JPH06169168A - Printed circuit copper foil and manufacture thereof - Google Patents
Printed circuit copper foil and manufacture thereofInfo
- Publication number
- JPH06169168A JPH06169168A JP4332219A JP33221992A JPH06169168A JP H06169168 A JPH06169168 A JP H06169168A JP 4332219 A JP4332219 A JP 4332219A JP 33221992 A JP33221992 A JP 33221992A JP H06169168 A JPH06169168 A JP H06169168A
- Authority
- JP
- Japan
- Prior art keywords
- copper
- copper foil
- nickel
- cobalt
- layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、印刷回路用銅箔及びそ
の製造方法に関するものであり、特には銅箔と樹脂基板
との接着強度を高めるために銅箔の被接着面に鉄、ニッ
ケル及びコバルトの１種或いは２種以上を含有する多数
の突起状（粒状又は節こぶ状、以下単に突起状と記載す
る）銅電着物からなる粗化処理層を形成した印刷回路用
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 a copper foil for a printed circuit and a method for producing the same, and in particular, in order to enhance the adhesive strength between the copper foil and the resin substrate, iron or nickel is applied to the adhered surface of the copper foil. And a copper foil for a printed circuit formed with a roughening treatment layer composed of a large number of protrusion-shaped (granular or nodular, hereinafter simply referred to as protrusions) copper electrodeposits containing one or more cobalt It relates to a manufacturing method.
【０００２】[0002]
【従来技術】印刷回路用銅箔は一般に、合成樹脂等の基
材に高温高圧下で積層接着され、その後目的とする回路
を形成するべくレジストを用いて所定の回路パターンを
スクリーン印刷した後、不要部を除去するために塩化第
二銅溶液等のエッチング液を使用してエッチング処理が
施される。最終的に、所要の素子が半田付けされて、エ
レクトロニクスデバイス用の種々の印刷回路板を形成す
る。印刷配線板用銅箔に対する品質要求は、樹脂基材と
接着される被接着面（粗化面）と光沢面とで異なる。2. Description of the Related Art Generally, a printed circuit copper foil is laminated and adhered to a base material such as a synthetic resin under high temperature and high pressure, and then a predetermined circuit pattern is screen-printed with a resist to form a target circuit. An etching process is performed using an etching solution such as a cupric chloride solution to remove unnecessary portions. Finally, the required elements are soldered to form various printed circuit boards for electronic devices. Quality requirements for copper foils for printed wiring boards differ between the adhered surface (roughened surface) to be adhered to the resin base material and the glossy surface.
【０００３】本発明が関与する粗化面に対する要求とし
ては、主として、 基材との引きはがし強さが高温加熱、湿式処理、半田
付け、薬品処理等の後でも充分なこと（剥離強度）、 保存時における酸化変色のないこと（防錆性）、 基材との積層、エッチング後に生じる所謂積層汚点の
ないこと（耐塩酸性） エッチングに際して粉落ちのないこと（粉落ち防止） 等が挙げられる。中でも、充分に高い引きはがし強度を
有することは被接着面の最も重要な基本的事項である。The requirements for the roughened surface to which the present invention relates are mainly that the peeling strength from the base material is sufficient even after high temperature heating, wet treatment, soldering, chemical treatment, etc. (peeling strength), There is no oxidative discoloration during storage (anti-rust property), lamination with a base material, no so-called laminated stain that occurs after etching (hydrochloric acid resistance), and no powder drop during etching (prevention of powder drop). Above all, having a sufficiently high peeling strength is the most important basic matter of the surface to be adhered.
【０００４】銅箔と樹脂基板との接着強度を高めるため
に、銅箔の被接着面には、多数の突起状銅電着物からな
る粗化処理層が形成されている。電解銅箔に粗化処理が
施される場合には、生箔自体がすでに凸部を有してお
り、その凸部の頂上部付近に突起状銅電着物が多数電着
して凸部を更に増強することになる。In order to increase the adhesive strength between the copper foil and the resin substrate, a roughening treatment layer composed of a large number of protruding copper electrodeposits is formed on the adhered surface of the copper foil. When the electrolytic copper foil is subjected to a roughening treatment, the green foil itself already has a convex portion, and a large number of protruding copper electrodeposits are electrodeposited near the top of the convex portion to form a convex portion. It will be further enhanced.
【０００５】有効な粗化処理として、特公昭５４−３８
０５３号、特公昭５３−３９３２７号等に砒素、アンチ
モン、ビスマス、セレンまたはテルルを含む酸性銅電解
浴中で限界電流密度前後で電解することが記載されてい
る。実用的には、砒酸が電解浴に添加されることが多
い。これにより生箔の凸部に多数の突起状銅電着物が形
成され、それにより接着強度が高まり、粗化処理方法と
して有効である。As an effective roughening treatment, Japanese Patent Publication No. 54-38
No. 053, Japanese Examined Patent Publication No. 53-39327 and the like describe electrolyzing in an acidic copper electrolytic bath containing arsenic, antimony, bismuth, selenium or tellurium around a limiting current density. Practically, arsenic acid is often added to the electrolytic bath. As a result, a large number of protruding copper electrodeposits are formed on the convex portions of the raw foil, which increases the adhesive strength and is effective as a roughening treatment method.
【０００６】[0006]
【発明が解決しようとする課題】しかしながら、砒素が
関与する場合、電解時に銅電着物中に砒素が数１００ｐ
ｐｍ取り込まれるため、銅箔の再生その他の処理時にま
たエッチング時に砒素が溶出したエッチング液の処分時
に存在する砒素が環境上また健康上重大な問題となる。
こうした毒性元素を含まない粗化処理法としてベンゾキ
ノリン類を微量添加した浴を使用する方法（特公昭５６
−４１１９６号）、モリブデン、バナジウム或いは両者
を添加した浴での処理（特公昭６２−５６６７７号、特
公昭６２−５６６７８号）、或いはパルスめっきでの粗
化処理（特開昭６３−１７５９７号、特開昭５８−１６
４７９７号）等が提唱されているが、剥離強度、粉落ち
その他の面でいまだ必ずしも充分ではない。However, when arsenic is involved, arsenic is contained in the copper electrodeposit at several hundreds of p during electrolysis.
Since pm is taken in, the arsenic present during the recycling of the copper foil or other processing and the disposal of the etching solution in which arsenic is eluted during etching becomes a serious environmental and health problem.
As a roughening treatment method that does not include such toxic elements, a method using a bath to which a small amount of benzoquinoline is added is used (Japanese Patent Publication Sho 56).
No. 41196), molybdenum, vanadium, or a bath containing both of them (Japanese Patent Publication No. 62-56677 and Japanese Patent Publication No. 62-56678), or roughening treatment by pulse plating (Japanese Patent Laid-Open No. 63-17597). JP-A-58-16
No. 4797) has been proposed, but it is not always sufficient in terms of peeling strength, powder falling and the like.
【０００７】本発明の課題は、印刷回路用銅箔の被接着
面について、環境問題を呈さず、しかも樹脂基板との間
で充分な接着強度を発現しそしてエッチングに際して粉
落ちを生じない粗化処理技術を確立することである。An object of the present invention is to roughen the adhered surface of a copper foil for a printed circuit without causing environmental problems, yet exhibiting sufficient adhesive strength with a resin substrate and causing no powder drop during etching. It is to establish processing technology.
【０００８】[0008]
【課題を解決するための手段】本発明者は、課題解決に
向けての検討の結果、鉄、ニッケル及びコバルトイオン
の１種或いは２種以上を含有する銅電解浴を用いて銅箔
の被接着面に多数の突起状銅電着物からなる粗化処理層
を形成すると、デンドライト（樹枝状の結晶）の発生を
抑制しそして丸みを帯びた突起が良好に電着し、銅箔と
樹脂基板との接着強度を向上しそして粉落ちを回避する
のに有用であることを見出すに至った。この知見に基づ
いて、本発明は、（１）銅箔の被接着面に鉄、ニッケル
及びコバルトの１種或いは２種以上を含有する多数の突
起状銅電着物からなる粗化処理層を有することを特徴と
する印刷回路用銅箔を提供するものである。Means for Solving the Problems As a result of studies aimed at solving the problems, the inventor of the present invention uses a copper electrolytic bath containing one or more of iron, nickel and cobalt ions to coat a copper foil. When a roughening treatment layer consisting of a large number of protruding copper electrodeposits is formed on the adhesive surface, dendrite (dendritic crystal) generation is suppressed and rounded protrusions are electrodeposited well, and copper foil and resin substrate It has been found to be useful for improving the adhesive strength with and avoiding powder drop. Based on this finding, the present invention has (1) a roughening treatment layer composed of a large number of protruding copper electrodeposits containing one or more of iron, nickel and cobalt on the surface to be adhered of a copper foil. The present invention provides a copper foil for a printed circuit characterized by the above.
