JP2004263300A - Copper foil for fine pattern printed wiring and manufacturing method thereof - Google Patents
Copper foil for fine pattern printed wiring and manufacturing method thereof Download PDFInfo
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Abstract
Description
本発明は、ファインパターンプリント配線用銅箔及びその製造方法に関するものである。 The present invention relates to a copper foil for fine pattern printed wiring and a method for producing the same.
通常、電解銅箔の製造は二工程からなる。第一工程として電解製箔装置により製箔を行い、第二工程として表面処理装置により密着性向上のための粗化処理、各種表面処理を行ってプリント配線板に使用される銅箔が製造される。
図１は電解銅箔製造の第一工程を示すもので、電解製箔装置と呼ばれる回転するドラム状の陰極（ステンレス又はチタン製）（カソード）２と、該陰極２に対して同心円状に配置された陽極（Ｐｂ又はＤＳＡ製）（アノード）１からなり、該陰極２と陽極１との間に銅めっき液３を通し、両極間に電流を流して、陰極２に所定の厚さに銅を析出させた後剥ぎ取り、銅箔４を製造する。この銅箔４を本明細書では未処理銅箔と言う。
未処理銅箔は、銅張り積層板に必要とされる性能を付与するため、第二工程として、図２に示すように電気化学的あるいは化学的に表面処理を連続的に行う。図２は未処理銅箔の表面を処理する表面処理装置で、未処理銅箔４を電解液５が充填された電解槽、電解液６が充填された電解槽を連続的に通過させ、電極７をアノードとし、銅箔自体をカソードとして表面処理を施し、表面処理銅箔８とする。このようにして表面処理を施した後の銅箔を本明細書では表面処理銅箔と言う。表面処理銅箔はプリント配線板に使用される。
Usually, the production of an electrolytic copper foil consists of two steps. The first step is to make a foil using an electrolytic foil making apparatus, and the second step is to perform a roughening treatment for improving adhesion and various surface treatments with a surface treatment device to produce copper foil used for printed wiring boards. You.
FIG. 1 shows the first step of the production of an electrolytic copper foil, in which a rotating drum-shaped cathode (made of stainless steel or titanium) (cathode) 2 called an electrolytic foil-making apparatus, and concentrically arranged with respect to the cathode 2 (Anode) 1 made of Pb or DSA, a
As a second step, the untreated copper foil is subjected to a surface treatment electrochemically or chemically as shown in FIG. 2 in order to impart the required performance to the copper-clad laminate. FIG. 2 shows a surface treatment apparatus for treating the surface of an untreated copper foil, in which an untreated copper foil 4 is continuously passed through an electrolytic bath filled with an electrolytic solution 5 and an electrolytic bath filled with an electrolytic solution 6, and Surface treatment is performed by using 7 as an anode and the copper foil itself as a cathode to obtain a surface-treated
未処理銅箔の表面処理方法は、銅箔を樹脂基板に強固に接合させるために、また、プリント配線板としての所要の電気特性、エッチング特性、耐熱性、耐薬品性を満足させるために、銅箔の樹脂基板との被接合面に粗化処理を施し、更には該粗化処理が施された面上に亜鉛めっきやニッケルめっき等を施し、また更に該亜鉛めっきやニッケルめっき等を施した面上にクロメート処理、シランカップリング剤処理等を施す。
一例として、酸性銅めっき浴中で銅箔を陰極とし、限界電流密度付近でいわゆる「やけめっき」を行うことにより銅箔の被接合表面を粗化面とする方法が開示されている（例えば特許文献１参照）。
また、やけめっきにより銅箔被接合面を粗化面とし、該粗化面の微細な突起群の表面を通常の銅めっきによる薄層（いわゆる「カプセル層」）で覆って、該粗化面の微細な突起群を銅箔に安定的に固定する方法が開示されている（例えば特許文献２参照）。これら一連の処理を本明細書では粗化処理と言う。
The surface treatment method of untreated copper foil is to bond the copper foil to the resin substrate firmly, and to satisfy the required electrical properties, etching properties, heat resistance, and chemical resistance as a printed wiring board. The surface to be joined to the resin substrate of the copper foil is subjected to a roughening treatment, and further, the surface subjected to the roughening treatment is subjected to zinc plating, nickel plating, or the like, and further subjected to the zinc plating, nickel plating, or the like. Chromate treatment, silane coupling agent treatment, etc., are performed on the thus-treated surface.
As an example, there has been disclosed a method in which a copper foil is used as a cathode in an acidic copper plating bath and so-called “burn plating” is performed near a critical current density to make a surface to be bonded of the copper foil roughened (for example, Patent Reference 1).
Further, the surface to be joined with the copper foil is roughened by burn plating, and the surface of the fine projections on the roughened surface is covered with a thin layer (so-called “capsule layer”) formed by ordinary copper plating. (See, for example, Patent Document 2). In this specification, a series of these processes is referred to as a roughening process.
上記のような表面処理銅箔を使用したプリント配線板は、通常次のようにして製造されている。
まず、ガラス・エポキシ樹脂やポリイミド樹脂などからなる電気絶縁性の基板の表面に、表面回路形成用の前記表面処理銅箔を置いたのち、加熱・加圧して銅張り積層板を製造する。
ついで、前記銅張り積層板に、スルーホールの穿設，スルーホールめっきを順次行ったのち、該銅張り積層板の表面にある銅箔にエッチング処理を行って所望する線幅と所望する線間ピッチを備えた配線パターンを形成し、最後に、ソルダーレジストの形成やその他の仕上間ピッチを備えた配線パターンを形成し、最後にソルダーレジストの形成やその他の仕上げ処理が行われる。
このとき用いる銅箔については、基板に熱圧着される側の表面を粗化面とし、この粗化面で該基板に対するアンカー効果を発揮させ、もって該基板と銅箔との接合強度を高めてプリント配線板としての信頼性を確保している。
更に最近では、銅箔の粗化面を予めエポキシ樹脂のような接着用樹脂で被覆し、該接着用樹脂を半硬化状態（Ｂステージ）の絶縁樹脂層にした樹脂付き銅箔を表面回路形成用の銅箔として用い、その絶縁樹脂層の側を基板に熱圧着してプリント配線板、とりわけビルドアッププリント配線板を製造することが行われている。
また、各種電子部品の高集積化に対応して、こうしたビルドアッププリント配線板では、配線パターンも高密度化が要求され、微細な線幅や線間ピッチの配線からなる配線パターン、いわゆるファインパターンのプリント配線板が要求されるようになってきている。例えば、半導体パッケージに使用されるプリント配線板の場合は、線幅や線間ピッチがそれぞれ１５μｍ前後という高密度極微細配線を有するプリント配線板が要求されている。
A printed wiring board using the surface-treated copper foil as described above is usually manufactured as follows.
First, the surface-treated copper foil for forming a surface circuit is placed on the surface of an electrically insulating substrate made of glass epoxy resin, polyimide resin, or the like, and then heated and pressed to produce a copper-clad laminate.
Next, through holes and through-hole plating are sequentially performed on the copper-clad laminate, and then copper foil on the surface of the copper-clad laminate is subjected to an etching treatment to obtain a desired line width and a desired line gap. A wiring pattern having a pitch is formed, and finally, a solder resist is formed and other wiring patterns having a finish pitch are formed. Finally, a solder resist is formed and other finishing processes are performed.
As for the copper foil used at this time, the surface on the side that is thermocompression-bonded to the substrate is a roughened surface, and the roughened surface exerts an anchoring effect on the substrate, thereby increasing the bonding strength between the substrate and the copper foil. The reliability as a printed wiring board is secured.
More recently, a copper foil with a resin in which a roughened surface of a copper foil is coated in advance with an adhesive resin such as an epoxy resin and the adhesive resin is a semi-cured (B stage) insulating resin layer is formed on a surface circuit. A printed wiring board, in particular, a build-up printed wiring board is manufactured by using the insulating resin layer side by thermocompression bonding to a substrate.
Also, in response to the high integration of various electronic components, such build-up printed wiring boards require high density wiring patterns, and wiring patterns composed of wiring with fine line width and line pitch, so-called fine pattern Printed wiring boards have been required. For example, in the case of a printed wiring board used for a semiconductor package, a printed wiring board having a high-density ultrafine wiring having a line width and a line pitch of about 15 μm is required.
