解銅箔の製
造工程において、銅箔の粗面の凹凸を減少させ、またこ
れを微細化しょうとする発想は存在しなかった。しか
し、上記のように銅張り積層板にフアィンピッチの配線
パターンを形成する要求がある以上、電解銅箔の製造工
程において、凹凸の激しい粗面の改良を行う必要が生じ
た。However, the rough surface of the conventional electrolytic copper foil as described above is inevitably formed in the manufacturing process, and is rather recommended from the viewpoint of improving the adhesive strength to the resin substrate. It is. Therefore, in the manufacturing process of the electrolytic copper foil, there was no idea to reduce the unevenness of the rough surface of the copper foil and to reduce the roughness. However, since there is a demand for forming a fine pitch wiring pattern on a copper-clad laminate as described above, it has become necessary to improve a rough surface having severe irregularities in a manufacturing process of an electrolytic copper foil.
【０００５】[0005]
【発明が解決しょうとする課題】本発明は上記のような
問題点に鑑みてなされたものであり、その目的とすると
ころは、電解銅箔を利用した銅張り積層板をエッチング
でフアィンピッチの配線パターンを形成する際に、エッ
チング時に下底が裾を引き樹脂基板側に比べ上底の方が
強くエッチングされ、配線のパターンの断面形状が上底
が狭く下底が広がるという台形状にエッチングされる現
象を防止し、ほぼ垂直なエッチング面が得られる銅張り
積層板用電解銅箔を提供することにある。SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and an object of the present invention is to provide a fine pitch wiring by etching a copper-clad laminate using an electrolytic copper foil. When forming the pattern, the lower bottom is etched during etching, the upper bottom is etched more strongly than the resin substrate side, and the cross-sectional shape of the wiring pattern is etched in a trapezoidal shape in which the upper bottom is narrow and the lower bottom is widened An object of the present invention is to provide an electrolytic copper foil for a copper-clad laminate, which can prevent a phenomenon that occurs and can obtain a substantially vertical etched surface.
【０００６】[0006]
【課題を解決するための手段】以上から、本発明は １ 電解銅箔を用いた銅張り積層板用電解銅箔であっ
て、該電解銅箔の粗面の表面粗さＲｚが１．５〜４．０
μｍであることを特徴とする銅張り積層板用電解銅箔 ２ 電解銅箔の粗面の表面粗さＲｚが２．５〜３．０μ
ｍであることを特徴とする上記１記載の銅張り積層板用
電解銅箔 ３ 前記電解銅箔の粗面が電解研磨面又は化学研磨面で
あることを特徴とする上記１又は２に記載の銅張り積層
板 ４ 電解銅箔を用いた銅張り積層板用電解銅箔であっ
て、該電解銅箔の粗面を電解研磨又は化学研磨し、さら
に電解研磨又は化学研磨した面を粗化処理し、その粗化
処理した面の粗さＲｚが１．５〜４．０μｍであること
を特徴とする上記３記載の銅張り積層板用電解銅箔 ５ 粗化処理した面の粗さＲｚが１．５〜２．５μｍで
あることを特徴とする上記４記載の銅張り積層板用電解
銅箔 ６ 粗化処理の粒子の大きさが１．５μｍ以下であるこ
とを特徴とする上記４又は５記載の銅張り積層板用電解
銅箔 ７ 電解銅箔の粗面を電解研磨又は化学研磨し、該電解
銅箔の粗面の表面粗さＲｚを１．５〜４．０μｍとする
ことを特徴とする銅張り積層板用電解銅箔の製造方法 ８ 電解銅箔の粗面を電解研磨又は化学研磨し、該電解
銅箔の粗面の表面粗さＲｚを１．５〜２．５μｍとする
ことを特徴とする上記７記載の銅張り積層板用電解銅箔
の製造方法 ９ 電解銅箔の粗面を電解研磨又は化学研磨し、さらに
電解研磨又は化学研磨した面を粗化処理し、その粗化処
理した面の粗さＲｚを１．５〜４．０μｍとすることを
特徴とする上記８記載の銅張り積層板用電解銅箔の製造
方法 １０ 粗化処理した面の粗さＲｚを１．５〜２．５μｍ
とすることを特徴とする上記９記載の銅張り積層板用電
解銅箔の製造方法 １１ 粗化処理の粒子の大きさが１．５μｍ以下である
ことを特徴とする上記９又は１０記載の銅張り積層板用
電解銅箔の製造方法 １２ 塩化物イオン濃度が２ｍｇ／ｌ以下である硫酸酸
性硫酸銅溶液を用いて電解銅箔を製造することを特徴と
する上記９〜１１のそれぞれに記載の銅張り積層板用電
解銅箔の製造方法。を提供する。As described above, the present invention relates to (1) an electrolytic copper foil for a copper-clad laminate using an electrolytic copper foil, wherein the rough surface of the electrolytic copper foil has a surface roughness Rz of 1.5; ~ 4.0
The electrolytic copper foil for a copper-clad laminate is characterized in that the surface roughness Rz of the rough surface of the electrolytic copper foil is 2.5 to 3.0 μm.