【０００９】更に、この粗化処理層の上に従来通り更に
処理層を形成することができ、この観点から、本発明は
（２）銅箔の被接着面に鉄、ニッケル及びコバルトの１
種或いは２種以上を含有する多数の突起状銅電着物から
なる粗化処理層と、該粗化処理層を被覆する銅、クロ
ム、ニッケル、鉄、コバルト及び亜鉛からなる群から選
択される１種乃至２種以上の金属または合金からなるト
リート層とを有することを特徴とする印刷回路用銅箔及
び（３）銅箔の被接着面に鉄、ニッケル及びコバルトの
１種或いは２種以上を含有する多数の突起状銅電着物か
らなる粗化処理層と、該粗化処理層を被覆する銅、クロ
ム、ニッケル、鉄、コバルト及び亜鉛からなる群から選
択される１種乃至２種以上の金属または合金からなるト
リート層と、該トリート層を被覆する防錆層とを有する
ことを特徴とする印刷回路用銅箔を提供する。Further, it is possible to further form a treatment layer on the roughening treatment layer in the conventional manner. From this viewpoint, the present invention provides (2) a surface of the copper foil to be adhered, which is composed of iron, nickel and cobalt.
Selected from the group consisting of copper, chromium, nickel, iron, cobalt and zinc for coating the roughening treatment layer, which is composed of a large number of protruding copper electrodeposits containing one or two or more species. A copper foil for a printed circuit, which comprises a treat layer comprising one or more kinds of metals or alloys, and (3) one or more kinds of iron, nickel and cobalt on the adhered surface of the copper foil. A roughening treatment layer comprising a large number of protruding copper electrodeposits contained, and one or more kinds selected from the group consisting of copper, chromium, nickel, iron, cobalt and zinc coating the roughening treatment layer. Provided is a copper foil for a printed circuit, which has a treat layer made of a metal or an alloy and an anticorrosive layer covering the treat layer.
【００１０】更に、印刷回路用銅箔を製造する方法とし
て（４）酸性銅電解浴において銅箔を陰極として限界電
流密度付近で電解して銅箔の被接着面に多数の突起状銅
電着物からなる粗化処理層を形成する印刷回路用銅箔の
製造方法において、電解浴中に鉄、ニッケル及びコバル
トイオンの１種或いは２種以上を０．１〜５０ｇ／ｌ存
在せしめることを特徴とする印刷回路用銅箔の製造方法
及び（５）形成された粗化処理層上に銅、クロム、ニッ
ケル、鉄、コバルト及び亜鉛からなる群から選択される
１種乃至２種以上の金属または合金からなるトリート層
を電解により形成し、必要に応じ更に防錆処理すること
を特徴とする上記の印刷回路用銅箔の製造方法を提供す
る。Further, as a method for producing a copper foil for a printed circuit, (4) a large number of protruding copper electrodeposits are formed on the adhered surface of the copper foil by electrolyzing in an acidic copper electrolytic bath using the copper foil as a cathode near the limiting current density. In the method for producing a copper foil for a printed circuit for forming a roughening treatment layer consisting of 0.1 to 50 g / l of one, two or more of iron, nickel and cobalt ions are present in the electrolytic bath. (5) One or more metals or alloys selected from the group consisting of copper, chromium, nickel, iron, cobalt and zinc on the formed roughening layer. A method for producing a copper foil for a printed circuit as described above, characterized in that a treat layer made of is electrolyzed and, if necessary, further subjected to anticorrosion treatment.
【００１１】[0011]
【作用】本発明に従えば、酸性銅電解浴中に鉄、ニッケ
ル及びコバルトイオンの１種或いは２種以上を０．１〜
５０ｇ／ｌ存在せしめて粗化処理層を構成することによ
り、突起状銅電着物が微量の鉄、ニッケル及びコバルト
の１種或いは２種以上を含有し、また銅電着時の核発生
を抑制してデンドライトの形成を抑制し、また電着突起
状粒子を丸めて、接着強度の向上に有用となり、またエ
ッチング時の粉落ちを防止する。鉄、ニッケル或いはコ
バルトイオンが電解浴に存在しないと、限界電流付近で
電解すると銅電着物は樹枝状となり、接着強度を改善す
るよりむしろ損なうことになる。粉落ちが生じると、エ
ッチング処理後銅の微粉が残るため電気的特性を損なう
危険がある。According to the present invention, one or more of iron, nickel and cobalt ions are added to the acidic copper electrolytic bath in an amount of 0.1 to 0.1%.
By forming a roughening treatment layer with 50 g / l being present, the protruding copper electrodeposit contains a trace amount of one or more of iron, nickel and cobalt, and suppresses nucleation during copper electrodeposition. The formation of dendrites is suppressed, and the electrodeposited projection-like particles are rounded, which is useful for improving the adhesive strength and prevents powder from falling off during etching. If iron, nickel or cobalt ions are not present in the electrolytic bath, the copper electrodeposition becomes dendritic when electrolyzed near the limiting current, and the adhesive strength is impaired rather than improved. When powder is removed, fine copper powder remains after the etching process, which may impair the electrical characteristics.
【００１２】[0012]
【実施例】本発明は、圧延銅箔及び電解銅箔いずれをも
対象としうるが、特には電解銅箔が対象とされる。電解
銅箔に固有に存在する多数の凸部を個々に更に増強する
のに有用である。従来のように砒素に代表される有毒元
素を含む銅電解浴を使用しての限界電流前後の電解によ
りこうした粗化処理層が効果的に形成されるが、砒素が
数１００ｐｐｍ粗化処理層にとり込まれるために環境及
び健康問題を呈したのである。EXAMPLES The present invention can be applied to both rolled copper foil and electrolytic copper foil, but in particular to electrolytic copper foil. It is useful for further strengthening individually the large number of protrusions inherent in the electrolytic copper foil. Such a roughening treatment layer is effectively formed by electrolysis before and after the limiting current using a copper electrolytic bath containing a toxic element typified by arsenic as in the past. It presents environmental and health problems due to its inclusion.
【００１３】図１は、電解銅箔の被接着面側の処理層の
例を概略的に示す。生箔１の被接着面には電解銅箔であ
るために、その表面全体にわたって凸部２が分布してい
る。この生箔上に粗化処理が行なわれる。本発明に従う
粗化処理により、凸部２の頂上部付近を主体として鉄、
ニッケル及びコバルトの１種或いは２種以上を含有する
多数の突起状銅電着物から構成される粗化処理層３が形
成され、凸部を増強する。圧延銅箔のような平滑な銅箔
に粗化処理が施された場合には電着物自体が突起部を構
成する。この後、多数の処理態様があるが、例えば突起
状銅電着物の脱落を防止するために薄い銅めっき層４が
形成され、そして後耐熱性その他の特性を付与するため
にクロム、ニッケル、鉄、コバルト及び亜鉛等の金属乃
至合金、例えば黄銅等のトリートめっき層５が形成さ
れ、最後にクロメート処理等に代表される防錆層６が形
成される。こうして処理された銅箔被接着面が樹脂基板
等に接着される。以下、各工程について詳述する。FIG. 1 schematically shows an example of a treatment layer on the surface to be adhered of an electrolytic copper foil. Since the surface of the raw foil 1 to be adhered is an electrolytic copper foil, the convex portions 2 are distributed over the entire surface thereof. A roughening process is performed on this raw foil. By the roughening treatment according to the present invention, iron mainly in the vicinity of the top of the convex portion 2,
A roughening treatment layer 3 composed of a large number of protruding copper electrodeposits containing one kind or two or more kinds of nickel and cobalt is formed to enhance the convex portion. When a smooth copper foil such as a rolled copper foil is subjected to a roughening treatment, the electrodeposit itself constitutes a protrusion. After this, there are many treatment modes, for example, a thin copper plating layer 4 is formed to prevent the protruding copper electrodeposits from falling off, and chromium, nickel, iron are added to impart post heat resistance and other properties. A metal or alloy such as cobalt and zinc, for example, a treat plating layer 5 such as brass is formed, and finally a rust preventive layer 6 typified by chromate treatment is formed. The copper foil adhered surface thus treated is adhered to a resin substrate or the like. Hereinafter, each step will be described in detail.