このようなプリント配線板形成用の銅箔として、表面の粗さが粗い銅箔を用いると、基板の表面までエッチングするために必要な時間が長くなり、その結果、図３に示すように基板Ｂに貼り合わされた銅箔Ａの配線パターンにおける側壁の垂直性が崩れて、次式：
Ｅｆ＝２Ｔ／（Ｗｂ−Ｗｔ）
（ここで、Ｔは銅箔の厚み、Ｗｂは形成された配線パターンのボトム幅、Ｗｔは形成された配線パターンのトップ幅である）で示されるエッチングファクター（Ｅｆ）が小さくなる。
このような問題は、形成する配線パターンにおける配線の線幅が広い場合にはそれほど深刻な問題にならないが、線幅が狭い配線パターンの場合には断線に結びつくことも起こり得る。
こうしたファインパターンの要求に対して、銅箔の性能でエッチング性に大きな影響のある要因の一つは表面の粗さである。特に、粗化処理を施して樹脂基板と接着する面の粗さの影響が大きい。銅箔の粗さに影響する要因には大きく分けて二つある。一つは未処理銅箔の粗面の表面粗さであり、もう一つは粗化処理（めっき処理）で付着した粒状の金属の付き方である。未処理銅箔の粗面の表面粗さが粗いと粗化処理後の銅箔表面の粗さも粗くなる。また、一般的に粒状の金属の付着量が多いと粗化処理後の銅箔表面の粗さは粗くなる。
未処理銅箔の粗面表面粗さは、銅箔を電解で製造する際のドラム状のカソードに銅を析出させる時の電解条件、特に電解液に加える添加剤によって決まるところが大きい。
また、粗化処理を構成する「やけめっき」の銅めっき液組成、めっき条件により、粒形状及び付き方は大きく影響を受ける。
When a copper foil having a rough surface is used as such a copper foil for forming a printed wiring board, the time required for etching to the surface of the substrate becomes longer, and as a result, as shown in FIG. The verticality of the side wall in the wiring pattern of the copper foil A bonded to B is broken, and the following formula is obtained.
Ef = 2T / (Wb-Wt)
(Where T is the thickness of the copper foil, Wb is the bottom width of the formed wiring pattern, and Wt is the top width of the formed wiring pattern), and the etching factor (Ef) becomes smaller.
Such a problem does not become a serious problem when the line width of the wiring in the wiring pattern to be formed is wide, but may cause disconnection in a wiring pattern with a small line width.
One of the factors that greatly affect the etching property in the performance of the copper foil in response to such fine pattern requirements is the surface roughness. In particular, the effect of the roughness of the surface that is subjected to the roughening treatment and adheres to the resin substrate is large. There are two main factors that affect the roughness of copper foil. One is the surface roughness of the rough surface of the untreated copper foil, and the other is how the granular metal adhered by the roughening treatment (plating treatment) is attached. If the surface roughness of the rough surface of the untreated copper foil is rough, the roughness of the copper foil surface after the roughening treatment also becomes rough. In general, when the amount of adhered granular metal is large, the roughness of the copper foil surface after the roughening treatment becomes rough.
The rough surface roughness of the untreated copper foil is largely determined by the electrolysis conditions when copper is deposited on the drum-shaped cathode when the copper foil is produced by electrolysis, particularly by the additive added to the electrolyte.
Further, the grain shape and the manner of attachment are greatly affected by the copper plating solution composition and plating conditions of the “burn plating” constituting the roughening treatment.
一般的に未処理銅箔は、光沢面と呼ぶ製造時にドラムに接触していた側の面は比較的平滑であるが、逆の面である銅めっき液と接触していた面は凹凸を有する。そこで、粗面を平滑化する試みとして、例えば、チオ尿素などの活性イオウを銅めっき液中に添加して電解銅箔を製造する方法が開示されている（例えば特許文献３参照）。しかし、この方法により製造された未処理銅箔の粗面は、凹凸のＲｚ値は確かに小さいが（なお、ここでいう表面粗さＲｚとはＪＩＳＢ０６０１２で規定する１０点平均粗さであり、以下同様である。）、図４に示すように被処理銅箔４の表面に山と谷の部分が存在する（以下これを本明細書では素地山と言う。）。
通常、こうした銅箔の素地山のピーク間距離は５μｍ未満であり、こうした表面に粗化処理を行うと微細粗化粒子層１２は図４に示すように素地山の頂点の部分に粗化粒子１２ａが集中して電析して、谷の部分には余り電析しない。
また、粗化処理を行う銅めっき液の液組成、めっき条件によっては、図４に符号１２ｂで示すように粗化粒子の異常析出が発生する。このような異常析出は、銅張積層板を作成し、エッチング後にいわゆる残銅となり、ファインパターンを切ることが出来ない。
また、光沢面は比較的平滑であることから、光沢面側に粒状の銅を付着させ樹脂基板との接合強度を上げる試みもなされている（例えば特許文献４参照）。
しかし、未処理箔の光沢面は一見光沢があり、平滑に見えるが、上記のように製造時にチタンドラムに接していた面であるので、ちょうどチタンドラムのレプリカになっている。従って、チタンドラムの表面キズの影響を受け、深いキズ状の欠陥が見られることがある。
こうした欠陥表面に粗化処理を行うと、図５に示すように凹凸のＲｚ値は確かに小さいが、キズ部分に粗化粒子１２ａの異常析出１２ｂが起こり、異常析出の部分はファインパターン作成時に残銅となり、ファインパターンの作成が困難になる。
Generally, untreated copper foil has a relatively smooth surface on the side that was in contact with the drum at the time of manufacture, which is called a glossy surface, but the surface that was in contact with the copper plating solution, which is the opposite surface, has irregularities. . Therefore, as an attempt to smooth the roughened surface, for example, a method of manufacturing an electrolytic copper foil by adding active sulfur such as thiourea to a copper plating solution has been disclosed (for example, see Patent Document 3). However, the rough surface of the untreated copper foil manufactured by this method has a small Rz value of the unevenness (the surface roughness Rz here is a 10-point average roughness defined by JIS B06012, The same applies to the following.), And peaks and valleys are present on the surface of the copper foil 4 to be treated as shown in FIG. 4 (hereinafter referred to as a base mountain in the present specification).
Normally, the distance between the peaks of the copper foil base mountain is less than 5 μm. When such a surface is subjected to the roughening treatment, the fine roughened
Further, depending on the composition of the copper plating solution to be subjected to the roughening treatment and the plating conditions, abnormal precipitation of the roughened particles occurs as shown by
Also, since the glossy surface is relatively smooth, attempts have been made to increase the bonding strength with a resin substrate by attaching granular copper to the glossy surface side (for example, see Patent Document 4).
However, the glossy surface of the untreated foil is glossy at first glance and looks smooth, but is a replica of the titanium drum because it is the surface that was in contact with the titanium drum at the time of manufacture as described above. Therefore, a deep scratch-like defect may be seen due to the influence of the surface scratch of the titanium drum.
When the roughening treatment is performed on such a defect surface, the Rz value of the irregularities is certainly small as shown in FIG. 5, but the
上記各特許文献で開示されている技術による銅箔、並びに粗化面の処理方法では、電子機器の小型化及び高性能化が進み、プリント基板の小型化及び高密度化が要求される近年のファインパターン化の要求には対応できず、樹脂基板との接着強度不足、ファインパターン形成時の残銅、配線ラインの足喰われ等の問題が指摘される。
本発明は、かかる従来の技術の課題を解決するためになされたもので、樹脂基板との間で充分な接着強度を有し、ファインパターン形成時の残銅、配線ラインの足喰われ等の問題を解消し、耐熱性、電気特性においても優れたファインパターンプリント配線用銅箔及びその製造方法を提供するものである。
In the method for treating copper foil and the roughened surface according to the technology disclosed in each of the above-mentioned patent documents, miniaturization and high performance of electronic devices have advanced, and in recent years, miniaturization and high density of printed circuit boards have been required. The demand for fine patterning cannot be met, and problems such as insufficient bonding strength with the resin substrate, residual copper at the time of forming the fine pattern, and bite of the wiring line are pointed out.
The present invention has been made in order to solve the problems of the conventional technology, has a sufficient adhesive strength with a resin substrate, copper remaining at the time of forming a fine pattern, such as a foot bite of a wiring line. An object of the present invention is to provide a copper foil for fine pattern printed wiring, which solves the problem and is excellent in heat resistance and electric characteristics, and a method for producing the same.
本発明のファインパターンプリント配線用銅箔は、未処理銅箔の表面に粗化処理を施してなるファインパターンプリント配線用銅箔であって、前記粗化処理を施す前の未処理銅箔の表面粗さが１０点平均粗さＲｚで２．５μｍ以下であり、素地山の最小ピーク間距離が５μｍ以上である電解銅箔であることを特徴とする。 The copper foil for fine pattern printed wiring of the present invention is a copper foil for fine pattern printed wiring obtained by subjecting the surface of an untreated copper foil to a roughening treatment, and the untreated copper foil before the roughening treatment is performed. The electrolytic copper foil has a surface roughness of 2.5 μm or less in terms of 10-point average roughness Rz, and a minimum peak-to-peak distance of the base mountain of 5 μm or more.