m, wherein the roughened surface of the electrolytic copper foil is an electrolytically polished surface or a chemically polished surface. Copper-clad laminate 4 An electrolytic copper foil for a copper-clad laminate using an electrolytic copper foil, wherein the roughened surface of the electrolytic copper foil is electrolytically polished or chemically polished, and the electrolytically polished or chemically polished surface is roughened. The electrolytic copper foil for a copper-clad laminate according to the above item 3, wherein the roughness Rz of the roughened surface is 1.5 to 4.0 μm. The electrolytic copper foil for a copper-clad laminate according to the above item 4, wherein the particle size of the roughening treatment is 1.5 μm or less. Electrolytic copper foil for a copper-clad laminate according to 5 7. The rough surface of the electrolytic copper foil is electrolytically or chemically polished to obtain a rough surface of the electrolytic copper foil. 8. A method for producing an electrolytic copper foil for a copper-clad laminate, characterized in that the surface roughness Rz of the copper foil is 1.5 to 4.0 μm. 9. The method for producing an electrolytic copper foil for a copper-clad laminate according to 7 above, wherein the surface roughness Rz of the rough surface is 1.5 to 2.5 μm. The copper-clad laminate according to the above item 8, wherein the polished surface is further subjected to a roughening treatment on the surface subjected to the electrolytic polishing or the chemical polishing, and the roughness Rz of the roughened surface is set to 1.5 to 4.0 μm. Method for producing electrolytic copper foil for use 10 Roughness Rz of roughened surface is 1.5 to 2.5 μm
11. The method for producing an electrolytic copper foil for a copper-clad laminate according to the above item 9, wherein the particle size of the roughening treatment is 1.5 μm or less. 12. The method for producing an electrolytic copper foil for a laminated laminate, wherein the electrolytic copper foil is produced using a sulfuric acid acidic copper sulfate solution having a chloride ion concentration of 2 mg / l or less. A method for producing an electrolytic copper foil for a copper-clad laminate. I will provide a.
【０００７】[0007]
【発明の実施の形態】電解銅箔は回転するドラムに銅を
電着させ、該ドラム上に析出した銅析出物を剥離して連
続的に製造されるが、上記の通りドラムに接していた側
の面が平坦な光沢面となり、その逆の面である電解液側
が凹凸の激しい粗面となる。この電解銅箔の析出初期の
段階の組織は、結晶粒径が小さくランダムに配向してい
るが、析出が進行するにしたがって結晶組織は析出方向
に向かって方向性を生じ、かつ結晶粒径が大きくなる傾
向がある。本発明においては、このような電解による結
晶組織の改善を行うことが必要であるとの知見から、電
解銅箔の製造工程において、上記のような凹凸の激しい
電解銅箔の粗面を電解研磨又は化学研磨し、該電解銅箔
の粗面の表面粗さＲｚを１．５〜４．０μｍとするもの
である。電解銅箔の粗面を電解研磨は化学研磨した後、
さらに研磨面を粗化処理し、その粗化処理した面の粗さ
Ｒｚを１．５〜４．０μｍとするのが望ましい。これに
よって、エッチングファクターを良好にさせるだけでな
く、ピール強度も向上させることができる。この場合、
電解研磨又は化学研磨後の粗化処理の粒子の大きさは
１．５μｍ以下であることが望ましい。BEST MODE FOR CARRYING OUT THE INVENTION Electrolytic copper foil is manufactured continuously by electrodepositing copper on a rotating drum and peeling off copper deposits deposited on the drum. The surface on the side is a flat glossy surface, and the opposite side, the electrolyte side, is a rough surface with severe irregularities. The structure at the initial stage of the deposition of the electrolytic copper foil has a small crystal grain size and is randomly oriented, but as the deposition proceeds, the crystal structure produces directionality in the direction of the deposition, and the crystal grain size is increased. Tends to be larger. In the present invention, from the knowledge that it is necessary to improve the crystal structure by such electrolysis, in the manufacturing process of the electrolytic copper foil, the rough surface of the electrolytic copper foil having severe irregularities as described above is electrolytically polished. Alternatively, it is chemically polished to make the surface roughness Rz of the rough surface of the electrolytic copper foil 1.5 to 4.0 μm. After the electrolytic polishing chemically polishing the rough surface of the electrolytic copper foil,
Further, it is desirable that the polished surface be subjected to a roughening treatment, and the roughness Rz of the roughened surface be set to 1.5 to 4.0 μm. As a result, not only the etching factor can be improved, but also the peel strength can be improved. in this case,
The size of the particles in the roughening treatment after the electrolytic polishing or the chemical polishing is desirably 1.5 μm or less.