【００１４】本発明に従う粗化処理用銅電解浴のめっき
条件は次の通りである： Ｃｕイオン：５〜５０ｇ／ｌ Ｈ2 ＳＯ4 ：１０〜１００ｇ／ｌ 鉄、ニッケル、コバルトイオン：０．１〜５０ｇ／ｌ 温度：室温〜５０℃ Ｄk ：５〜８０Ａ／ｄｍ2 時間：１〜３０秒 銅電解浴中に存在させる鉄、ニッケル、またはコバルト
イオン或いはその組合せの濃度は０．１〜５０ｇ／ｌが
適当であり、好ましくは０．５〜３０ｇ／ｌである。添
加量が０．１ｇ／ｌ未満では接着強度を増すのに充分な
効果はなく、他方５０ｇ／ｌを超えてもその効果に顕著
な向上はなくまた経済的負担が増大する。鉄、ニッケル
またはコバルトの供給源として、硫酸塩、塩化物、硝酸
塩等の使用が可能である。例えば、硫酸塩としては、硫
酸ニッケル（７水塩）、硫酸コバルト（７水塩）、硫酸
第一鉄（７水塩）等が使用される。The plating conditions of the copper electrolytic bath for roughening treatment according to the present invention are as follows: Cu ion: 5 to 50 g / l H 2 SO 4 : 10 to 100 g / l Iron, nickel, cobalt ions: 0. 1 to 50 g / l Temperature: room temperature to 50 ° C. D k : 5 to 80 A / dm 2 hours: 1 to 30 seconds The concentration of iron, nickel, or cobalt ions or a combination thereof present in the copper electrolytic bath is 0.1. 50 g / l is suitable, preferably 0.5 to 30 g / l. If the amount added is less than 0.1 g / l, the effect is not sufficient to increase the adhesive strength, while if it exceeds 50 g / l, the effect is not significantly improved and the economic burden increases. As a source of iron, nickel or cobalt, it is possible to use sulfate, chloride, nitrate and the like. For example, as the sulfate, nickel sulfate (heptahydrate), cobalt sulfate (heptahydrate), ferrous sulfate (heptahydrate) and the like are used.
【００１５】上記のような粗化処理後、粗化面に銅、ク
ロム、ニッケル、鉄、コバルト及び亜鉛からなる群から
選択される１種乃至２種以上の金属層または合金層を形
成するトリート処理を行うことが好ましい。例えば、粗
化処理層の突起状銅電着物の脱落を防止するために電着
物を覆って薄い銅層が被覆され、その上にクロム、ニッ
ケル、鉄、コバルト或いは亜鉛の金属層、或いは銅−ニ
ッケル、銅−コバルト、銅−ニッケル−コバルト、銅−
亜鉛等に代表され得る合金層が形成されうる（例えば、
特公昭５６−９０２８号、特開昭５４−１３９７１号、
特開平２−２９２８９４号、特開平２−２９２８９５
号、特公昭５１−３５７１１号、特公昭５４−６７０１
号参照）。こうしたトリート処理層は銅箔の最終性状を
決定するものとしてまた障壁層としての役割を果たす。After the above-described roughening treatment, a treat for forming one or more metal layers or alloy layers selected from the group consisting of copper, chromium, nickel, iron, cobalt and zinc on the roughened surface. Treatment is preferred. For example, a thin copper layer is coated over the electrodeposit in order to prevent the protruding copper electrodeposit of the roughening treatment layer from falling off, and a metal layer of chromium, nickel, iron, cobalt or zinc, or a copper layer. Nickel, copper-cobalt, copper-nickel-cobalt, copper-
An alloy layer typified by zinc or the like may be formed (for example,
JP-B-56-9028, JP-A-54-13971,
JP-A-2-292894, JP-A-2-292895
No. 51-35711, 54-6701
No.). Such treated layers serve as determinants of the final properties of the copper foil and as barrier layers.
【００１６】例えば、亜鉛被膜を例にとると、亜鉛電気
めっきおよび無電解めっきいずれでも行いうるが、粗化
面片面にのみ被膜を形成するためには亜鉛電解操作によ
る方が便宜である。また、厚さの精確な制御、厚さの一
様性、付着層の緻密化等の観点からも電解操作が好まし
い。亜鉛電解操作は、硫酸亜鉛めっき浴や塩化亜鉛めっ
き浴に代表される酸性亜鉛めっき浴、シアン化亜鉛めっ
き浴のようなアルカリ性亜鉛めっき浴、あるいはピロリ
ン酸亜鉛めっき浴が使用しうるが、もっとも一般的に使
用される硫酸亜鉛浴で充分である。硫酸亜鉛浴を使用し
た場合の好ましい亜鉛電解条件は下記の通りである。 ＺｎＳＯ4 ・７Ｈ2 Ｏ：５０〜３５０ｇ／ｌ ｐＨ（硫酸）：２．５〜４．５ 浴温度：４０〜６０℃ 陰 極：銅箔 陽 極：亜鉛または不溶性陽極 陰極電流密度：０．０５〜０．４Ａ／dm2 時 間：１０〜３０秒 亜鉛被覆量は、１５〜１５００μg ／dm2 とすることが
好ましく、特に好ましくは１５〜４００μg ／dm2 であ
る。亜鉛被覆量は、積層時の樹脂基板の種類によって異
なる。例えばフェノール樹脂基板用は、１５〜６０μg
／dm2 とし、ガラスエポキシ樹脂基板用は６０〜１５０
０μg ／dm2 、特に好ましくは６０〜４００μg ／dm2
とする。[0016] For example, in the case of a zinc coating, either zinc electroplating or electroless plating can be performed, but zinc electrolytic operation is more convenient for forming a coating only on one surface of the roughened surface. Further, the electrolysis operation is preferable from the viewpoints of precise control of thickness, thickness uniformity, densification of the adhesion layer and the like. Zinc electrolysis can be performed using an acidic zinc plating bath represented by a zinc sulfate plating bath or a zinc chloride plating bath, an alkaline zinc plating bath such as a zinc cyanide plating bath, or a zinc pyrophosphate plating bath. A commonly used zinc sulfate bath is sufficient. The preferable zinc electrolysis conditions when using a zinc sulfate bath are as follows. ZnSO 4 · 7H 2 O: 50~350g / l pH ( sulfate): 2.5-4.5 bath temperature: 40 to 60 ° C. Yin electrode: copper cation electrode: zinc or insoluble anode Cathode current density: 0.05 ~0.4A / dm between 2:00: 10 to 30 seconds of zinc coating amount is preferably set to 15~1500μg / dm 2, particularly preferably 15~400μg / dm 2. The amount of zinc coating varies depending on the type of resin substrate at the time of stacking. For example, for phenol resin substrates, 15-60 μg
/ Dm 2 , 60-150 for glass epoxy resin substrate
0 Pg / dm 2, particularly preferably 60~400μg / dm 2
And
【００１７】合金層の一例としてＣｕ−Ｚｎトリート処
理の電解液組成及び条件例を挙げておく： ＮａＣＮ ：１０〜３０ｇ／ｌ ＮａＯＨ ：４０〜１００ｇ／ｌ ＣｕＣＮ ：６０〜１２０ｇ／ｌ Ｚｎ（ＣＮ）2 ：１〜１０ｇ／ｌ ｐＨ ：１０〜１３ 温度 ：６０〜８０℃ Ｄk ：１〜１０Ａ／ｄｍ2 As an example of the alloy layer, an electrolytic solution composition and conditions for Cu-Zn treatment are given: NaCN: 10 to 30 g / l NaOH: 40 to 100 g / l CuCN: 60 to 120 g / l Zn (CN) 2 : 1 to 10 g / l pH: 10 to 13 Temperature: 60 to 80 ° C. D k : 1 to 10 A / dm 2
【００１８】更に、好ましくは、このトリート処理層表
面上に防錆層が形成される。公知の防錆処理の任意のも
のが適用可能である。クロメート処理液は現在使用され
ている様々の処理液いずれも使用しうるが、好ましいク
ロメート処理条件例を以下に示す： Ｋ2 Ｃｒ2 Ｏ7 （或いはＮａ2 Ｃｒ2 Ｏ7 、ＣｒＯ
3 ）：０．２〜２０ｇ／ｌ 酸：りん酸あるいは硫酸、有機酸 ｐＨ：１．０〜３．５ 浴温度：２０〜４０℃ 電流密度：０．１〜０．５Ａ／dm2 時間：１０〜６０秒 陽極：鉛板、Ｐｔ−Ｔｉ板、ステンレス鋼板 クロム酸化物付着量はクロム量として５０μg ／dm2 以
下で充分であり、好ましくは１５〜３０μg ／dm2 とさ
れる。クロム量が３０μg ／dm2 を超えると防錆力は向
上するがエッチング性が低下する。Further, preferably, a rust preventive layer is formed on the surface of the treated layer. Any known rustproofing treatment can be applied. The chromate treatment liquid may be any of various treatment liquids currently used, but preferable chromate treatment condition examples are as follows: K 2 Cr 2 O 7 (or Na 2 Cr 2 O 7 , CrO)
3 ): 0.2 to 20 g / l Acid: phosphoric acid or sulfuric acid, organic acid pH: 1.0 to 3.5 Bath temperature: 20 to 40 ° C. Current density: 0.1 to 0.5 A / dm 2 hours: 10-60 seconds anode: lead plates, Pt-Ti plate, stainless steel plate chromium oxide coating weight is sufficient 50 [mu] g / dm 2 or less as the amount of chromium, and preferably from 15~30μg / dm 2. When the amount of chromium exceeds 30 μg / dm 2 , the rust preventive power is improved but the etching property is deteriorated.