また、本発明のファインパターンプリント配線用銅箔は、未処理銅箔の表面に粗化処理を施してなるファインパターンプリント配線用銅箔であって、前記粗化処理を施す前の前記未処理銅箔の表面粗さが１０点平均粗さＲｚで２．５μｍ以下であり、素地山の最小ピーク間距離が５μｍ以上あり、表面に平均粒径２μｍ以下の結晶粒が表出する電解銅箔であることを特徴とする。 Further, the copper foil for fine pattern printed wiring of the present invention is a copper foil for fine pattern printed wiring obtained by subjecting a surface of an untreated copper foil to a roughening treatment, and the untreated copper foil before the roughening treatment is performed. Electrodeposited copper foil having a surface roughness of copper foil of 2.5 μm or less in terms of 10-point average roughness Rz, a minimum peak-to-peak distance of 5 μm or more, and crystal grains having an average grain size of 2 μm or less on the surface It is characterized by being.
前記未処理銅箔の少なくとも一方の表面に、粗化処理としてモリブデンと、鉄、コバルト、ニッケル、タングステンの内の少なくとも一種を含有する銅のやけめっきにより銅のやけめっき層が成膜されていることが好ましい。
また、好適には前記やけめっき層の上に銅のめっき層が成膜されていると良い。
On at least one surface of the untreated copper foil, molybdenum as a roughening treatment, iron, cobalt, nickel, a copper plating layer containing at least one of tungsten, a copper plating layer is formed. Is preferred.
Preferably, a copper plating layer is formed on the burnt plating layer.
本発明のファインパターンプリント配線用銅箔の製造方法は、メルカプト基を有する化合物、塩化物イオン、並びに分子量１０，０００以下の低分子量膠又は／及び高分子多糖類を添加した銅めっき液で、電流密度範囲が５０Ａ／ｄｍ２以上１００Ａ／ｄｍ２以下で製箔した電解未処理銅箔表面に粗化処理を施すことを特徴とする。 The method for producing a copper foil for fine pattern printed wiring of the present invention comprises a copper plating solution to which a compound having a mercapto group, chloride ions, and a low molecular weight glue having a molecular weight of 10,000 or less and / or a high molecular weight polysaccharide are added. It is characterized in that a roughening treatment is applied to the surface of the electrolytically untreated copper foil produced at a current density range of 50 A / dm 2 or more and 100 A / dm 2 or less.
また、本発明のファインパターンプリント配線用銅箔の製造方法は、表面粗さが１０点平均粗さＲｚで２．５μｍ以下であり、素地山の最小ピーク間距離が５μｍ以上である未処理電解銅箔の少なくとも一方の表面に、０．００１〜５ｇ−Ｍｏ／ｌ、０．０１〜１０ｇ−Ｍ／ｌ（Ｍ＝Ｆｅ及び／又はＣｏ及び／又はＮｉ）、０．１〜１ｐｐｍＷの内の少なくとも１種を含有するめっき浴で、めっき液温度を１０〜３０℃に保って、未処理電解銅箔を陰極とし、該浴の限界電流密度付近の電流密度で電解して銅のやけめっき層を設けることを特徴とする製造方法である。 The method for producing a copper foil for fine pattern printed wiring according to the present invention is characterized in that the untreated electrolytic copper foil has a surface roughness of 2.5 μm or less in terms of a 10-point average roughness Rz and a minimum peak-to-peak distance of 5 μm or more. On at least one surface of the copper foil, 0.001 to 5 g-Mo / l, 0.01 to 10 g-M / l (M = Fe and / or Co and / or Ni), and 0.1 to 1 ppmW In a plating bath containing at least one kind, a plating solution temperature is maintained at 10 to 30 ° C., an untreated electrolytic copper foil is used as a cathode, and electrolysis is carried out at a current density near the limit current density of the bath, and a copper burnt plating layer is formed. Is provided.
更に、本発明のファインパターンプリント配線用銅箔の製造方法は、表面粗さが１０点平均粗さＲｚで２．５μｍ以下であり、素地山の最小ピーク間距離が５μｍ以上であり、表面に平均粒径２μｍ以下の結晶粒が表出する未処理電解銅箔の少なくとも一方の表面に、０．００１〜５ｇ−Ｍｏ／ｌ、０．０１〜１０ｇ−Ｍ／ｌ（Ｍ＝Ｆｅ及び／又はＣｏ及び／又はＮｉ）、０．１〜１ｐｐｍＷの内の少なくとも１種を含有するめっき浴で、めっき液温度を１０〜３０℃に保って、未処理電解銅箔を陰極とし、該浴の限界電流密度付近の電流密度で電解して銅のやけめっき層を設けることを特徴とする製造方法である。 Furthermore, in the method for producing a copper foil for fine pattern printed wiring of the present invention, the surface roughness is 2.5 μm or less in terms of a 10-point average roughness Rz, the minimum peak-to-peak distance of the base mountain is 5 μm or more, 0.001-5 g-Mo / l, 0.01-10 g-M / l (M = Fe and / or Co and / or Ni), in a plating bath containing at least one of 0.1 to 1 ppmW, the plating solution temperature is maintained at 10 to 30 ° C., the untreated electrolytic copper foil is used as a cathode, and the limit of the bath is obtained. It is a manufacturing method characterized by providing a copper burnt plating layer by electrolysis at a current density near the current density.
本発明の銅箔は、樹脂基板との間で充分な接着強度を有し、電子機器の小型化及び高性能化が進み、プリント基板の小型化及び高密度化が要求される近年のファインパターン化の要求に対応し、ファインパターン形成時の足残り、配線ラインの足喰われ等の問題がなく、耐熱性、電気特性においても優れ、特にファインパターンプリント配線用として優れた銅箔である。
更に本発明は前記銅箔の優れた製造方法を提供し、特にファインパターンプリント配線用として優れた銅箔を効率良く製造することができる優れた効果を有するものである。
The copper foil of the present invention has a sufficient adhesive strength with a resin substrate, miniaturization and high performance of electronic devices are advanced, and recent fine patterns that require miniaturization and high density of printed circuit boards are required. It is a copper foil that meets the demands for the formation of a fine pattern, has no problems such as a foot residue at the time of forming a fine pattern, and has no problems such as a bite of a wiring line, and has excellent heat resistance and electrical characteristics, and is particularly excellent for fine pattern printed wiring.
Further, the present invention provides an excellent method for producing the copper foil, and particularly has an excellent effect of efficiently producing an excellent copper foil for fine pattern printed wiring.
先ず本発明ファインパターンプリント配線用銅箔の製造方法につき説明する。
本発明で使用するメルカプト基を有する化合物としては、３−メルカプト１−プロパンスルホン酸塩が好適である。３−メルカプト１−プロパンスルホン酸塩は、ＨＳ（ＣＨ2）3 ＳＯ3 Ｎａ等で示される化合物を挙げることができる。このような化合物は、単独では銅の結晶を微細化する効果はそれほどないが、他の有機化合物と組み合わせて用いることにより、銅の結晶を微細化し、凹凸の少ないめっき表面を得ることができる。メルカプト基を有する化合物は当該分子が硫酸銅電解液中の銅イオンと反応し、錯体となることにより、或いはめっき界面に作用して過電圧を上昇させることによって銅の結晶を微細化し、凹凸の少ないめっき面を形成するものと推定される。
First, a method for producing a copper foil for fine pattern printed wiring of the present invention will be described.
As the compound having a mercapto group used in the present invention, 3-mercapto 1-propanesulfonic acid salt is preferable. 3-mercapto 1-propane sulfonate, there can be mentioned a compound represented by HS (CH 2) 3 SO 3 Na and the like. Such a compound alone is not so effective in refining the copper crystal, but when used in combination with other organic compounds, the copper crystal can be miniaturized and a plated surface with less unevenness can be obtained. The compound having a mercapto group makes the copper crystal finer by reacting the molecule with a copper ion in the copper sulfate electrolyte and forming a complex, or by acting on the plating interface to increase the overvoltage, thereby reducing irregularities. It is presumed to form a plated surface.
本発明で使用する高分子多糖類としては、デンプン、セルロース、植物ゴムなどの炭水化物で、一般に水中でコロイドとなるものが好ましい。工業的に安価に提供されているものとして、デンプンでは食用デンプン、工業用デンプン、デキストリン、セルロースとしては水溶性セルロースエーテル（カルボキシメチルセルロースナトリウム、カルボキシメチルヒドロキシエチルセルロースエーテル等）、また、植物ゴムとしてはアラビアゴムやトラカンドゴムが好ましい。
上記高分子多糖類は、メルカプト基を有する化合物と組み合わせることにより、銅の結晶を微細化し、凹凸のないめっき面を形成する。更に結晶の微細化に加えて、これらの高分子多糖類には、製造された銅箔の脆化を防止する働きがある。これらの高分子多糖類は銅箔に蓄積される内部応力を緩和するため、陰極から剥離され巻き取られる際の破れや銅箔が丸まってしまう現象を防止するばかりでなく、常温及び高温の伸び率も改善する。
The high molecular polysaccharide used in the present invention is preferably a carbohydrate such as starch, cellulose, or vegetable rubber, which is generally a colloid in water. Industrially provided at low cost, starch is edible starch, industrial starch, dextrin, water-soluble cellulose ether (such as sodium carboxymethylcellulose, carboxymethylhydroxyethylcellulose ether) as cellulose, and Arabic as vegetable rubber. Rubber and trakand rubber are preferred.