【０００８】Ｒｚが４．０μｍを超えると、銅張り積層
板のエッチングの際、精度良くフアィンピッチの配線パ
ターンを形成するという本発明の効果が十分に得ること
ができず、またＲｚが１．５μｍ未満では、樹脂基板と
の接着強度が低下するのでＲｚを１．５μｍ以上とす
る。好ましくは該電解銅箔の粗面又は粗化面の表面粗さ
Ｒｚを１．５〜２．５μｍとするのが良い。これによ
り、従来の電解銅箔の製造工程で必然的に形成されてい
た粗面の激しい凹凸を緩和させ、電解銅箔を利用した銅
張り積層板をエッチングにより配線パターンを形成する
際、上底が狭く下底が広がるという台形状のエッチング
現象を効果的に防止することが可能となり、ほぼ垂直な
エッチング面が得られる。If Rz exceeds 4.0 μm, the effect of the present invention of forming a fine-pitch wiring pattern with high accuracy during etching of the copper-clad laminate cannot be sufficiently obtained. If it is less than 1, the bonding strength with the resin substrate is reduced, so Rz is set to 1.5 μm or more. Preferably, the surface roughness Rz of the roughened or roughened surface of the electrolytic copper foil is set to 1.5 to 2.5 μm. This alleviates the rough irregularities that are inevitably formed in the conventional electrolytic copper foil manufacturing process, and when forming a wiring pattern by etching a copper-clad laminate using electrolytic copper foil, And the trapezoidal etching phenomenon that the bottom is widened can be effectively prevented, and a substantially vertical etching surface can be obtained.
【０００９】電解銅箔の粗面を研磨する場合、例えば電
解銅箔の表面粗化等の連続的な複数の電気化学的表面処
理の中に電解研磨工程を設け、該工程の電解液中で銅箔
から電流を集電するための陰極板（電極に直結した）を
銅箔に対面して配置し、液中集電法により電解研磨を行
うことができる。これによって、連続的な銅箔の電解研
磨を効果的に実施できる。本発明は上記の通り、電解銅
箔の粗面の表面粗さを低減するのが目的であるが、必要
に応じて電解銅箔の粗面の粗化処理又は光沢面の各種電
気化学的表面処理を併用することは何ら問題がなく、本
発明はこれらを包含するものである。また、上記の電解
研磨に替えて化学研磨を実施しても同様の効果を得るこ
とができる。In the case of polishing the rough surface of the electrolytic copper foil, an electrolytic polishing step is provided in a plurality of continuous electrochemical surface treatments such as surface roughening of the electrolytic copper foil, and the electrolytic polishing in the electrolytic solution in the step is performed. A cathode plate (directly connected to an electrode) for collecting current from the copper foil is placed facing the copper foil, and electrolytic polishing can be performed by a submerged current collection method. Thereby, continuous electropolishing of the copper foil can be effectively performed. The present invention, as described above, aims to reduce the surface roughness of the rough surface of the electrolytic copper foil, but if necessary, roughening treatment of the rough surface of the electrolytic copper foil or various electrochemical surfaces of the glossy surface There is no problem in using the treatment in combination, and the present invention includes these. The same effect can be obtained by performing chemical polishing in place of the above electrolytic polishing.
【００１０】電解研磨条件の一例を示すと、次の通りで
ある。 （研磨液） Ｈ３ＰＯ３ ： ７０ｖｏｌ％ 水 ： ３０ｖｏｌ％ （研磨条件） 電流密度（Ｄｋ）：１０〜２０Ａ／ｄｍ２ 時 間： ３０〜６０秒 電 圧： ３Ｖ また、電解研磨又は化学研磨した面の粗化処理には、従
来公知の（例えば、特許番号１９２７３４０号に記載さ
れている）微細な粗化処理を施すことができる。具体的
な粗化処理の例として、次のＣｕ−Ｃｏ−Ｎｉ三元系合
金めっきを挙げることができる。しかし、本発明の粗化
処理はこれ以外の処理を使用することができ、本発明の
条件に適合するものであれば、特に制限はない。 （浴組成及びめっき条件） Ｃｕ： １０〜２０ｇ／ｌ Ｃｏ： １〜１０ｇ／ｌ Ｎｉ： １〜１０ｇ／ｌ ｐＨ： １〜４ 温度： ４０〜５０°Ｃ 電流密度Ｄｋ： ２０〜３０Ａ／ｄｍ２ 時間： １〜５秒An example of the electropolishing conditions is as follows. (Polishing liquid) H 3 PO 3: 70vol% Water: 30 vol% (Polishing conditions) Current density (D k): 10~20A / dm between 2:00: 30-60 sec Voltage: 3V Further, electrolytic polishing or chemical polishing For the surface roughening treatment, a conventionally known fine roughening treatment (for example, described in Japanese Patent No. 1927340) can be performed. As a specific example of the roughening treatment, the following Cu-Co-Ni ternary alloy plating can be given. However, any other treatment can be used for the roughening treatment of the present invention, and there is no particular limitation as long as it meets the conditions of the present invention. (Bath composition and plating conditions) Cu: 10 to 20 g / l Co: 1 to 10 g / l Ni: 1 to 10 g / l pH: 1 to 4 Temperature: 40 to 50 ° C Current density Dk: 20 to 30 A / dm 2 Time: 1-5 seconds
【００１１】さらに本発明は、前記電解銅箔の電解研磨
に加えて、さらに塩化物イオン濃度を２ｍｇ／ｌ以下と
する硫酸酸性硫酸銅溶液を用いて電解銅箔を製造する技
術を併用することが、一層効果的であることを見出し
た。この塩化物イオン濃度を制限することにより、電解
銅箔の結晶組織が微細となり、特定方向に結晶成長せ
ず、凹凸の少ない組織を得ることができる。これによっ
て、電解研磨の量を適宜調整することができ、上底が狭
く下底が広がるという台形状にエッチングされるという
現象を防止することができ、フアィンピッチの配線パタ
ーンを効果的に形成することができる。Further, in the present invention, in addition to the electropolishing of the electrolytic copper foil, a technique for producing an electrolytic copper foil using a sulfuric acid acidic copper sulfate solution having a chloride ion concentration of 2 mg / l or less is also used. Was found to be even more effective. By limiting the chloride ion concentration, the crystal structure of the electrodeposited copper foil becomes fine, and a crystal structure having few irregularities without crystal growth in a specific direction can be obtained. This makes it possible to appropriately adjust the amount of electrolytic polishing, prevent a trapezoidal etching in which the upper bottom is narrow and the lower bottom is widened, and effectively form a fine-pitch wiring pattern. Can be.