【００１９】有用な防錆方法として、本件出願人は、電
解亜鉛・クロム処理による亜鉛及び／又は酸化亜鉛とク
ロム酸化物との混合皮膜処理を提唱し（特公昭５８−７
０７７号）、多くの成果を挙げてきた。更に、特開平２
−２９４４９０号は、長期間高温多湿条件下での黒点発
生を防止することを目的として、浸漬クロメート処理に
よりクロム酸化物皮膜を形成し、続いて電解亜鉛・クロ
ム処理により亜鉛及び／又は酸化亜鉛とクロム酸化物と
の混合皮膜を形成することを開示する。As a useful rust preventive method, the present applicant has proposed a mixed film treatment of zinc and / or zinc oxide and chromium oxide by electrolytic zinc / chromium treatment (Japanese Patent Publication No. 58-7).
No. 077), many achievements have been made. Furthermore, JP-A-2
No. 294490, for the purpose of preventing the generation of black spots under high temperature and high humidity conditions for a long period of time, a chromium oxide film is formed by immersion chromate treatment, and then zinc and / or zinc oxide is formed by electrolytic zinc / chromium treatment. Forming a mixed film with chromium oxide is disclosed.
【００２０】最後に、必要に応じ、銅箔と樹脂基板との
接着力の改善を主目的として、防錆層上にシランカップ
リング剤を塗布するシラン処理が施される。塗布方法
は、シランカップリング剤溶液のスプレーによる吹付
け、コーターでの塗布、浸漬、流しかけ等いずれでもよ
い。例えば、特公昭６０−１５６５４号は、銅箔の粗面
側にクロメート処理を施した後シランカップリング剤処
理を行なうことによって銅箔と樹脂基板との接着力を改
善することを記載している。詳細はこれを参照された
い。Finally, if necessary, a silane treatment for applying a silane coupling agent onto the anticorrosive layer is performed mainly for the purpose of improving the adhesive force between the copper foil and the resin substrate. The coating method may be spraying of a silane coupling agent solution, coating with a coater, dipping, pouring, or the like. For example, Japanese Examined Patent Publication No. 60-15654 describes that the adhesion between the copper foil and the resin substrate is improved by subjecting the rough surface side of the copper foil to a chromate treatment and then a silane coupling agent treatment. . For details, refer to this.
【００２１】こうして粗化面を被膜処理された銅箔は、
光沢面を必要に応じ処理した後、粗化面に接着剤を塗布
して樹脂基板に加熱圧着することにより印刷回路用銅張
り積層板とされ、所定の加工操作を経た後、印刷回路板
として使用に供される。光沢面の処理方法としては、ク
ロメート処理を含む各種化成処理、銅とのキレート化反
応を利用した有機剤処理、銅より卑な金属ないし合金の
被覆処理等その面において要求される特定水準に応じて
適当なものが選ばれる。The copper foil coated on the roughened surface in this way is
After processing the glossy surface as necessary, apply an adhesive to the roughened surface and heat press bond to the resin substrate to make a copper clad laminate for printed circuits, and after a predetermined processing operation, as a printed circuit board Be used. As a treatment method for glossy surface, various chemical conversion treatments including chromate treatment, organic agent treatment utilizing chelation reaction with copper, coating treatment of metals or alloys that are baser than copper, etc. Appropriate one is selected.
【００２２】この後、必要に応じて、銅箔の延性を改善
する目的で焼鈍処理を施すこともある。Thereafter, if necessary, an annealing treatment may be performed for the purpose of improving the ductility of the copper foil.
【００２３】本発明による鉄、ニッケル又はコバルトイ
オン或いはその組合せを含有する銅電解浴で粗化した銅
箔は、その処理は均一であり、ムラもなく優秀な基板特
性を示した。即ち、銅箔とガラス布基材エポキシ樹脂で
積層板を作製した場合、良好な接着性及び耐熱性を示
し、デンドライトの発達を抑えた丸みのある銅電着物が
形成されるので、接着強度は高くまたエッチング後の基
板の電気的特性や粉落ちの問題がなく良好な性状を示し
た。２．４ｋｇ／ｃｍ以上の引きはがし強さが得られ、
特にＮｉ，Ｃｏについては２．６０〜２．７８ｋｇ／ｃ
ｍもの高水準の引きはがし強さが得られた。The copper foil roughened with a copper electrolytic bath containing iron, nickel or cobalt ions or a combination thereof according to the present invention was uniformly treated and showed excellent substrate characteristics without unevenness. That is, when a laminate is prepared from a copper foil and a glass cloth-based epoxy resin, it shows good adhesiveness and heat resistance, and a rounded copper electrodeposit with suppressed dendrite development is formed. It was high and showed good properties without problems such as electrical characteristics of the substrate after etching and powder falling off. A peeling strength of 2.4 kg / cm or more is obtained,
Especially for Ni and Co, 2.60 to 2.78 kg / c
A high level of peel strength was obtained.
【００２４】以下、実施例及び比較例を示す。Examples and comparative examples will be shown below.
【００２５】（実施例１）硫酸銅（５水塩）１００ｇ／
ｌ、硫酸１００ｇ／ｌ及び硫酸ニッケル（７水塩）１０
ｇ／ｌを含む水溶液を３０℃で電解浴として使用し、厚
さ７０μｍの電解銅箔の被接着面に電流密度２０Ａ／ｄ
ｍ2 で１０秒間めっきした。このようにして得られた銅
箔を分析したところ、箔全体に対するニッケルの含有量
は約２ｐｐｍ（突起状銅電着物中のＮｉ含有量は、約
０．０２ｗｔ％）であった。得られた銅箔の粗化面の突
起状銅電着物の電着状況を示す電子顕微鏡写真を図２に
示す。また、ガラス布基材エポキシ樹脂で加熱・加圧し
て銅張り積層板を作製し、引きはがし強さ及び粉落ち特
性を測定した。結果を表１に示す。(Example 1) 100 g of copper sulfate (pentahydrate) /
1, sulfuric acid 100 g / l and nickel sulfate (heptahydrate) 10
An aqueous solution containing g / l was used as an electrolytic bath at 30 ° C., and a current density of 20 A / d was applied to the adhered surface of an electrolytic copper foil having a thickness of 70 μm.
Plated at m 2 for 10 seconds. When the copper foil thus obtained was analyzed, the content of nickel in the entire foil was about 2 ppm (the content of Ni in the protruding copper electrodeposit was about 0.02 wt%). An electron micrograph showing the electrodeposition state of the protruding copper electrodeposit on the roughened surface of the obtained copper foil is shown in FIG. Further, a copper-clad laminate was prepared by heating and pressurizing with a glass cloth base epoxy resin, and peeling strength and powder falling property were measured. The results are shown in Table 1.
【００２６】（実施例２）硫酸銅（５水塩）１００ｇ／
ｌ、硫酸１００ｇ／ｌ及び硫酸コバルト（７水塩）５ｇ
／ｌを含む水溶液を３０℃で電解浴として使用し、厚さ
７０μｍの電解銅箔の被接着面に電流密度１０Ａ／ｄｍ
2 で２０秒間めっきした。このようにして得られた銅箔
を分析したところ、箔全体に対するコバルトの含有量は
約１ｐｐｍ（突起状銅電着物中のＣｏ含有量は、約０．
０１ｗｔ％）であった。得られた銅箔の粗化面の突起状
銅電着物の電着状況を示す電子顕微鏡写真を図３に示
す。また、ガラス布基材エポキシ樹脂で加熱・加圧して
銅張り積層板を作製し、引きはがし強さ及び粉落ち特性
を測定した。結果を表１に示す。(Example 2) 100 g of copper sulfate (pentahydrate) /
1, sulfuric acid 100 g / l and cobalt sulfate (heptahydrate) 5 g
An aqueous solution containing 1 / l was used as an electrolytic bath at 30 ° C., and the current density was 10 A / dm on the adhered surface of an electrolytic copper foil having a thickness of 70 μm.
Plated at 2 for 20 seconds. When the copper foil thus obtained was analyzed, the cobalt content in the entire foil was about 1 ppm (the Co content in the protruding copper electrodeposit was about 0.
It was 01 wt%). An electron micrograph showing the electrodeposition state of the protruding copper electrodeposit on the roughened surface of the obtained copper foil is shown in FIG. Further, a copper-clad laminate was prepared by heating and pressurizing with a glass cloth base epoxy resin, and peeling strength and powder falling property were measured. The results are shown in Table 1.
【００２７】（実施例３）硫酸銅（５水塩）１００ｇ／
ｌ、硫酸１００ｇ／ｌ及び硫酸第１鉄（７水塩）２０ｇ
／ｌを含む水溶液を３０℃で電解浴として使用し、厚さ
７０μｍの電解銅箔の被接着面に電流密度２０Ａ／ｄｍ
2 で１０秒間めっきした。このようにして得られた銅箔
を分析したところ、箔全体に対する鉄の含有量は約４ｐ
ｐｍ（突起状銅電着物中のＦｅ含有量は、約０．０３ｗ
ｔ％）であった。得られた銅箔の粗化面の突起状銅電着
物の電着状況を示す電子顕微鏡写真を図４に示す。ま
た、ガラス布基材エポキシ樹脂で加熱・加圧して銅張り
積層板を作製し、引きはがし強さ及び粉落ち特性を測定
した。結果を表１に示す。(Example 3) 100 g of copper sulfate (pentahydrate) /
1, sulfuric acid 100 g / l and ferrous sulfate (7 hydrate) 20 g
An aqueous solution containing 1 / l was used as an electrolytic bath at 30 ° C., and a current density of 20 A / dm was applied to the adhered surface of an electrolytic copper foil having a thickness of 70 μm.