When the high molecular polysaccharide is combined with a compound having a mercapto group, the crystal of copper is refined to form a plated surface without irregularities. Further, in addition to the refinement of the crystal, these high-molecular polysaccharides have a function of preventing embrittlement of the produced copper foil. These high-molecular-weight polysaccharides reduce internal stress accumulated in the copper foil, which not only prevents tearing and winding of the copper foil when peeled off from the cathode and winding, but also elongation at room temperature and high temperature. The rate also improves.
本発明で使用する低分子量膠は、一般に提供されている膠、或いはゼラチンを酵素や酸もしくはアルカリで分解し、その分子量を小さくした膠で、例えばニッピゼラチン社製の「ＰＢＦ」や米国Ｐｅｔｅｒ−Ｃｏｏｐｅｒ社製の「ＰＣＲＡ」として市販されているものが使用できる。これらの膠の分子量は１万以下で、低分子量のためゼリー強度が著しく低いのが特徴である。
通常の膠は、マイクロポロシティーの防止や粗面の粗さを抑え、形状を整える効果があるが、伸び特性を低下させるという弊害もある。しかしながら通常の膠（やゼラチン）として市販されているものよりも分子量の小さい膠を使用すると、伸び特性などを大きく犠牲にせず、マイクロポロシティーの防止や粗面の粗さを抑えて形状を整える効果がある。
なお、メルカプト基を有する化合物に高分子多糖類と低分子量膠を同時に加えると、それぞれを単独で加えるよりも、銅箔の高温伸び率が改善されるとともに、マイクロポロシティーの防止や細かで均一な凹凸面を得ることが可能となる。
The low molecular weight glue used in the present invention is generally provided glue or glue obtained by decomposing gelatin with an enzyme, acid or alkali to reduce its molecular weight. For example, "PBF" manufactured by Nippi Gelatin Co., Ltd. and US Peter- A commercially available “PCRA” manufactured by Cooper Corporation can be used. These glues have a molecular weight of 10,000 or less, and are characterized by extremely low jelly strength due to their low molecular weight.
Ordinary glue has the effect of preventing microporosity, suppressing the roughness of the rough surface, and adjusting the shape, but also has the adverse effect of reducing elongation characteristics. However, if a glue having a smaller molecular weight than that of a commercially available glue (or gelatin) is used, the shape is adjusted by preventing microporosity and suppressing the roughness of the rough surface without greatly sacrificing the elongation properties. effective.
The simultaneous addition of high-molecular-weight polysaccharides and low-molecular-weight glue to a compound having a mercapto group improves the high-temperature elongation of the copper foil and prevents microporosity and improves fineness and uniformity compared to adding each alone. It is possible to obtain a rough surface.
更に、上記の他、電解液に更に塩化物イオンを添加する。電解液中に塩化物イオンがまったく存在しないと、所望される銅箔粗面がロープロファイル化できないからである。その添加量としては、数ｐｐｍで効果が出てくるが、広い電流密度範囲で安定してロープロファイル銅箔を製造するためには、１０〜６０ｐｐｍの範囲に保つことが好ましい。６０ｐｐｍを越える添加量でもロープロファイル化されるが、添加量を増加したほどにはその効果に著しい増進が認められず、逆に添加量が過剰になると、樹枝状の電析が起こり、或いは限界電流密度が低下するので好ましくない。 Further, in addition to the above, chloride ions are further added to the electrolytic solution. If no chloride ions are present in the electrolytic solution, the desired copper foil rough surface cannot be reduced in profile. The effect is obtained when the amount of addition is several ppm. However, in order to stably produce a low-profile copper foil in a wide current density range, it is preferable to keep the amount in the range of 10 to 60 ppm. Even if the addition amount exceeds 60 ppm, a low profile is obtained, but the effect is not remarkably enhanced as the addition amount is increased. Conversely, if the addition amount is excessive, dendritic electrodeposition occurs or the limit is increased. This is not preferable because the current density decreases.
上述したように、電解液にメルカプト基を有する化合物、高分子多糖類、低分子量膠と微量の塩化物イオンを併用添加することにより、ファインパターン化のためのロープロファイル銅箔に求められる種々の特性が高いレベルで実現できる。更には、本発明により製造された銅箔（以下未処理銅箔という）の析出面の表面粗度ＲZ は該未処理銅箔の光沢面の表面粗度ＲZ と同程度か、それより小さい箔となるため、析出面上に後述する粗化処理を施した後の表面処理銅箔は従来のものに比較して更にロープロファイルとなり、大きなエッチングファクターを持った箔となる。 As described above, by adding a compound having a mercapto group, a high-molecular-weight polysaccharide, a low-molecular-weight glue and a small amount of chloride ion to the electrolytic solution in combination, various types of low-profile copper foils required for fine patterning can be obtained. The characteristics can be realized at a high level. Furthermore, the surface roughness R Z of the deposition surface of the copper foil produced according to the present invention (hereinafter referred to as untreated copper foil) is approximately the same as the surface roughness R Z of the glossy surface of the untreated copper foil, or Since the foil is small, the surface-treated copper foil after the roughening treatment described below is performed on the deposition surface has a lower profile than that of a conventional copper foil, and has a large etching factor.
本発明者等は、既にこの未処理銅箔の製造方法については特許第３３１３２２７号を取得している。しかし、上記特許に示す方法は粗面の粗さは低くなっても、粗面上にうねりが存在し、必ずしもファインパターン用銅箔として適切ではなかった。
その原因は、図６に示すように、この発明による箔を使用して、１５μｍ前後のファインパターン８を作成しようとすると、パターンの直線性があまり良くないという欠点が明らかになってきた。この直線性の悪さは銅箔表面のうねりと密接な関係があると考えられる。すなわち、うねりの山の部分は箔が厚く、谷の部分は箔が薄くなっている。こうした銅箔を使用してファインパターンを作成すると、山の部分の銅箔は溶けにくく、谷の部分に相当する銅箔は溶けやすく、直線性が悪くなると考えられる。ファインパターン用の銅箔として適切な銅箔は、表面粗さが低いとともに、こうしたうねりがなく、なだらかであることが理想で、うねりのない箔が最適である。
The present inventors have already obtained Japanese Patent No. 3313227 for a method for producing this untreated copper foil. However, the method disclosed in the above-mentioned patent has undulations on the rough surface even if the roughness of the rough surface is low, and is not necessarily suitable as a copper foil for fine patterns.
As a cause, as shown in FIG. 6, it has become apparent that when a
本発明者はこうしたうねりのない表面処理銅箔を追求した結果、粗化処理を施す前の未処理銅箔は、その表面粗さが１０点平均粗さＲｚで２．５μｍ以下であり、素地山の最小ピーク間距離が５μｍ以上である電解銅箔である未処理銅箔に粗化処理を施すことで理想的なうねりのないファインパターン用銅箔が得られることを突き止め、さらには、粗化処理を施す前の前記未処理銅箔は、その表面粗さが１０点平均粗さＲｚで２．５μｍ以下であり、素地山の最小ピーク間距離が５μｍ以上あり、表面に平均粒径２μｍ以下の結晶粒が表出する電解銅箔であることが好適であることを突き止め、本発明を完成した。 The present inventor pursued such a surface-treated copper foil without undulation. As a result, the untreated copper foil before the roughening treatment had a surface roughness of 2.5 μm or less in terms of 10-point average roughness Rz, It is ascertained that roughening treatment is performed on an untreated copper foil, which is an electrolytic copper foil having a minimum peak-to-peak distance of 5 μm or more, to obtain an ideal undulation-free fine pattern copper foil. The untreated copper foil before being subjected to the surface treatment has a surface roughness of 2.5 μm or less in terms of a 10-point average roughness Rz, a minimum peak-to-peak distance of a base mountain of 5 μm or more, and an average particle size of 2 μm on the surface. The present inventors have found that it is preferable to use an electrolytic copper foil in which the following crystal grains appear, and have completed the present invention.
本発明において、未処理銅箔の表面のＲｚが２．５μｍ以下でなおかつ素地山の最小ピーク間距離が５μｍ以上必要な理由は、粗化粒子を電析した時に、素地山の頂点の部分に粗化粒子が集中することなく、全体的に均一に粗化粒子が電析するためである。
また、表面に平均粒径２μｍ以下の結晶粒が表出していると、その上に粗化粒子を電析した時に下地（極薄銅箔）の結晶粒の影響を受け、微細な粒を電析させることが可能である。
このような本発明の銅箔は、極細幅のパターンを切った場合、直線性が非常に良好である。その理由は、未処理箔にうねりがないため、箔の厚さにばらつきが少なく、しかも未処理銅箔上に付着している銅粒が小さく、粒径がそろっているため、極細幅のパターンを切った場合、エッチングによる銅箔の溶解のばらつきが少ないためであると考えられる。
In the present invention, the reason why the Rz of the surface of the untreated copper foil is 2.5 μm or less and the minimum peak-to-peak distance of the green body is required to be 5 μm or more is that when roughened particles are electrodeposited, This is because the roughened particles are uniformly deposited as a whole without being concentrated.