【００１２】この場合塩化物イオン濃度が２ｍｇ／ｌを
超えると、塩化物イオン濃度を制限する効果が殆ど期待
できない。したがって、塩化物イオン濃度が２ｍｇ／ｌ
以下とする必要がある。好ましくは塩化物イオン濃度が
０．５ｍｇ／ｌ以下である。また、銅箔の製造において
通常使用されているにかわの添加量を、０．５ｍｇ／ｌ
以下、好ましくは０．２ｍｇ／ｌ以下とすることによ
り、前記特定方向の結晶成長を抑制し凹凸の少ない電解
銅箔を得ることに、より有効であることが分かった。に
かわの添加量が０．５ｍｇ／ｌを超えると、それによる
効果が殆ど期待できない。したがって、０．５ｍｇ／ｌ
以下とする必要がある。このような塩化物イオン濃度と
にかわの量を減少させた電解銅箔の製造工程により得ら
れた銅箔は、耐折曲げ性に優れており、また加熱処理に
よる再結晶性も良好であるという効果もあることが確認
できた。In this case, if the chloride ion concentration exceeds 2 mg / l, almost no effect of limiting the chloride ion concentration can be expected. Therefore, when the chloride ion concentration is 2 mg / l
It is necessary to: Preferably, the chloride ion concentration is 0.5 mg / l or less. The amount of glue usually used in the production of copper foil was 0.5 mg / l.
It has been found that setting the content to 0.2 mg / l or less is more effective in suppressing the crystal growth in the specific direction and obtaining an electrolytic copper foil with less unevenness. When the amount of glue exceeds 0.5 mg / l, the effect due to this is hardly expected. Therefore, 0.5 mg / l
It is necessary to: It is said that the copper foil obtained by the production process of the electrolytic copper foil with the reduced chloride ion concentration and the amount of glue has excellent bending resistance and also has good recrystallization by heat treatment. It was confirmed that there was an effect.
【００１３】電解銅箔の製造工程における好ましい電解
液組成と電解条件の一例を示すと、次の通りである。 （電解液組成） 硫酸銅（ＣｕＳＯ４・５Ｈ２Ｏ）：２００〜６００ｇ／
ｌ 硫酸（Ｈ２ＳＯ４）：２０〜２００ｇ／ｌ 塩化物イオン（Ｃｌ−）：２ｍｇ／ｌ以下、好ましくは
０．５ｍｇ／ｌ以下 にかわ：添加せず。または添加する場合には、０．５ｍ
ｇ／ｌ以下、好ましくは０．２ｍｇ／ｌ以下 （電解条件） 電解液温度：２０〜７０°Ｃ 電流密度：５０〜２００Ａ／ｄｍ２ 電解時間：１０〜３００秒 アノード：鉛（Ｐｂ）An example of a preferred electrolytic solution composition and electrolytic conditions in the production process of the electrolytic copper foil is as follows. (Electrolyte composition) copper sulfate (CuSO 4 · 5H 2 O) : 200~600g /
1 Sulfuric acid (H 2 SO 4 ): 20 to 200 g / l Chloride ion (Cl − ): 2 mg / l or less, preferably 0.5 mg / l or less Glue: not added. Or 0.5m if added
g / l or less, preferably 0.2 mg / l or less (Electrolysis conditions) Electrolyte temperature: 20 to 70 ° C Current density: 50 to 200 A / dm 2 Electrolysis time: 10 to 300 seconds Anode: Lead (Pb)
【００１４】[0014]
【実施例】次に、実施例に基づいて説明する。なお、本
実施例は好適な一例を示すもので、本発明はこれらの実
施例に限定されるものではない。したがって、本発明の
技術思想に含まれる変形、他の実施例又は態様は、全て
本発明に含まれる。Next, an embodiment will be described. Note that the present embodiment shows a preferred example, and the present invention is not limited to these embodiments. Therefore, all modifications, other examples or aspects included in the technical concept of the present invention are included in the present invention.