Plated at 2 for 10 seconds. When the copper foil thus obtained was analyzed, the iron content in the entire foil was about 4 p.
pm (Fe content in the protruding copper electrodeposition is about 0.03w
t%). An electron micrograph showing the electrodeposition state of the protruding copper electrodeposit on the roughened surface of the obtained copper foil is shown in FIG. Further, a copper-clad laminate was prepared by heating and pressurizing with a glass cloth base epoxy resin, and peeling strength and powder falling property were measured. The results are shown in Table 1.
【００２８】（実施例４）硫酸銅（５水塩）１００ｇ／
ｌ、硫酸１００ｇ／ｌ、硫酸ニッケル（７水塩）５ｇ／
ｌ及び硫酸コバルト（７水塩）５ｇ／ｌを含む水溶液を
３０℃で電解浴として使用し、厚さ７０μｍの電解銅箔
の被接着面に電流密度１０Ａ／ｄｍ2 で２０秒間めっき
した。このようにして得られた銅箔を分析したところ、
箔全体に対するニッケル及びコバルトの含有量はそれぞ
れ約１ｐｐｍ（突起状銅電着物中のＮｉ及びＣｏの含有
量は、それぞれ約０．０１ｗｔ％）であった。得られた
銅箔の粗化面の突起状銅電着物の電着状況を示す電子顕
微鏡写真を図５に示す。また、ガラス布基材エポキシ樹
脂で加熱・加圧して銅張り積層板を作製し、引きはがし
強さ及び粉落ち特性を測定した。結果を表１に示す。Example 4 Copper sulfate (pentahydrate) 100 g /
1, sulfuric acid 100 g / l, nickel sulfate (heptahydrate) 5 g /
1 and an aqueous solution containing 5 g / l of cobalt sulfate (heptahydrate) were used as an electrolytic bath at 30 ° C., and an adhered surface of an electrolytic copper foil having a thickness of 70 μm was plated at a current density of 10 A / dm 2 for 20 seconds. When the copper foil thus obtained was analyzed,
The contents of nickel and cobalt with respect to the entire foil were each about 1 ppm (the contents of Ni and Co in the protruding copper electrodeposition were each about 0.01 wt%). An electron micrograph showing the electrodeposition state of the protruding copper electrodeposit on the roughened surface of the obtained copper foil is shown in FIG. Further, a copper-clad laminate was prepared by heating and pressurizing with a glass cloth base epoxy resin, and peeling strength and powder falling property were measured. The results are shown in Table 1.
【００２９】（比較例１）添加物を含まない例として、
硫酸銅（５水塩）１００ｇ／ｌ及び硫酸１００ｇ／ｌを
含む水溶液を３０℃で電解浴として使用し、厚さ７０μ
ｍの電解銅箔の被接着面に電流密度２０Ａ／ｄｍ2 で１
０秒間めっきした。得られた銅箔の粗化面の突起状銅電
着物の電着状況を示す電子顕微鏡写真を図６に示す。ま
た、ガラス布基材エポキシ樹脂で加熱・加圧して銅張り
積層板を作製し、引きはがし強さ及び粉落ち特性を測定
した。結果を表１に示す。図６には、樹枝状電着物が観
察される。(Comparative Example 1) As an example containing no additives,
An aqueous solution containing 100 g / l of copper sulfate (pentahydrate) and 100 g / l of sulfuric acid was used as an electrolytic bath at 30 ° C. and had a thickness of 70 μm.
1 with a current density of 20 A / dm 2 on the surface to be adhered of electrolytic copper foil of m
Plated for 0 seconds. An electron micrograph showing the electrodeposition state of the protruding copper electrodeposit on the roughened surface of the obtained copper foil is shown in FIG. Further, a copper-clad laminate was prepared by heating and pressurizing with a glass cloth base epoxy resin, and peeling strength and powder falling property were measured. The results are shown in Table 1. In FIG. 6, a dendritic electrodeposit is observed.
【００３０】（比較例２）従来からの砒素を含む例とし
て、硫酸銅（５水塩）１００ｇ／ｌ、硫酸１００ｇ／ｌ
及び砒酸３ｇ／ｌを含む水溶液を３０℃で電解浴として
使用し、厚さ７０μｍの電解銅箔の被接着面に電流密度
２０Ａ／ｄｍ2 で１０秒間めっきした。このようにして
得られた銅箔を分析したところ、箔全体に対する砒素の
含有量は約２００ｐｐｍ（突起状銅電着物中のＡｓ含有
量は、約１．２ｗｔ％）であった。得られた銅箔の粗化
面の突起状銅電着物の電着状況を示す電子顕微鏡写真を
図７に示す。また、ガラス布基材エポキシ樹脂で加熱・
加圧して銅張り積層板を作製し、引きはがし強さ及び粉
落ち特性を測定した。結果を表１に示す。Comparative Example 2 As an example containing conventional arsenic, copper sulfate (pentahydrate) 100 g / l, sulfuric acid 100 g / l
An aqueous solution containing 3 g / l of arsenic acid and 30 g of arsenic acid was used as an electrolytic bath, and an adhered surface of an electrolytic copper foil having a thickness of 70 μm was plated at a current density of 20 A / dm 2 for 10 seconds. When the copper foil thus obtained was analyzed, the content of arsenic in the entire foil was about 200 ppm (the As content in the protruding copper electrodeposit was about 1.2 wt%). An electron micrograph showing the electrodeposition state of the protruding copper electrodeposit on the roughened surface of the obtained copper foil is shown in FIG. 7. Also, heating with glass cloth base epoxy resin
A copper-clad laminate was prepared by pressurizing, and the peel strength and the powder falling property were measured. The results are shown in Table 1.
【００３１】[0031]
【表１】 [Table 1]
【００３２】[0032]
【発明の効果】本発明による鉄、ニッケル又はコバルト
イオン或いはその組合せを含有する銅電解浴で粗化した
銅箔は、その処理は均一であり、ムラもなく優秀な基板
特性を示す。銅箔とガラス布基材エポキシ樹脂で積層板
を作製した場合、良好な接着性及び耐熱性を示し、デン
ドライトの発達を抑えた丸みのある電着物が形成される
ので、接着強度は非常に高くまたエッチング後の基板の
電気的特性や粉落ちの問題がない。The copper foil roughened with the copper electrolytic bath containing iron, nickel or cobalt ions or the combination thereof according to the present invention has a uniform treatment and shows excellent substrate characteristics without unevenness. When a laminate is made of copper foil and glass cloth-based epoxy resin, it shows good adhesiveness and heat resistance, and a rounded electrodeposit with suppressed dendrite formation is formed, so the adhesive strength is very high. Further, there is no problem of electrical characteristics of the substrate after etching and powder drop.
【図面の簡単な説明】[Brief description of drawings]
【図１】電解銅箔の被接着面側の処理層の例を概略的に
示す断面図である。FIG. 1 is a cross-sectional view schematically showing an example of a treatment layer on a surface to be adhered of an electrolytic copper foil.
【図２】実施例１において得られた銅箔の粗化面の粒子
構造を示す電子顕微鏡写真である（倍率：３０００
倍）。FIG. 2 is an electron micrograph showing the grain structure of the roughened surface of the copper foil obtained in Example 1 (magnification: 3000).
Times).
【図３】実施例２において得られた銅箔の粗化面の粒子
構造を示す電子顕微鏡写真である（倍率：３０００
倍）。FIG. 3 is an electron micrograph showing the grain structure of the roughened surface of the copper foil obtained in Example 2 (magnification: 3000).
Times).
【図４】実施例３において得られた銅箔の粗化面の粒子
構造を示す電子顕微鏡写真である（倍率：３０００
倍）。FIG. 4 is an electron micrograph showing a grain structure of a roughened surface of a copper foil obtained in Example 3 (magnification: 3000).
Times).
【図５】実施例４において得られた銅箔の粗化面の粒子
構造を示す電子顕微鏡写真である（倍率：３０００
倍）。5 is an electron micrograph showing the grain structure of the roughened surface of the copper foil obtained in Example 4 (magnification: 3000).
Times).
【図６】比較例１において得られた銅箔の粗化面の粒子
構造を示す電子顕微鏡写真である（倍率：３０００
倍）。FIG. 6 is an electron micrograph showing a grain structure of a roughened surface of a copper foil obtained in Comparative Example 1 (magnification: 3000).
Times).
【図７】比較例２において得られた銅箔の粗化面の粒子
構造を示す電子顕微鏡写真である（倍率：３０００
倍）。7 is an electron micrograph showing the grain structure of the roughened surface of the copper foil obtained in Comparative Example 2 (magnification: 3000).
Times).