Also, if crystal grains having an average particle diameter of 2 μm or less are exposed on the surface, fine grains are affected by the crystal grains of the underlayer (ultra-thin copper foil) when roughened particles are electrodeposited thereon. Can be analyzed.
Such a copper foil of the present invention has very good linearity when a pattern having an extremely fine width is cut. The reason is that there is no undulation in the untreated foil, so the thickness of the foil has little variation, and the copper particles adhered on the untreated copper foil are small and the grain size is uniform, so the pattern of ultra-fine width This is considered to be due to the fact that the variation in the dissolution of the copper foil due to etching is small when cutting is performed.
本発明の表面処理銅箔を得るための基礎となる未処理銅箔の製造方法は、メルカプト基を有する化合物、塩化物イオン、及び必要に応じて低分子量膠、高分子多糖類を添加した銅電解液で製造した電解銅箔であり、製箔時の電流密度範囲が５０Ａ／ｄｍ２以上１００Ａ／ｄｍ２で製造する。
ここで電流密度が５０Ａ／ｄｍ２を下回るところでは、うねりが目立つようになり、うねりの山と山のピーク間隔も狭くなる。電流密度が高い程うねりはなくなるが、過大に電流密度を上げ過ぎると、製箔時にチタンドラム界面への液中銅の供給が間に合わなくなり限界電流密度を超え、やけ状のめっきとなり、或いは粉状のめっきとなり、実用上１００Ａ／ｄｍ２程度が限界である。また、こうした電流密度でうねりを少なくするためには、めっき液の流速が重要な要素である。めっき液の流速を０．０５ｍ／分〜５ｍ／分、さらに好ましくは０．２ｍ／分〜２ｍ／分にすることが好ましい。
これは、０．０５ｍ／分を下回るとうねりが目立つようになり、５ｍ／分を超えるのは設備構造上無理があり、実用的でないからである。
The method for producing an untreated copper foil, which is the basis for obtaining the surface-treated copper foil of the present invention, comprises a compound having a mercapto group, chloride ions, and, if necessary, low-molecular-weight glue and copper to which a high-molecular-weight polysaccharide is added. It is an electrolytic copper foil manufactured using an electrolytic solution, and is manufactured at a current density range of 50 A / dm 2 or more and 100 A / dm 2 during foil making.
Here, when the current density is lower than 50 A / dm 2 , the undulation becomes conspicuous, and the peak interval between the undulations becomes narrow. If the current density is too high, the undulation will be eliminated, but if the current density is excessively increased, the supply of copper in the liquid to the titanium drum interface will not be in time during foil making, exceeding the limit current density, resulting in burnt plating or powdery The practical limit is about 100 A / dm 2 . In order to reduce the undulation at such a current density, the flow rate of the plating solution is an important factor. It is preferable that the flow rate of the plating solution is 0.05 m / min to 5 m / min, more preferably 0.2 m / min to 2 m / min.
This is because if it is less than 0.05 m / min, the undulation becomes conspicuous, and if it exceeds 5 m / min, it is not practical because of the facility structure.
未処理銅箔の表面に粗化処理を施す方法としては、未処理箔の少なくとも一方の表面に、モリブデン、鉄、コバルト、ニッケル、タングステンの内の少なくとも１種を含有する銅めっき浴で、めっき液温度を１０〜３０℃に保ち、被処理銅箔を陰極とし、該浴の限界電流密度付近の電流密度で電解し、銅のやけめっき層として銅合金粒子を突起群として付着させる製造方法である。
さらに、やけめっき層の上を銅の薄めっき層で覆って、該突起群の粉落ちを防止すると良い。
粗化処理のやけめっき電解液には、従来酸性銅めっき浴のめっき液中にセレン、テルル、ヒ素、アンチモン、ビスマスの少なくとも一種を０．０１〜１ｇ−Ｍ／ｌ（Ｍ＝Ｓｅ、Ｔｅ、Ａｓ、Ｓｂ、Ｂｉ）添加する方法が知られている（特公昭５３−３９３２７号公報参照）。
As a method of performing a roughening treatment on the surface of the untreated copper foil, at least one surface of the untreated foil is plated with a copper plating bath containing at least one of molybdenum, iron, cobalt, nickel, and tungsten. Keeping the solution temperature at 10 to 30 ° C., using a copper foil to be treated as a cathode, electrolyzing at a current density near the critical current density of the bath, and attaching a copper alloy particle as a group of protrusions as a copper burnt plating layer. is there.
Further, it is preferable to cover the burnt plating layer with a thin copper plating layer to prevent the protrusions from falling off.
Conventionally, as a rough plating electrolytic solution, at least one of selenium, tellurium, arsenic, antimony, and bismuth is contained in a plating solution of a conventional acidic copper plating bath in an amount of 0.01 to 1 g-M / l (M = Se, Te, A method of adding As, Sb, Bi) is known (see Japanese Patent Publication No. 53-39327).
しかし、この電解液を使用して本発明による未処理銅箔上にやけめっきを施しても、樹脂基板との密着強度が充分でない。またこれらの添加剤を使用しない場合は、密着力は比較的良くなるが、異常電析が発生する。
また、本発明者等は、モリブデンと、鉄、コバルト、ニッケル、タングステンの内の少なくとも１種を含有する銅めっき浴使用したやけめっきを、通常の未処理箔（凹凸のある箔）に行う方法を既に見いだしている（特開平１１−２５６３８９公報参照）が、このめっき液を使用しても、未処理銅箔を本願に示す未処理銅箔を使用し、さらにめっき液温度を１０〜３０℃にしないとファインパターンに適した粗化処理とはならない。
上記温度範囲に設定して、初めて粗化処理粒径が小さく、大きさが揃った、異常電析のない粗化処理を行うことができる。
However, even if the untreated copper foil according to the present invention is subjected to burn plating using this electrolytic solution, the adhesion strength to the resin substrate is not sufficient. When these additives are not used, the adhesion is relatively good, but abnormal electrodeposition occurs.
In addition, the present inventors provide a method of performing burnt plating using a copper plating bath containing molybdenum and at least one of iron, cobalt, nickel, and tungsten on a normal untreated foil (a foil having irregularities). (See Japanese Patent Application Laid-Open No. 11-256389), even if this plating solution is used, the untreated copper foil is used as the untreated copper foil described in the present application, and the plating solution temperature is further increased to 10 to 30 ° C. Otherwise, a roughening process suitable for a fine pattern will not be obtained.
By setting the temperature in the above-mentioned temperature range, it is possible to perform a roughening treatment having a small grain size, a uniform size and no abnormal electrodeposition for the first time.
本願発明による未処理銅箔上に設けるやけめっき層の見かけ膜厚は、０．２〜２．５μm であることが好ましく、０．４〜１．５μm であることが更に好ましい。ここで、「見かけ膜厚」とは、「やけめっき」の処理電流を流した時に電析する粒状のめっき層を平滑めっきに換算して求めた膜厚である。 The apparent thickness of the burnt plating layer provided on the untreated copper foil according to the present invention is preferably from 0.2 to 2.5 μm, more preferably from 0.4 to 1.5 μm. Here, the “apparent film thickness” is a film thickness obtained by converting a granular plating layer that is deposited when a processing current of “burn plating” is applied into a smooth plating.
本発明の銅箔は、前記のやけめっき層の上に銅のめっき層（いわゆる「カプセル層」）を形成したものであってもよく、カプセル層の見かけ膜厚は、０．２〜２．５μmであることが好ましく、０．４〜１．５μm であることが更に好ましい。 The copper foil of the present invention may be one in which a copper plating layer (so-called “capsule layer”) is formed on the above-mentioned burnt plating layer. It is preferably 5 μm, more preferably 0.4 to 1.5 μm.
なお、本発明の銅箔は、所望により、更に前記のやけめっき層又はカプセル層の上にニッケル又はその合金のめっき層、亜鉛又はその合金のめっき層、コバルト又はその合金のめっき層、クロム又はその合金のめっき層を形成したものであってもよく、更にはこれらカプセル層又は前記各種金属、合金めっき層の上にクロメート処理、シランカップリング剤処理を施したものであってもよい。このように本発明の銅箔表面には、ニッケル、亜鉛、コバルト、クロム又はその合金の少なくとも何れか一つのめっき層を所望により施すことで、目的とする性能を有するファインパターンプリント配線に適した表面処理銅箔とすることができる。 In addition, the copper foil of the present invention, if desired, further nickel or its alloy plating layer, zinc or its alloy plating layer, cobalt or its alloy plating layer, chromium or A plated layer of the alloy may be formed, and further, a chromate treatment or a silane coupling agent treatment may be performed on these capsule layers or the various metal or alloy plated layers. Thus, on the copper foil surface of the present invention, by applying at least one plating layer of nickel, zinc, cobalt, chromium or an alloy thereof as desired, it is suitable for fine pattern printed wiring having the intended performance It can be a surface-treated copper foil.