【００１５】（実施例１）ドラム型カソードを用いて連
続的に厚さ１８〜１２μｍの電解銅箔を製造した。電解
液組成は、硫酸銅（ＣｕＳＯ４・５Ｈ２Ｏ）：５００ｇ
／ｌ、硫酸（Ｈ２ＳＯ４）：１００ｇ／ｌ、塩化物イオ
ン（Ｃｌ−）：０．４５ｍｇ／ｌ、にかわ：０．５ｍｇ
／Ｌ。 電解液温度：６０°Ｃ、電流密度：１００Ａ／ｄｍ２の
条件で電解した。これによって得られた電解銅箔の粗面
の表面粗さはＲｚ４．４〜４．８μｍであった。なお、
光沢面の表面粗さはＲｚ１．２μｍであった。この試料
をさらに５個に分け、研磨液としてＨ３ＰＯ３：７０ｖ
ｏｌ％、水：３０ｖｏｌ％を使用し、研磨条件を電流密
度：１０〜２０Ａ／ｄｍ２、時間：３０〜６０秒、電
圧：３Ｖの範囲で変化させ、前記５個の試料についてそ
れぞれ電解銅箔の粗面の電解研磨を実施し、さらにこれ
らの処理面に、上記の微細な粗化処理を施して、該粗面
の最終の表面粗さをＲｚ４．０μｍ、Ｒｚ３．５μｍ、
Ｒｚ２．５μｍ、Ｒｚ２．０μｍ、Ｒｚ１．５μｍと
し、これらをそれぞれ試料１、試料２、試料３、試料
４、試料５とした。(Example 1) An electrolytic copper foil having a thickness of 18 to 12 µm was manufactured continuously using a drum type cathode. Electrolyte composition, copper sulfate (CuSO 4 · 5H 2 O) : 500g
/ L, sulfuric acid (H 2 SO 4 ): 100 g / l, chloride ion (Cl − ): 0.45 mg / l, glue: 0.5 mg
/ L. Electrolysis was performed under the conditions of an electrolyte temperature: 60 ° C. and a current density: 100 A / dm 2 . The surface roughness of the rough surface of the electrolytic copper foil thus obtained was Rz 4.4 to 4.8 μm. In addition,
The surface roughness of the glossy surface was Rz 1.2 μm. This sample was further divided into five pieces, and H 3 PO 3 : 70 v was used as a polishing liquid.
ol%, water: 30 vol%, and the polishing conditions were changed in the range of current density: 10 to 20 A / dm 2 , time: 30 to 60 seconds, and voltage: 3 V. Electrolytic copper foil was used for each of the five samples. Is subjected to electropolishing, and these treated surfaces are subjected to the above-mentioned fine roughening treatment, so that the final surface roughness of the roughened surface is Rz 4.0 μm, Rz 3.5 μm,
Rz 2.5 μm, Rz 2.0 μm, and Rz 1.5 μm, which were designated as Sample 1, Sample 2, Sample 3, Sample 4, and Sample 5, respectively.
【００１６】上記によって得られた試料１、試料２、試
料３、試料４、試料５の電解銅箔の粗面側をガラス・エ
ポキシ樹脂基板の片面に加圧接着して各銅張り積層板を
作製した。さらに、この銅張り積層板にドライフィルム
をラミネートし、レジスト幅１００μｍ、回路間隔１０
０μｍのパターンフイルムを使用してＵＶ露光により回
路パターンを作製した。次に、これらを塩化銅エッチン
グ液を用いてエッチングした。この結果、得られた配線
パターンの上底と下底の長さは、それぞれ表１に示す通
りとなった。同様に、エッチングファクター（ａ／ｂ）
も同表１に示す。なお、これらは、各試料について１０
個のテスト結果の平均値を示す。The copper-clad laminates of each of the sample 1, sample 2, sample 3, sample 4, and sample 5 obtained above were bonded by pressing the rough side of the electrolytic copper foil to one surface of a glass epoxy resin substrate. Produced. Further, a dry film was laminated on the copper-clad laminate, and a resist width of 100 μm and a circuit interval of 10
A circuit pattern was prepared by UV exposure using a 0 μm pattern film. Next, these were etched using a copper chloride etching solution. As a result, the lengths of the upper and lower bottoms of the obtained wiring pattern were as shown in Table 1, respectively. Similarly, etching factor (a / b)
Table 1 also shows. Note that these are 10
Shows the average of the test results.
【００１７】（比較例１）実施例１と同一の条件で作製
した電解銅箔（粗面の表面粗さはＲｚ４．５μｍであっ
た。光沢面の表面粗さはＲｚ１．２μｍ）を使用し、こ
の試料をさらに２個に分け、実施例１と同様の研磨液で
あるＨ３ＰＯ３：７０ｖｏｌ％、水：３０ｖｏｌ％を使
用し、研磨条件を電流密度：１０〜２０Ａ／ｄｍ２、時
間：３０〜６０秒、電圧：３Ｖの範囲で変化させ、前記
２個の試料についてそれぞれ電解銅箔の粗面の電解研磨
を実施し、さらにこれらの処理面に実施例と同様の微細
な粗化処理を施して、該粗面の最終の表面粗さをＲｚ
４．２μｍ、Ｒｚ１．０μｍの試料６、試料７を作製し
た。上記によって得られた試料６及び試料７の電解銅箔
の粗面側をガラス・エポキシ樹脂基板の片面に加圧接着
して各銅張り積層板を作製した。この銅張り積層板にド
ライフィルムをラミネートし、レジスト幅１００μｍ、
回路間隔１００μｍのパターンフイルムを使用してＵＶ
露光により回路パターンを作製した。さらにこれらを、
塩化銅エッチング液を用いてエッチングした。この結果
得られた配線パターンの上底と下底の長さは、それぞれ
表１に示す通りとなった。同様に、エッチングファクタ
ー（ａ／ｂ）も同表１に示す。なお、これらは、各試料
について１０個のテスト結果の平均値を示す。Comparative Example 1 An electrolytic copper foil (rough surface roughness Rz 4.5 μm; glossy surface roughness Rz 1.2 μm) produced under the same conditions as in Example 1 was used. divide the sample further two, example 1 and the same polishing solution in which H 3 PO 3: 70vol%, water: using a 30 vol%, the current density polishing conditions: 10~20A / dm 2, time : Within a range of 30 to 60 seconds and a voltage of 3 V, the two samples were subjected to electrolytic polishing of the roughened surface of the electrolytic copper foil, and the roughened surfaces of these treated surfaces were finely roughened as in the example. Treatment to give the final surface roughness of the rough surface Rz
Samples 6 and 7 each having 4.2 μm and Rz of 1.0 μm were prepared. The copper-clad laminates were prepared by pressure bonding the rough sides of the electrolytic copper foils of Samples 6 and 7 obtained above to one surface of the glass epoxy resin substrate. A dry film is laminated on this copper-clad laminate, and the resist width is 100 μm.