１ 生箔 ２ 凸部 ３ 粗化処理層 ４ 銅めっき層 ５ トリート処理めっき層 ６ 防錆層 1 Raw Foil 2 Convex 3 Roughening Layer 4 Copper Plating Layer 5 Treating Plating Layer 6 Anticorrosion Layer
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成６年１月１９日[Submission date] January 19, 1994
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】全文[Correction target item name] Full text
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【書類名】 明細書[Document name] Statement
【発明の名称】 印刷回路用銅箔及びその製造方法Title: Copper foil for printed circuit and method for manufacturing the same
【特許請求の範囲】[Claims]
【発明の詳細な説明】Detailed Description of the Invention
【０００１】[0001]
【産業上の利用分野】本発明は、印刷回路用銅箔及びそ
の製造方法に関するものであり、特には銅箔と樹脂基板
との接着強度を高めるために銅箔の被接着面に鉄、ニッ
ケル及びコバルトの１種或いは２種以上を含有する多数
の突起状（粒状又は節こぶ状、以下単に突起状と記載す
る）銅電着物からなる粗化処理層を形成した印刷回路用
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 a copper foil for a printed circuit and a method for producing the same, and in particular, in order to enhance the adhesive strength between the copper foil and the resin substrate, iron or nickel is applied to the adhered surface of the copper foil. And a copper foil for a printed circuit formed with a roughening treatment layer composed of a large number of protrusion-shaped (granular or nodular, hereinafter simply referred to as protrusions) copper electrodeposits containing one or more cobalt It relates to a manufacturing method.
【０００２】[0002]
【従来技術】印刷回路用銅箔は一般に、合成樹脂等の基
材に高温高圧下で積層接着され、その後目的とする回路
を形成するべくレジストを用いて所定の回路パターンを
スクリーン印刷した後、不要部を除去するために塩化第
二銅溶液等のエッチング液を使用してエッチング処理が
施される。最終的に、所要の素子が半田付けされて、エ
レクトロニクスデバイス用の種々の印刷回路板を形成す
る。印刷配線板用銅箔に対する品質要求は、樹脂基材と
接着される被接着面（粗化面）と光沢面とで異なる。2. Description of the Related Art Generally, a printed circuit copper foil is laminated and adhered to a base material such as a synthetic resin under high temperature and high pressure, and then a predetermined circuit pattern is screen-printed with a resist to form a target circuit. An etching process is performed using an etching solution such as a cupric chloride solution to remove unnecessary portions. Finally, the required elements are soldered to form various printed circuit boards for electronic devices. Quality requirements for copper foils for printed wiring boards differ between the adhered surface (roughened surface) to be adhered to the resin base material and the glossy surface.
【０００３】本発明が関与する粗化面に対する要求とし
ては、主として、 基材との引きはがし強さが高温加熱、湿式処理、半田
付け、薬品処理等の後でも充分なこと（剥離強度）、 保存時における酸化変色のないこと（防錆性）、 基材との積層、エッチング後に生じる所謂積層汚点の
ないこと（耐塩酸性） エッチングに際して粉落ちのないこと（粉落ち防止） 等が挙げられる。中でも、充分に高い引きはがし強度を
有することは被接着面の最も重要な基本的事項である。The requirements for the roughened surface to which the present invention relates are mainly that the peeling strength from the base material is sufficient even after high temperature heating, wet treatment, soldering, chemical treatment, etc. (peeling strength), There is no oxidative discoloration during storage (anti-rust property), lamination with a base material, no so-called laminated stain that occurs after etching (hydrochloric acid resistance), and no powder drop during etching (prevention of powder drop). Above all, having a sufficiently high peeling strength is the most important basic matter of the surface to be adhered.
【０００４】銅箔と樹脂基板との接着強度を高めるため
に、銅箔の被接着面には、多数の突起状銅電着物からな
る粗化処理層が形成されている。電解銅箔に粗化処理が
施される場合には、生箔自体がすでに凸部を有してお
り、その凸部の頂上部付近に突起状銅電着物が多数電着
して凸部を更に増強することになる。In order to increase the adhesive strength between the copper foil and the resin substrate, a roughening treatment layer composed of a large number of protruding copper electrodeposits is formed on the adhered surface of the copper foil. When the electrolytic copper foil is subjected to a roughening treatment, the green foil itself already has a convex portion, and a large number of protruding copper electrodeposits are electrodeposited near the top of the convex portion to form a convex portion. It will be further enhanced.
【０００５】有効な粗化処理として、特公昭５４−３８
０５３号、特公昭５３−３９３２７号等に砒素、アンチ
モン、ビスマス、セレンまたはテルルを含む酸性銅箔電
解中で限界電流密度前後で電解することが記載されてい
る。実用的には、砒酸が電解浴に添加されることが多
い。これにより生箔の凸部に多数の突起状銅電着物が形
成され、それにより接着強度が高まり、粗化処理方法と
して有効である。As an effective roughening treatment, Japanese Patent Publication No. 54-38
No. 053, Japanese Examined Patent Publication No. 53-39327 and the like describe electrolyzing around an limiting current density in an acidic copper foil electrolysis containing arsenic, antimony, bismuth, selenium or tellurium. Practically, arsenic acid is often added to the electrolytic bath. As a result, a large number of protruding copper electrodeposits are formed on the convex portions of the raw foil, which increases the adhesive strength and is effective as a roughening treatment method.
【０００６】[0006]
【発明が解決しようとする課題】しかしながら、砒素が
関与する場合、電解時に銅電着物中に砒素が数１００ｐ
ｐｍ取り込まれるため、銅箔の再生その他の処理時にま
たエッチング時に砒素が溶出したエッチング液の処分時
に存在する砒素が環境上また健康上重大な問題となる。
こうした毒性元素を含まない粗化処理法としてベンゾキ
ノリン類を微量添加した浴を使用する方法（特公昭５６
−４１１９６号）、モリブデン、バナジウム或いは両者
を添加した浴での処理（特公昭６２−５６６７７号、特
公昭６２−５６６７８号）、或いはパルスめっきでの粗
化処理（特開昭６３−１７５９７号、特開昭５８−１６
４７９７号）等が提唱されているが、剥離強度、粉落ち
その他の面でいまだ必ずしも充分ではない。However, when arsenic is involved, arsenic is contained in the copper electrodeposit at several hundreds of p during electrolysis.
Since pm is taken in, the arsenic present during the recycling of the copper foil or other processing and the disposal of the etching solution in which arsenic is eluted during etching becomes a serious environmental and health problem.
As a roughening treatment method that does not include such toxic elements, a method using a bath to which a small amount of benzoquinoline is added is used (Japanese Patent Publication Sho 56).
No. 41196), molybdenum, vanadium, or a bath containing both of them (Japanese Patent Publication No. 62-56677 and Japanese Patent Publication No. 62-56678), or roughening treatment by pulse plating (Japanese Patent Laid-Open No. 63-17597). JP-A-58-16
No. 4797) has been proposed, but it is not always sufficient in terms of peeling strength, powder falling and the like.
【０００７】本発明の課題は、印刷回路用銅箔の被接着
面について、環境問題を呈さず、しかも樹脂基板との間
で充分な接着強度を発現しそしてエッチングに際して粉
落ちを生じない粗化処理技術を確立することである。An object of the present invention is to roughen the adhered surface of a copper foil for a printed circuit without causing environmental problems, yet exhibiting sufficient adhesive strength with a resin substrate and causing no powder drop during etching. It is to establish processing technology.
【０００８】[0008]
【課題を解決するための手段】本発明者は、課題解決に
向けての検討の結果、鉄、ニッケル及びコバルトイオン
の１種或いは２種以上を含有する銅電解浴を用いて銅箔
の被接着面に多数の突起状銅電着物からなる粗化処理層
を形成すると、デンドライト（樹枝基板結晶）の発生を
抑制しそして丸みを帯びた突起が良好に電着し、銅箔と
樹脂基板との接着強度を向上しそして粉落ちを回避する
のに有用であることを見出すに至った。この知見に基づ
いて、本発明は、（１）銅箔の被接着面に鉄、ニッケル
及びコバルトの１種或いは２種以上を含有する多数の突
起状銅電着物からなる粗化処理層を有することを特徴と
する印刷回路用銅箔を提供するものである。Means for Solving the Problems As a result of studies aimed at solving the problems, the inventor of the present invention uses a copper electrolytic bath containing one or more of iron, nickel and cobalt ions to coat a copper foil. When a roughening treatment layer consisting of a large number of protruding copper electrodeposits is formed on the adhesive surface, the generation of dendrites (dendritic substrate crystals) is suppressed and the rounded protrusions are electrodeposited well, and copper foil and resin substrate It has been found to be useful for improving the adhesive strength of and preventing powder drop. Based on this finding, the present invention has (1) a roughening treatment layer composed of a large number of protruding copper electrodeposits containing one or more of iron, nickel and cobalt on the surface to be adhered of a copper foil. The present invention provides a copper foil for a printed circuit characterized by the above.