一方、本発明のやけめっき層を形成する方法は、酸性銅電解浴を用い、被処理銅箔を陰極とし、該電解浴の限界電流密度付近の電流密度で電解して銅箔表面に銅のやけめっき層を形成する製造方法であり、該電解浴の電解液中にモリブデン、鉄、コバルト、ニッケル、タングステンの少なくとも１種を含有させると良い。
ここで、モリブデンの濃度は０．００１〜５ｇ−Ｍｏ／ｌが好ましい。モリブデンの濃度が０．００１−Ｍｏ／ｌ未満では所望の効果が顕著でなく、一方５−Ｍｏ／ｌを超えて添加しても所望の効果がその存在量の増加に比し顕著に増大しないので経済的ではない。更にやけめっき層が粉状化しやすくなるので好ましくない。
鉄、コバルト、ニッケルは０．１〜１０ｇ−Ｍ／ｌ（ＭはＦｅ、Ｃｏ、Ｎｉ）含有させるのが好ましく、タングステンの濃度は０．１ｐｐｍ〜１ｐｐｍ含有させるのが好ましい。上記鉄等の規定濃度外の挙動はモリブデンのそれと同様である。
On the other hand, the method of forming the burnt plating layer of the present invention uses an acidic copper electrolytic bath, uses the copper foil to be treated as a cathode, performs electrolysis at a current density near the limit current density of the electrolytic bath, and forms copper on the copper foil surface. This is a manufacturing method for forming a burnt plating layer, and it is preferable that at least one of molybdenum, iron, cobalt, nickel, and tungsten is contained in the electrolytic solution of the electrolytic bath.
Here, the concentration of molybdenum is preferably 0.001 to 5 g-Mo / l. When the concentration of molybdenum is less than 0.001-Mo / l, the desired effect is not remarkable. On the other hand, even when the molybdenum is added in excess of 5-Mo / l, the desired effect does not increase remarkably as compared with the increase in the abundance. Not so economical. Further, it is not preferable because the burnt plating layer easily becomes powdery.
Iron, cobalt, and nickel are preferably contained at 0.1 to 10 g-M / l (M is Fe, Co, Ni), and the concentration of tungsten is preferably contained at 0.1 ppm to 1 ppm. The behavior of iron and the like outside the specified concentration is the same as that of molybdenum.
なお、これらの添加剤は電解液に溶解するものであれば特に限定されないが、代表的な化合物としては下記のものが挙げられる。
１．モリブデン ：モリブデン酸ナトリウム（２水塩）
２．鉄 ：硫酸第１鉄（７水塩）
３．コバルト ：硫酸コバルト（７水塩）
４．ニッケル ：硫酸ニッケル（７水塩）
５．タングステン：タングステン酸ナトリウム（２水塩）
In addition, these additives are not particularly limited as long as they are soluble in the electrolytic solution, but typical compounds include the following.
1. Molybdenum: sodium molybdate (dihydrate)
2. Iron: Ferrous sulfate (7-hydrate)
3. Cobalt: cobalt sulfate (heptahydrate)
4. Nickel: Nickel sulfate (heptahydrate)
5. Tungsten: sodium tungstate (dihydrate)
酸性銅電解浴としては、鉱酸であればいずれの酸でも使用し得るが、通常は、硫酸浴（銅として硫酸銅含有）を用いることが好ましい。
一例として、酸性銅電解浴の液条件を例示すると、
１．銅 ：５〜５０ｇ−Ｃｕ／ｌ
２．モリブデン：０．００１〜５ｇ−Ｍｏ／ｌ
３．その他 ：０．０１〜１０ｇ−Ｍ／ｌ(Ｍ＝Ｆｅ，Ｃｏ，Ｎｉ)又は０．1ｐｐｍ〜１ｐｐｍ−Ｗ、の一種以上
４．酸 ：１０〜２００ｇ−Ｈ２ＳＯ４／ｌ
５．液温 ：１０〜３０℃
As the acidic copper electrolytic bath, any acid can be used as long as it is a mineral acid, but usually, a sulfuric acid bath (containing copper sulfate as copper) is preferably used.
As an example, when the liquid conditions of the acidic copper electrolytic bath are exemplified,
1. Copper: 5 to 50 g-Cu / l
2. Molybdenum: 0.001-5 g-Mo / l
3. Others: at least one of 0.01 to 10 g-M / l (M = Fe, Co, Ni) or 0.1 ppm to 1 ppm-W. Acid: 10~200g-H 2 SO 4 / l
5. Liquid temperature: 10-30 ° C
本発明の銅箔の製造方法においては、前記のやけめっき層を形成する工程に次いで、該やけめっき層の上に銅のめっき層を設けてもよい。
また、本発明の銅箔の製造方法においては、前記のやけめっき層を形成する工程に次いで、該やけめっき層の上にニッケル又はその合金のめっき層、亜鉛又はその合金のめっき層、コバルト又はその合金のめっき層、若しくはクロム又はその合金のめっき層を形成する工程を加えてもよい。
In the method for producing a copper foil of the present invention, a copper plating layer may be provided on the burnt plating layer, following the step of forming the burnt plating layer.
Further, in the method for producing a copper foil of the present invention, following the step of forming the burnt plating layer, a nickel or its alloy plating layer, zinc or its alloy plating layer, cobalt or A step of forming a plating layer of the alloy or a plating layer of chromium or an alloy thereof may be added.
更に前記銅のめっき層形成工程に次いで、ニッケル又はその合金のめっき層、亜鉛又はその合金のめっき層若しくはコバルト又はその合金のめっき層、若しくはクロム又はその合金のめっき層を形成する工程を加えてもよい。
更にまた前記銅のめっき層或いは前記ニッケル、亜鉛、コバルト、クロム又はそれらの合金のめっき層の形成工程に次いで、その上にクロメート処理、シランカップリング剤処理工程を設けてもよい。これら工程の条件は、公知の方法に従って設定することができる。
Further, following the copper plating layer forming step, a step of forming a plating layer of nickel or its alloy, a plating layer of zinc or its alloy or a plating layer of cobalt or its alloy, or a plating layer of chromium or its alloy is added Is also good.
Furthermore, after the step of forming the copper plating layer or the plating layer of nickel, zinc, cobalt, chromium, or an alloy thereof, a chromate treatment and a silane coupling agent treatment may be provided thereon. The conditions of these steps can be set according to a known method.
以下に、本発明を実施例に基づき更に詳しく説明する。ただし、本発明はこれらに限定されるものではない。
[実施例]
Hereinafter, the present invention will be described in more detail based on examples. However, the present invention is not limited to these.
[Example]
（１）未処理銅箔の製造
ａ．実施例１〜４
銅７０〜１３０ｇ／ｌ−硫酸８０〜１４０ｇ／ｌの酸性銅電解浴に表１に示す組成の添加剤を添加した。表中、ＭＰＳは３−メルカプト１−プロパンスルホン酸ナトリウム、ＨＥＣ（高分子多糖類）はヒドロキシエチルセルロース、膠は分子量３，０００の低分子量膠である。ＭＰＳ、ＨＥＣ（高分子多糖類）、膠及び塩化物イオンを表１に示す濃度となるように、それぞれ添加し製箔用電解液を調製した。なお、塩化物イオン濃度を全て３０ｐｐｍに調整したが、塩化物イオン濃度は上述したようにこの濃度に限定されるものではない。
調製した電解液を用い、アノードには貴金属酸化物被覆チタン電極、カソードにはチタン製回転ドラムを用いて表１に示す電解条件の下に、１２μｍ厚みの未処理銅箔を電解製箔によって製造した。
[比較例]
(1) Production of untreated copper foil a. Examples 1-4
An additive having the composition shown in Table 1 was added to an acidic copper electrolytic bath containing 70 to 130 g / l of copper and 80 to 140 g / l of sulfuric acid. In the table, MPS is sodium 3-mercapto 1-propanesulfonate, HEC (high molecular weight polysaccharide) is hydroxyethyl cellulose, and glue is a low molecular weight glue having a molecular weight of 3,000. MPS, HEC (high molecular polysaccharide), glue, and chloride ions were added to the respective concentrations shown in Table 1 to prepare an electrolytic solution for foil making. The chloride ion concentration was adjusted to 30 ppm in all cases, but the chloride ion concentration is not limited to this concentration as described above.