UV using a pattern film with a circuit interval of 100 μm
A circuit pattern was prepared by exposure. In addition, these
Etching was performed using a copper chloride etching solution. The lengths of the upper and lower bottoms of the wiring pattern obtained as a result are as shown in Table 1, respectively. Similarly, Table 1 also shows the etching factors (a / b). In addition, these show the average value of ten test results about each sample.
【００１８】[0018]
【表１】 [Table 1]
【００１９】上記表１から明らかなように、本発明の実
施例（試料No．１〜５）においては、エッチングファク
ター（ａ／ｂ）は、６．３〜７．９と良好であり、表面
粗さ（Ｒｚ）が小さくなるにしたがって、その数値は大
きくなる。逆にピール強度は小さくなるが、０．９７〜
０．８１ｋｇ／ｃｍの範囲にあり、良好である。総合的
な評価としては、ピール強度及びエッチングファクター
が優れており、銅張り積層板をエッチングで配線パター
ンを形成する際に、配線断面において台形状のエッチン
グ現象を効果的に抑止することができ、ほぼ垂直なエッ
チング面が得られ、フアィンピッチの配線パターンの形
成に好適な銅張り積層板用電解銅箔を得ることができ
る。これに対し、比較例の試料No．６の表面粗さがＲｚ
４．２μｍのものは、エッチングファクターが５．９と
悪くなり、配線断面において台形状のエッチング現象を
生ずることとなる。比較例の試料No．７の表面粗さがＲ
ｚ１．０μｍのものは、エッチングファクターが良好で
あるが、ピール強度が０．５０（ｋｇ／ｃｍ）に低下す
るという問題が生じた。したがって、この試料No．７は
銅張り積層板用電解銅箔として適切でない。上記におい
て、電解銅箔の粗面の電解研磨を実施し、さらにこれら
の処理面に、微細な粗化処理を施したものを例示した
が、粗化処理をしない場合でも電解銅箔の粗面の表面粗
さＲｚが１．５〜４．０μｍであるものはいずれも優れ
たピール強度とエッチングファクターを示した。As is clear from Table 1, in the examples of the present invention (samples Nos. 1 to 5), the etching factor (a / b) was as good as 6.3 to 7.9, and the surface was excellent. The numerical value increases as the roughness (Rz) decreases. Conversely, the peel strength is small, but 0.97 ~
It is in the range of 0.81 kg / cm, which is good. As a comprehensive evaluation, peel strength and etching factor are excellent, and when forming a wiring pattern by etching a copper clad laminate, it is possible to effectively suppress trapezoidal etching phenomenon in the wiring cross section, A substantially vertical etched surface is obtained, and an electrolytic copper foil for a copper-clad laminate suitable for forming a fine-pitch wiring pattern can be obtained. On the other hand, the sample No. The surface roughness of Rz is 6.
In the case of 4.2 μm, the etching factor is as poor as 5.9, and a trapezoidal etching phenomenon occurs in the cross section of the wiring. Sample No. of Comparative Example 7 has a surface roughness of R
Those having a z of 1.0 μm have a good etching factor, but have a problem that the peel strength is reduced to 0.50 (kg / cm). Therefore, this sample No. 7 is not suitable as an electrolytic copper foil for a copper-clad laminate. In the above, the electrolytic polishing of the roughened surface of the electrolytic copper foil was performed, and the roughened surface of the electrolytic copper foil was further subjected to fine roughening treatment. Each having a surface roughness Rz of 1.5 to 4.0 μm exhibited excellent peel strength and etching factor.
【００２０】[0020]
【発明の効果】本発明の銅張り積層板用電解銅箔は、該
銅張り積層板をエッチングで配線パターンを形成する際
に、配線断面において上底が狭く下底が広がるという従
来の銅張り積層板で見られた台形状のエッチング現象を
効果的に抑止することができ、ほぼ垂直なエッチング面
が得られるフアィンピッチの配線パターンの形成に好適
な銅張り積層板用電解銅箔を得ることができる。The electrolytic copper foil for a copper-clad laminate according to the present invention is a conventional copper-clad laminate in which, when a wiring pattern is formed by etching the copper-clad laminate, the upper bottom is narrow and the lower bottom is wide in the cross section of the wiring. It is possible to effectively suppress the trapezoidal etching phenomenon seen in the laminate and obtain an electrolytic copper foil for a copper-clad laminate suitable for forming a fine pitch wiring pattern in which a substantially vertical etched surface is obtained. it can.