【０００９】更に、この粗化処理層の上に従来通り更に
処理層を形成することができ、この観点から、本発明は
（２）銅箔の被接着面に鉄、ニッケル及びコバルトの１
種或いは２種以上を含有する多数の突起状銅電着物から
なる粗化処理層と、該突起状銅電着物の脱落を防止する
ため該粗化処理層を被覆する銅めっき層と、該銅めっき
層を被覆しそして銅、クロム、ニッケル、鉄、コバルト
及び亜鉛からなる群から選択される１種乃至２種以上の
金属または合金からなるトリート層とを有することを特
徴とする印刷回路用銅箔及び（３）銅箔の被接着面に
鉄、ニッケル及びコバルトの１種或いは２種以上を含有
する多数の突起状銅電着物からなる粗化処理層と、該突
起状銅電着物の脱落を防止するため該粗化処理層を被覆
する銅めっき層と、該銅めっき層を被覆しそして銅、ク
ロム、ニッケル、鉄、コバルト及び亜鉛からなる群から
選択される１種乃至２種以上の金属または合金からなる
トリート層と、該トリート層を被覆する防錆層とを有す
ることを特徴とする印刷回路用銅箔を提供する。Further, it is possible to further form a treatment layer on the roughening treatment layer in the conventional manner. From this viewpoint, the present invention provides (2) a surface of the copper foil to be adhered, which is composed of iron, nickel and cobalt.
Or a roughening treatment layer comprising a large number of protruding copper electrodeposits containing two or more kinds, a copper plating layer covering the roughening treatment layer for preventing the protruding copper electrodeposition from falling off, and the copper A copper for printed circuit, comprising a plated layer and a treat layer made of one or more metals or alloys selected from the group consisting of copper, chromium, nickel, iron, cobalt and zinc. Roughening treatment layer composed of a large number of protruding copper electrodeposits containing one or more of iron, nickel and cobalt on the adherend surface of the foil and (3) copper foil, and the protruding copper electrodeposits falling off To prevent the roughening treatment layer, and one or more selected from the group consisting of copper, chromium, nickel, iron, cobalt and zinc, which coats the copper plating layer and is selected from the group consisting of copper, chromium, nickel, iron, cobalt and zinc. A treat layer made of a metal or an alloy, Providing a copper foil for printed circuit; and a rust-preventive layer covering the over coat layer.
【００１０】更に、印刷回路用銅箔を製造する方法とし
て（４）酸性銅電解浴において銅箔を陰極として限界電
流密度付近で電解して銅箔の被接着面に多数の突起状銅
電着物からなる粗化処理層を形成する印刷回路用銅箔の
製造方法において、電解浴中に鉄、ニッケル及びコバル
トイオンの１種或いは２種以上を０．１〜５０ｇ／ｌ存
在せしめることを特徴とする印刷回路用銅箔の製造方法
及び（５）形成された粗化処理層上に、銅めっき層を形
成した後、銅、クロム、ニッケル、鉄、コバルト及び亜
鉛からなる群から選択される１種乃至２種以上の金属ま
たは合金からなるトリート層を電解により形成し、必要
に応じ更に防錆処理することを特徴とする上記の印刷回
路用銅箔の製造方法を提供する。Further, as a method for producing a copper foil for a printed circuit, (4) a large number of protruding copper electrodeposits are formed on the adhered surface of the copper foil by electrolyzing in an acidic copper electrolytic bath using the copper foil as a cathode near the limiting current density. In the method for producing a copper foil for a printed circuit for forming a roughening treatment layer consisting of 0.1 to 50 g / l of one, two or more of iron, nickel and cobalt ions are present in the electrolytic bath. A method for producing a copper foil for a printed circuit, and (5) after forming a copper plating layer on the roughening treatment layer thus formed, it is selected from the group consisting of copper, chromium, nickel, iron, cobalt and zinc 1 There is provided a method for producing a copper foil for a printed circuit as described above, characterized in that a treat layer made of one or more kinds of metals or alloys is formed by electrolysis, and if necessary, rustproofing treatment is further performed.
【００１１】[0011]
【作用】本発明に従えば、酸性銅電解浴中に鉄、ニッケ
ル及びコバルトイオンの１種或いは２種以上を０．１〜
５０ｇ／ｌ存在せしめて粗化処理層を構成することによ
り、突起状銅電着物が微量の鉄、ニッケル及びコバルト
の１種或いは２種以上を含有し、また銅電着時の核発生
を抑制してデンドライトの形成を抑制し、また電着突起
状粒子を丸めて、接着強度の向上に有用となり、またエ
ッチング時の粉落ちを防止する。鉄、ニッケル或いはコ
バルトイオンが電解浴に存在しないと、限界電流付近で
電解すると銅電着物は樹枝状となり、接着強度を改善す
るよりむしろ損なうことになる。粉落ちが生じると、エ
ッチング処理後銅の微粉が残るため電気的特性を損なう
危険がある。According to the present invention, one or more of iron, nickel and cobalt ions are added to the acidic copper electrolytic bath in an amount of 0.1 to 0.1%.
By forming a roughening treatment layer with 50 g / l being present, the protruding copper electrodeposit contains a trace amount of one or more of iron, nickel and cobalt, and suppresses nucleation during copper electrodeposition. The formation of dendrites is suppressed, and the electrodeposited projection-like particles are rounded, which is useful for improving the adhesive strength and prevents powder from falling off during etching. If iron, nickel or cobalt ions are not present in the electrolytic bath, the copper electrodeposition becomes dendritic when electrolyzed near the limiting current, and the adhesive strength is impaired rather than improved. When powder is removed, fine copper powder remains after the etching process, which may impair the electrical characteristics.
【００１２】[0012]
【実施例】本発明は、圧延銅箔及び電解銅箔いずれをも
対象としうるが、特には電解銅箔が対象とされる。電解
銅箔に固有に存在する多数の凸部を個々に更に増強する
のに有用である。従来のように砒素に代表される有毒元
素を含む銅電解浴を使用しての限界電流前後の電解によ
りこうした粗化処理層が効果的に形成されるが、砒素が
数１００ｐｐｍ粗化処理層にとり込まれるために環境及
び健康問題を呈したのである。EXAMPLES The present invention can be applied to both rolled copper foil and electrolytic copper foil, but in particular to electrolytic copper foil. It is useful for further strengthening individually the large number of protrusions inherent in the electrolytic copper foil. Such a roughening treatment layer is effectively formed by electrolysis before and after the limiting current using a copper electrolytic bath containing a toxic element typified by arsenic as in the past. It presents environmental and health problems due to its inclusion.
【００１３】図１は、電解銅箔の被接着面側の処理層の
例を概略的に示す。生箔１の被接着面には電解銅箔であ
るために、その表面全体にわたって凸部２が分布してい
る。この生箔上に粗化処理が行なわれる。本発明に従う
粗化処理により、凸部２の頂上部付近を主体として鉄、
ニッケル及びコバルトの１種或いは２種以上を含有する
多数の突起状銅電着物から構成される粗化処理層３が形
成され、凸部を増強する。圧延銅箔のような平滑な銅箔
に粗化処理が施された場合には電着物自体が突起部を構
成する。この後、多数の処理態様があるが、例えば突起
状銅電着物の脱落を防止するために薄い銅めっき層４が
形成され、そして後耐熱性その他の特性を付与するため
に銅、クロム、ニッケル、鉄、コバルト及び亜鉛等の金
属乃至合金、例えば黄銅等のトリートめっき層５が形成
され、最後にクロメート処理等に代表される防錆層６が
形成される。こうして処理された銅箔被接着面が樹脂基
板等に接着される。以下、各工程について詳述する。FIG. 1 schematically shows an example of a treatment layer on the surface to be adhered of an electrolytic copper foil. Since the surface of the raw foil 1 to be adhered is an electrolytic copper foil, the convex portions 2 are distributed over the entire surface thereof. A roughening process is performed on this raw foil. By the roughening treatment according to the present invention, iron mainly in the vicinity of the top of the convex portion 2,
A roughening treatment layer 3 composed of a large number of protruding copper electrodeposits containing one kind or two or more kinds of nickel and cobalt is formed to enhance the convex portion. When a smooth copper foil such as a rolled copper foil is subjected to a roughening treatment, the electrodeposit itself constitutes a protrusion. After this, there are many treatment modes. For example, a thin copper plating layer 4 is formed to prevent the protruding copper electrodeposits from falling off, and copper, chromium, nickel are added to impart post heat resistance and other properties. A metal or alloy such as iron, cobalt and zinc, for example, a treat plating layer 5 such as brass is formed, and finally a rust preventive layer 6 typified by chromate treatment is formed. The copper foil adhered surface thus treated is adhered to a resin substrate or the like. Hereinafter, each step will be described in detail.