Using the prepared electrolytic solution, an untreated copper foil having a thickness of 12 μm was manufactured by electrolytic foil under the electrolytic conditions shown in Table 1 using a noble metal oxide-coated titanium electrode for the anode and a titanium rotary drum for the cathode. did.
[Comparative example]
ｂ．比較例１〜４
銅７０〜１３０ｇ／ｌ−硫酸８０〜１４０ｇ／ｌの酸性銅電解浴に表１に示す組成の添加剤（膠は分子量６０，０００の膠を使用）を添加し、実施例と同様の製法で比較例の未処理銅箔を製造した。
b. Comparative Examples 1-4
An additive having the composition shown in Table 1 (glue having a molecular weight of 60,000 was used) was added to an acidic copper electrolytic bath containing 70 to 130 g / l of copper and 80 to 140 g / l of sulfuric acid. An untreated copper foil of a comparative example was manufactured.
各実施例、比較例で製造した未処理銅箔の表面粗さＲZ 、Ｒa は表面粗さ計（小坂研究所製ＳＥ−３Ｃ型）を用いて測定した（ここで、表面粗さＲZ 、Ｒa とは、ＪＩＳ Ｂ ０６０１-1994 「表面粗さの定義と表示」に規定されたＲZ 、Ｒa である）。
幅方向の常温での伸び率、及び１８０°Ｃの温度における５分間保持後での伸び率並びに各々の温度での引張り強さは引張り試験機（インストロン社製１１２２型）を用いて、それぞれ測定した。結果を表２に示す。
Each embodiment, the surface roughness R Z of the untreated copper foil produced in Comparative Example, R a surface roughness meter (manufactured by Kosaka Kenkyusho SE-3C type) as described previously (here, the surface roughness R Z, and R a is a JIS B 0601 -1994 "surface roughness defined to display" a defined R Z, R a).
The elongation at room temperature in the width direction, the elongation after holding at 180 ° C. for 5 minutes, and the tensile strength at each temperature were measured using a tensile tester (Model 1122 manufactured by Instron). It was measured. Table 2 shows the results.
表２から明らかなように未処理銅箔の粗面の粗さＲｚは低い。さらにうねりが小さい。 As is clear from Table 2, the roughness Rz of the rough surface of the untreated copper foil is low. Furthermore, the swell is small.
（２）やけめっき層の形成
実施例１〜４及び比較例１〜４で製造した未処理銅箔に表３の条件にて直流による陰極電解処理を施し、該未処理銅箔の粗面上に微細な突起群からなるやけめっき層を電析させた。
(2) Formation of burnt plating layer The untreated copper foils manufactured in Examples 1 to 4 and Comparative Examples 1 to 4 were subjected to a cathodic electrolysis treatment with a direct current under the conditions shown in Table 3, and on the rough surface of the untreated copper foil. A burnt plating layer composed of a group of fine projections was deposited.
表３ 粗化液組成
（３）カプセルめっきの形成
粗面上に微細な突起群が形成された前記の表面処理銅箔に下記の条件にて直流による陰極電解処理を施し、微細な突起群を銅の薄層で覆った。
電解液と電流条件
Electrolyte and current conditions
（５）性能測定
表１の実施例１の方法にて作成した未処理銅箔を用いて表３の粗化液中にて同一条件下で粗化処理を施した箔についてのＦＲ−４基板とのピール強度を表４に示す。
(5) Performance measurement FR-4 substrate on foil subjected to roughening treatment under the same conditions in the roughening solution of Table 3 using untreated copper foil prepared by the method of Example 1 in Table 1. Table 4 shows the peel strength.
表４ ＦＲ−４とのピール強度
銅箔のピール強度の測定は、銅箔をＦＲ−４基板に張り付けた後１０mm幅で行った。各実施例に於いて比較例よりも低粗度・高ピール強度を有する銅箔が得られている。
しかしながら、前述したように近年の銅箔のファインパターン化に於いて、銅箔に求められる特性は多様化しており、例えば異常析出の無いこと、局部的なラインの剥離が無いこと、エッチング性に優れること、直線性に優れること等が要求されている。
本発明に於ける銅箔についてこれらの項目についての評価を行った。
実施例１〜４、比較例１〜４で作成した未処理箔に実施例Ａ、比較例Ｈの粗化処理を施した箔について評価した結果を表５、６に示した。
The peel strength of the copper foil was measured at a width of 10 mm after attaching the copper foil to the FR-4 substrate. In each example, a copper foil having lower roughness and higher peel strength than the comparative example was obtained.
However, as described above, in the recent fine patterning of copper foil, the characteristics required for copper foil have been diversified, and for example, there is no abnormal deposition, no local line peeling, and etching properties. It is required to be excellent and to have excellent linearity.
The copper foil in the present invention was evaluated for these items.
Tables 5 and 6 show the evaluation results of the untreated foils prepared in Examples 1 to 4 and Comparative Examples 1 to 4 which were subjected to the roughening treatment of Example A and Comparative Example H.
ピール強度
銅箔のピール強度を測定した。測定は、銅箔をＦＲ−４基板に張り付けた後、１０ｍｍ幅で行った。実施例１〜４と比較例１〜２ではむしろ比較例の方がピール強度は大きい。
比較例の方がピール強度が大きいのは、粗化前の銅箔表面に山谷（凹凸）があるため、山の部分に粗化粒子が集中して電析し、谷の部分には粗化粒子がほとんど電析していないが、測定が１０ｍｍ幅と広い幅であるため粗化粒子のアンカー効果によりピール強度が大きくなっているものである。なお比較例３は銅箔の光沢面上に粗化処理を行っているので、本発明と同様表面の山谷（凹凸）がなく、ピール強度自体は本発明例と同程度である。しかし、この銅箔の場合は異常電析が避けられないという致命的欠陥がある。
また、本発明による粗化処理液を用いてやけめっきを行った表５の値に比較して、従来の粗化処理液を用いてやけめっきを行った表６の結果を比較してわかるように、未処理箔の表面がフラットな箔にやけめっきを行った場合、本発明めっき浴による方がピール強度が高い。これは、Ｒｚそのものの値はそれほど差がないが、本発明法によるやけめっきの方が粒子形状が球状（従来のやけめっきは偏平状）に近いためである。
しかし、３０μｍ幅以下というような極細幅になってくると、山谷（凹凸）がある箔のピール強度は、以下に示すように減少してくる。
Peel strength The peel strength of the copper foil was measured. The measurement was performed with a width of 10 mm after attaching the copper foil to the FR-4 substrate. In Examples 1 to 4 and Comparative Examples 1 and 2, the peel strength of the comparative example is rather large.
The peel strength of the comparative example is higher because the copper foil surface before roughening has peaks and valleys (irregularities), so roughened particles are concentrated on the peaks and electrodeposited, and the valleys are roughened. Although particles were hardly electrodeposited, the peel strength was increased by the anchor effect of the roughened particles because the measurement was as wide as 10 mm. In Comparative Example 3, since the roughening treatment was performed on the glossy surface of the copper foil, there were no peaks and valleys (irregularities) on the surface similarly to the present invention, and the peel strength itself was almost the same as that of the present invention. However, this copper foil has a fatal defect that abnormal electrodeposition cannot be avoided.
In addition, as compared with the values in Table 5 in which burnt plating was performed using the roughening treatment solution according to the present invention, the results in Table 6 in which burnt plating was performed using the conventional roughening treatment solution were compared. In addition, when the untreated foil is subjected to burn plating on a flat surface, the peel strength of the plating bath of the present invention is higher. This is because although the value of Rz itself is not so different, the particle shape of the burnt plating according to the present invention is closer to a spherical shape (conventional burnt plating is flat).
However, as the width becomes extremely thin, such as 30 μm or less, the peel strength of a foil having peaks and valleys (irregularities) decreases as shown below.
剥離強度
前記した比較例で作成した銅箔の剥離強度は、幅が３０μｍ以下というような極細幅になってくるとピール強度が減少する。その原因は、線幅が細くなるに従って線幅内での粗化粒子の付着量がまばらになるためである。このような現象を確認するためにテープ剥離テストをライン／スペース＝３０μｍ／３０μｍとした本発明表面処理銅箔並びに比較例の銅箔で作成したプリント配線板により実施し、その結果を表５，６に併記した。
なお、テープ剥離テスト（テープ粘着力＝０．８０ｋＮ／ｍのテープを使用した。）は、上記のＬ／Ｓ＝３０／３０のテストパターンに、粘着テープを貼り付けて引き剥がした時、パターンが樹脂基板から剥離するかどうかで評価した。
表５に示したようにライン／スペース＝３０／３０μｍというような極細幅になると、本発明の銅箔に比較して比較例の銅箔配線は剥離し易くなっている。
なお、表６では粗化処理の形状が本発明例と異なり、粗化処理の粒形状が扁平なものとなり、１０ｍｍ幅でのピール強度自体が低く、ライン／スペース＝３０／３０μｍでも剥離が起こってしまい、本発明のように、未処理箔と粗化処理の組み合わせで初めて良好な密着性とファインパターン性が達成できるのである。
Peel Strength The peel strength of the copper foil prepared in the comparative example described above decreases as the width becomes as thin as 30 μm or less. The reason for this is that as the line width becomes narrower, the amount of the roughened particles adhered within the line width becomes sparse. In order to confirm such a phenomenon, a tape peeling test was performed using a surface-treated copper foil of the present invention in which the line / space was 30 μm / 30 μm and a printed wiring board made of a copper foil of a comparative example. Also described in No. 6.