【図１】従来の電解銅箔を利用した銅張り積層板のエッ
チングによる配線パターン断面の説明図である。FIG. 1 is an explanatory view of a cross section of a wiring pattern obtained by etching a conventional copper-clad laminate using an electrolytic copper foil.
【図２】理想的な銅張り積層板のエッチングによる配線
パターン断面の説明図である。FIG. 2 is an explanatory diagram of a wiring pattern cross section obtained by etching an ideal copper-clad laminate.
【図３】エッチングファクターの概略説明図である。FIG. 3 is a schematic explanatory diagram of an etching factor.
１、５ 上底 ２、６ 下底 ３ 銅箔 ４ 樹脂基板 ５ 上底 ６ 下底 ａ 配線パターン（銅箔）の厚さ ｂ 裾に幅広く過剰にエッチングされた部位の幅 1, 5 Upper bottom 2, 6 Lower bottom 3 Copper foil 4 Resin substrate 5 Upper bottom 6 Lower bottom
Claims (12)
箔であって、該電解銅箔の粗面の表面粗さＲｚが１．５
〜４．０μｍであることを特徴とする銅張り積層板用電
解銅箔。1. An electrolytic copper foil for a copper-clad laminate using an electrolytic copper foil, wherein the rough surface of the electrolytic copper foil has a surface roughness Rz of 1.5.
An electrolytic copper foil for a copper-clad laminate, having a thickness of from 4.0 to 4.0 μm.
〜２．５μｍであることを特徴とする請求項１記載の銅
張り積層板用電解銅箔。2. The roughened surface of the electrolytic copper foil has a surface roughness Rz of 1.5.
The electrolytic copper foil for a copper-clad laminate according to claim 1, wherein the thickness is from 2.5 to 2.5 m.
学研磨面であることを特徴とする請求項１又は２に記載
の銅張り積層板。3. The copper clad laminate according to claim 1, wherein the roughened surface of the electrolytic copper foil is an electropolished surface or a chemically polished surface.
箔であって、該電解銅箔の粗面を電解研磨又は化学研磨
し、さらに電解研磨又は化学研磨した面を粗化処理し、
その粗化処理した面の粗さＲｚが１．５〜４．０μｍで
あることを特徴とする請求項３記載の銅張り積層板用電
解銅箔。4. An electrolytic copper foil for a copper-clad laminate using an electrolytic copper foil, wherein the roughened surface of the electrolytic copper foil is electrolytically polished or chemically polished, and the electrolytically polished or chemically polished surface is roughened. And
The electrolytic copper foil for a copper-clad laminate according to claim 3, wherein the roughened surface has a roughness Rz of 1.5 to 4.0 µm.
２．５μｍであることを特徴とする請求項４記載の銅張
り積層板用電解銅箔。5. A roughened surface having a roughness Rz of 1.5 to 1.5.
The electrolytic copper foil for a copper-clad laminate according to claim 4, wherein the thickness is 2.5 µm.
下であることを特徴とする請求項４又は５記載の銅張り
積層板用電解銅箔。6. The electrolytic copper foil for a copper-clad laminate according to claim 4, wherein the size of the particles in the roughening treatment is 1.5 μm or less.
し、該電解銅箔の粗面の表面粗さＲｚを１．５〜４．０
μｍとすることを特徴とする銅張り積層板用電解銅箔の
製造方法。7. The roughened surface of the electrolytic copper foil is electropolished or chemically polished, and the roughened surface of the electrolytic copper foil has a surface roughness Rz of 1.5 to 4.0.
A method for producing an electrolytic copper foil for a copper-clad laminate, characterized by having a thickness of μm.
し、該電解銅箔の粗面の表面粗さＲｚを１．５〜２．５
μｍとすることを特徴とする請求項７記載の銅張り積層
板用電解銅箔の製造方法。8. A roughened surface of the electrolytic copper foil is electropolished or chemically polished, and a surface roughness Rz of the roughened surface of the electrolytic copper foil is 1.5 to 2.5.
The method for producing an electrolytic copper foil for a copper-clad laminate according to claim 7, wherein the thickness is set to μm.
し、さらに電解研磨又は化学研磨した面を粗化処理し、
その粗化処理した面の粗さＲｚを１．５〜４．０μｍと
することを特徴とする請求項８記載の銅張り積層板用電
解銅箔の製造方法。9. A roughened surface of the electrolytic copper foil is subjected to electrolytic polishing or chemical polishing, and the electrolytically polished or chemically polished surface is roughened.
The method for producing an electrolytic copper foil for a copper-clad laminate according to claim 8, wherein the roughness Rz of the roughened surface is set to 1.5 to 4.0 µm.
２．５μｍとすることを特徴とする請求項９記載の銅張
り積層板用電解銅箔の製造方法。10. A roughened surface having a roughness Rz of 1.5 to
The method for producing an electrolytic copper foil for a copper-clad laminate according to claim 9, wherein the thickness is 2.5 μm.