In addition, the tape peeling test (a tape having a tape adhesive force of 0.80 kN / m was used) was performed by applying a pressure-sensitive adhesive tape to the test pattern of L / S = 30/30 and peeling off the test pattern. Was evaluated based on whether or not the resin was separated from the resin substrate.
As shown in Table 5, when the line / space has an extremely narrow width of 30/30 μm, the copper foil wiring of the comparative example is more easily peeled than the copper foil of the present invention.
In Table 6, the shape of the roughening treatment is different from that of the present invention, the grain shape of the roughening treatment is flat, the peel strength itself at a width of 10 mm is low, and peeling occurs even at line / space = 30/30 μm. Thus, as in the present invention, good adhesion and fine pattern properties can be achieved only by a combination of an untreated foil and a roughening treatment.
エッチング性の評価
各銅箔をＦＲ−４基板にプレス接着した後、銅箔表面に、ライン／スペース＝１０／１０μｍ、１５／１５μｍ、２０／２０μｍ、２５／２５μｍ、３０／３０μｍ、３５／３５μｍ、４０／４０μｍ、４５／４５μｍ、５０／５０μｍのテストパターン（ライン長さ３０ｍｍ、ライン本数１０本）を印刷し、塩化銅のエッチング液でエッチングを行った。
１０本のラインがブリッジすることなくエッチングできた場合の線幅を数値で表５，６に示した。実施例で作成した表面処理銅箔では１５μｍまでエッチング可能であるのに対し、比較例で作成した銅箔では２５μｍが最低であった。
Evaluation of etching property After press-bonding each copper foil to FR-4 substrate, line / space = 10/10 μm, 15/15 μm, 20/20 μm, 25/25 μm, 30/30 μm, 35/35 μm on the copper foil surface. , 40/40 μm, 45/45 μm, and 50/50 μm test patterns (line length: 30 mm, number of lines: 10) were printed and etched with a copper chloride etchant.
Tables 5 and 6 show numerical values of the line widths when 10 lines could be etched without bridging. In the case of the surface-treated copper foil prepared in the example, etching was possible up to 15 μm, whereas in the case of the copper foil prepared in the comparative example, the minimum was 25 μm.
なお、上記で作成したパターンについて、パターンの直線性について×１００の実体顕微鏡で調査し、表５，６にパターンの直線性として示した。直線性に優れるものを○とし、図６のようにパターンが波打っているものを×とした。本発明の高電流密度で製箔した銅箔実施例１〜４は、従来の低電流密度で製箔した銅箔比較例４に比較し、パターンの波打ちがなく直線性に優れている。この直線性に優れる点はファインパターンになるほど重要な要素になる。パターンの波打ちがひどくなると、隣同士のパターンの短絡に結びつくからである。 In addition, about the pattern created above, the linearity of the pattern was investigated with a x100 stereomicroscope, and shown in Tables 5 and 6 as the linearity of the pattern. A sample having excellent linearity was evaluated as ○, and a sample having a wavy pattern as shown in FIG. 6 was evaluated as ×. The copper foils of Examples 1 to 4 manufactured at a high current density according to the present invention have no pattern undulation and are excellent in linearity as compared with the conventional copper foil manufactured at a low current density of Comparative Example 4. This excellent linearity becomes a more important factor as the finer pattern becomes. This is because if the pattern is severely wavy, it may lead to a short circuit between adjacent patterns.
上述したように、本発明はライン／スペースが１５μｍの極細幅までエッチングが可能であり、なおかつ１５μｍのラインをエッチングした後でも、１５μｍラインに粗化粒子が多数付着しているため、粗さが低いにもかかわらず、微細ラインと配線基板とが高い密着強度を持ち、なおかつパターンの直線性に優れることから本発明表面処理銅箔により、超ファインパターンのプリント配線板、および超ファインパターンの多層プリント配線板を提供することができるものである。 As described above, according to the present invention, the line / space can be etched to an ultra-fine width of 15 μm, and even after etching the 15 μm line, a large number of coarse particles adhere to the 15 μm line. Despite being low, the fine lines and the wiring board have high adhesion strength, and because of the excellent linearity of the pattern, the surface-treated copper foil of the present invention provides a printed wiring board with an ultra-fine pattern, and a multilayer with an ultra-fine pattern. It is possible to provide a printed wiring board.
本発明表面処理銅箔を用いることによりファインパターン回路に適用可能な表面粗度が非常に小さく、なおかつ高ピール強度を有する銅箔及びその製造方法を提供することが出来る。
本発明に従えば、ファインパターンプリント配線用銅箔としての所定の性能を充分に満足する環境に優れた銅箔及びそのための製造方法を提供することができる。
本発明は上述したように、樹脂基板との間で充分なピール強度を有し、電子機器の小型化及び高性能化が進み、プリント基板の小型化及び高密度化が要求される近年のファインパターン化の要求に対応し、ファインパターン形成時の足残り、配線ラインの足喰われ等の問題がなく、耐熱性、電気特性においても優れたファインパターンプリント配線用銅箔を提供し、更に該銅箔の優れた製造方法を提供するものである。
By using the surface-treated copper foil of the present invention, it is possible to provide a copper foil having a very small surface roughness applicable to fine pattern circuits and having high peel strength, and a method for producing the same.
ADVANTAGE OF THE INVENTION According to this invention, the copper foil excellent in environment which fully satisfies the predetermined performance as a copper foil for fine pattern printed wiring, and its manufacturing method can be provided.
As described above, the present invention has a sufficient peel strength with a resin substrate, advances in miniaturization and high performance of electronic devices, and has been required in recent years for miniaturization and high density of printed circuit boards. In response to the demand for patterning, there is no problem such as a foot residue at the time of forming a fine pattern, a biting of a wiring line, and the like, and a copper foil for fine pattern printed wiring excellent in heat resistance and electrical characteristics is provided. An object of the present invention is to provide an excellent method for producing a copper foil.
１ 電極
２ 電極（ドラム）
３ 電解液
４ 未処理銅箔
５ 電解槽
６ 電解槽
７ 電極
８ 表面処理銅箔
Ｂ 樹脂基板
１２ 粒子
1
3 electrolytic solution 4 untreated copper foil 5 electrolytic bath 6 electrolytic bath 7
Claims (8)
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| JP2004263296A (en) * | 2003-02-12 | 2004-09-24 | Furukawa Techno Research Kk | Copper foil for fine pattern printed wiring and manufacturing method thereof |
| JP2006222185A (en) * | 2005-02-09 | 2006-08-24 | Furukawa Circuit Foil Kk | Polyimide flexible copper clad laminate, copper foil therefor, and polyimide flexible printed wiring board |
| JP2007131946A (en) * | 2005-10-14 | 2007-05-31 | Mitsui Mining & Smelting Co Ltd | Flexible copper-clad laminate, flexible printed wiring board obtained using the flexible copper-clad laminate, film carrier tape obtained using the flexible copper-clad laminate, and semiconductor device obtained using the flexible copper-clad laminate , Method for producing flexible copper clad laminate and method for producing film carrier tape |
| JP2007294873A (en) * | 2006-03-30 | 2007-11-08 | Nippon Steel Chem Co Ltd | Manufacturing method of flexible printed wiring board |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11256389A (en) * | 1998-03-09 | 1999-09-21 | Furukawa Circuit Foil Kk | Copper foil for printed circuit board and its production |
| JP2002322586A (en) * | 1995-09-22 | 2002-11-08 | Furukawa Circuit Foil Kk | Electrolytic copper foil for fine pattern and its manufacturing method |
| JP2003311880A (en) * | 2002-04-23 | 2003-11-06 | Matsushita Electric Works Ltd | Metal foil-clad laminated sheet for high frequency, printed wiring board, and multilayered printed wiring board |
-
2004
- 2004-02-12 JP JP2004035367A patent/JP2004263300A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002322586A (en) * | 1995-09-22 | 2002-11-08 | Furukawa Circuit Foil Kk | Electrolytic copper foil for fine pattern and its manufacturing method |
| JPH11256389A (en) * | 1998-03-09 | 1999-09-21 | Furukawa Circuit Foil Kk | Copper foil for printed circuit board and its production |
| JP2003311880A (en) * | 2002-04-23 | 2003-11-06 | Matsushita Electric Works Ltd | Metal foil-clad laminated sheet for high frequency, printed wiring board, and multilayered printed wiring board |
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