以下であることを特徴とする請求項９又は１０記載の銅
張り積層板用電解銅箔の製造方法。11. The particle size of the roughening treatment is 1.5 μm.
The method for producing an electrolytic copper foil for a copper-clad laminate according to claim 9 or 10, wherein:
ある硫酸酸性硫酸銅溶液を用いて電解銅箔を製造するこ
とを特徴とする請求項９〜１１のそれぞれに記載の銅張
り積層板用電解銅箔の製造方法。12. The copper clad laminate according to claim 9, wherein an electrolytic copper foil is produced using a sulfuric acid acidic copper sulfate solution having a chloride ion concentration of 2 mg / l or less. Manufacturing method of electrolytic copper foil.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000302122A JP2002105699A (en) | 2000-10-02 | 2000-10-02 | Electrolytic copper foil for copper-clad laminate, and manufacturing method thereof |
| TW90122570A TW574441B (en) | 2000-10-02 | 2001-09-12 | Electrolytic copper foil for copper-clad laminate, and manufacturing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000302122A JP2002105699A (en) | 2000-10-02 | 2000-10-02 | Electrolytic copper foil for copper-clad laminate, and manufacturing method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2002105699A true JP2002105699A (en) | 2002-04-10 |
Family
ID=18783533
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000302122A Pending JP2002105699A (en) | 2000-10-02 | 2000-10-02 | Electrolytic copper foil for copper-clad laminate, and manufacturing method thereof |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP2002105699A (en) |
| TW (1) | TW574441B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004238647A (en) * | 2003-02-04 | 2004-08-26 | Furukawa Techno Research Kk | Smoothened copper foil, and production method therefor |
| KR101042785B1 (en) | 2006-03-30 | 2011-06-20 | 신닛테츠가가쿠 가부시키가이샤 | Method of manufacturing flexible printed wiring board |
| JP2011210983A (en) * | 2010-03-30 | 2011-10-20 | Jx Nippon Mining & Metals Corp | Copper foil for printed wiring board which forms circuit with superior electrical transmission characteristic, and layered body using the same |
| CN117580275A (en) * | 2023-12-27 | 2024-02-20 | 湖北金禄科技有限公司 | Pattern transfer pretreatment process of circuit board, circuit board and preparation method thereof |
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| JPH07188969A (en) * | 1993-10-22 | 1995-07-25 | Gould Electron Inc | Electrodeposited copper foil and its preparation |
| JPH07268678A (en) * | 1994-03-31 | 1995-10-17 | Mitsui Mining & Smelting Co Ltd | Electrolytic copper foil for printed circuit board and its production |
| JPH09195096A (en) * | 1996-01-16 | 1997-07-29 | Mitsui Mining & Smelting Co Ltd | Electrolytic copper foil for printed circuit board and its production |
| JPH09272994A (en) * | 1996-04-05 | 1997-10-21 | Furukawa Electric Co Ltd:The | Electrolytic copper foil for fine pattern |
| JPH1036992A (en) * | 1996-07-19 | 1998-02-10 | Japan Energy Corp | Electrolytic copper foil and its production |
| JPH11340596A (en) * | 1998-05-21 | 1999-12-10 | Furukawa Electric Co Ltd:The | Copper foil for printed circuit board and copper foil attached with resin |
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- 2001-09-12 TW TW90122570A patent/TW574441B/en active
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|---|---|---|---|---|
| JPH07188969A (en) * | 1993-10-22 | 1995-07-25 | Gould Electron Inc | Electrodeposited copper foil and its preparation |
| JPH07268678A (en) * | 1994-03-31 | 1995-10-17 | Mitsui Mining & Smelting Co Ltd | Electrolytic copper foil for printed circuit board and its production |
| JPH09195096A (en) * | 1996-01-16 | 1997-07-29 | Mitsui Mining & Smelting Co Ltd | Electrolytic copper foil for printed circuit board and its production |
| JPH09272994A (en) * | 1996-04-05 | 1997-10-21 | Furukawa Electric Co Ltd:The | Electrolytic copper foil for fine pattern |
| JPH1036992A (en) * | 1996-07-19 | 1998-02-10 | Japan Energy Corp | Electrolytic copper foil and its production |
| JPH11340596A (en) * | 1998-05-21 | 1999-12-10 | Furukawa Electric Co Ltd:The | Copper foil for printed circuit board and copper foil attached with resin |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004238647A (en) * | 2003-02-04 | 2004-08-26 | Furukawa Techno Research Kk | Smoothened copper foil, and production method therefor |
| KR101042785B1 (en) | 2006-03-30 | 2011-06-20 | 신닛테츠가가쿠 가부시키가이샤 | Method of manufacturing flexible printed wiring board |
| JP2011210983A (en) * | 2010-03-30 | 2011-10-20 | Jx Nippon Mining & Metals Corp | Copper foil for printed wiring board which forms circuit with superior electrical transmission characteristic, and layered body using the same |
| CN117580275A (en) * | 2023-12-27 | 2024-02-20 | 湖北金禄科技有限公司 | Pattern transfer pretreatment process of circuit board, circuit board and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| TW574441B (en) | 2004-02-01 |
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