【００１４】本発明に従う粗化処理用銅電解浴のめっき
条件は次の通りである： Ｃｕイオン：５〜５０ｇ／ｌ Ｈ２ＳＯ４：１０〜１００ｇ／ｌ 鉄、ニッケル、コバルトイオン：０．１〜５０ｇ／ｌ 温度：室温〜５０℃ Ｄｋ：５〜８０Ａ／ｄｍ２ 時間：１〜３０秒 銅電解浴中に存在させる鉄、ニッケル、またはコバルト
イオン或いはその組合せの濃度は０．１〜５０ｇ／ｌが
適当であり、好ましくは０．５〜３０ｇ／ｌである。添
加量が０．１ｇ／ｌ未満では接着強度を増すのに充分な
効果はなく、他方５０ｇ／ｌを超えてもその効果に顕著
な向上はなくまた経済的負担が増大する。鉄、ニッケル
またはコバルトの供給源として、硫酸塩、塩化物、硝酸
塩等の使用が可能である。例えば、硫酸塩としては、硫
酸ニッケル（７水塩）、硫酸コバルト（７水塩）、硫酸
第一鉄（７水塩）等が使用される。The plating conditions of the copper electrolytic bath for roughening treatment according to the present invention are as follows: Cu ion: 5 to 50 g / l H 2 SO 4 : 10 to 100 g / l Iron, nickel, cobalt ion: 0. 1 to 50 g / l Temperature: room temperature to 50 ° C. D k : 5 to 80 A / dm 2 hours: 1 to 30 seconds The concentration of iron, nickel, or cobalt ions or a combination thereof to be present in the copper electrolytic bath is 0.1. 50 g / l is suitable, preferably 0.5 to 30 g / l. If the amount added is less than 0.1 g / l, the effect is not sufficient to increase the adhesive strength, while if it exceeds 50 g / l, the effect is not significantly improved and the economic burden increases. As a source of iron, nickel or cobalt, it is possible to use sulfate, chloride, nitrate and the like. For example, as the sulfate, nickel sulfate (heptahydrate), cobalt sulfate (heptahydrate), ferrous sulfate (heptahydrate) and the like are used.
【００１５】上記のような粗化処理後、粗化面に、銅め
っき層を形成した後、銅、クロム、ニッケル、鉄、コバ
ルト及び亜鉛からなる群から選択される１種乃至２主以
上の金属層または合金層を形成するトリート処理を行う
ことが好ましい。例えば、特公称６２−５６６７７号等
に記載されている公知の方法で粗化処理層の突起状銅電
着物の脱落を防止するために電着物を覆って薄い銅めっ
き層が被覆され、その上に銅、クロム、ニッケル、鉄、
コバルト或いは亜鉛の金属層、或いは銅−ニッケル、銅
−コバルト、銅−ニッケル−コバルト、銅−亜鉛等に代
表され得る合金層が形成されうる（例えば、特公昭５６
−９０２８号、特開昭５４−１３９７１号、特開平２−
２９２８９４号、特開平２−２９２８９５号、特公昭５
１−３５７１１号、特公昭５４−６７０１号参照）。こ
うしたトリート処理層は銅箔の最終性状を決定するもの
としてまた障壁層としての役割を果たす。After the roughening treatment as described above, a copper plating layer is formed on the roughened surface, and one or more main components selected from the group consisting of copper, chromium, nickel, iron, cobalt and zinc are used. It is preferable to perform a treat treatment for forming a metal layer or an alloy layer. For example, a thin copper plating layer is coated over the electrodeposited material in order to prevent the protruding copper electrodeposited material of the roughening treatment layer from falling off by a known method described in Japanese Patent No. 62-56677 and the like. Copper, chrome, nickel, iron,
A metal layer of cobalt or zinc or an alloy layer typified by copper-nickel, copper-cobalt, copper-nickel-cobalt, copper-zinc, etc. may be formed (for example, Japanese Patent Publication No. 56-56).
-9028, JP-A-54-13971, JP-A-2-
292894, JP-A-2-292895, JP-B-5
1-35711, Japanese Examined Patent Publication No. 54-6701). Such treated layers serve as determinants of the final properties of the copper foil and as barrier layers.
【００１６】例えば、亜鉛被膜を例にとると、亜鉛電気
めっきおよび無電解めっきいずれでも行いうるが、粗化
面片面にのみ被膜を形成するためには亜鉛電解操作によ
る方が便宜である。また、厚さの精確な制御、厚さの一
様性、付着層の緻密化等の観点からも電解操作が好まし
い。亜鉛電解操作は、硫酸亜鉛めっき浴や塩化亜鉛めっ
き浴に代表される酸性亜鉛めっき浴、シアン化亜鉛めっ
き浴のようなアルカリ性亜鉛めっき浴、あるいはピロリ
ン酸亜鉛めっき浴が使用しうるが、もっとも一般的に使
用される硫酸亜鉛浴で充分である。硫酸亜鉛浴を使用し
た場合の好ましい亜鉛電解条件は下記の通りである。 ＺｎＳＯ４・７Ｈ２Ｏ：５０〜３５０ｇ／ｌ ｐＨ（硫酸）：２．５〜４．５ 浴温度：４０〜６０℃ 陰 極：銅箔 陽 極：亜鉛または不溶性陽極 陰極電流密度：０．０５〜０．４Ａ／ｄｍ２ 時 間：１０〜３０秒 亜鉛被覆量は、１５〜１５００μｇ／ｄｍ２とすること
が好ましく、特に好ましくは１５〜４００μｇ／ｄｍ２
である。亜鉛被覆量は、積層時の樹脂基板の種類によっ
て異なる。例えばフェノール樹脂基板用は、１５〜６０
μｇ／ｄｍ２とし、ガラスエポキシ樹脂基板用は６０〜
１５００μｇ／ｄｍ２、特に好ましくは６０〜４００μ
ｇ／ｄｍ２とする。[0016] For example, in the case of a zinc coating, either zinc electroplating or electroless plating can be performed, but zinc electrolytic operation is more convenient for forming a coating only on one surface of the roughened surface. Further, the electrolysis operation is preferable from the viewpoints of precise control of thickness, thickness uniformity, densification of the adhesion layer, and the like. Zinc electrolysis can be performed using an acidic zinc plating bath represented by a zinc sulfate plating bath or a zinc chloride plating bath, an alkaline zinc plating bath such as a zinc cyanide plating bath, or a zinc pyrophosphate plating bath. A commonly used zinc sulfate bath is sufficient. The preferable zinc electrolysis conditions when using a zinc sulfate bath are as follows. ZnSO 4 · 7H 2 O: 50~350g / l pH ( sulfate): 2.5-4.5 bath temperature: 40 to 60 ° C. Yin electrode: copper cation electrode: zinc or insoluble anode Cathode current density: 0.05 ~0.4A / dm between 2:00: 10 to 30 seconds of zinc coating amount is preferably set to 15~1500μg / dm 2, particularly preferably 15~400μg / dm 2
Is. The amount of zinc coating varies depending on the type of resin substrate at the time of stacking. For example, for phenol resin substrates, 15 to 60
μg / dm 2 for glass epoxy resin substrate 60 ~
1500 μg / dm 2 , particularly preferably 60 to 400 μ
g / dm 2 .
【００１７】合金層の一例としてＣｕ−Ｚｎトリート処
理の電解液組成及び条件例を挙げておく： ＮａＣＮ ：１０〜３０ｇ／ｌ ＮａＯＨ ：４０〜１００ｇ／ｌ ＣｕＣＮ ：６０〜１２０ｇ／ｌ Ｚｎ（ＣＮ）２：１〜１０ｇ／ｌ ｐＨ ：１０〜１３ 温度 ：６０〜８０℃ Ｄｋ ：１〜１０Ａ／ｄｍ２ As an example of the alloy layer, an electrolytic solution composition and conditions for Cu-Zn treatment are given: NaCN: 10 to 30 g / l NaOH: 40 to 100 g / l CuCN: 60 to 120 g / l Zn (CN) 2 : 1 to 10 g / l pH: 10 to 13 Temperature: 60 to 80 ° C. D k : 1 to 10 A / dm 2
【００１８】更に、好ましくは、このトリート処理層表
面上に防錆層が形成される。公知の防錆処理の任意のも
のが適用可能である。クロメート処理液は現在使用され
ている様々の処理液いずれも使用しうるが、好ましいク
ロメート処理条件例を以下に示す： Ｋ２Ｃｒ２Ｏ７（或いはＮａ２Ｃｒ２Ｏ７、Ｃｒ
Ｏ３）：０．２〜２０ｇ／ｌ 酸：りん酸あるいは硫酸、有機酸 ｐＨ：１．０〜３．５ 浴温度：２０〜４０℃ 電流密度：０．１〜０．５Ａ／ｄｍ２ 時間：１０〜６０秒 陽極：鉛板、Ｐｔ−Ｔｉ板、ステンレス鋼板 クロム酸化物付着量はクロム量として５０μｇ／ｄｍ２
以下で充分であり、好ましくは１５〜３０μｇ／ｄｍ２
とされる。クロム量が３０μｇ／ｄｍ２を超えると防錆
力は向上するがエッチング性が低下する。Further, preferably, a rust preventive layer is formed on the surface of the treated layer. Any known rustproofing treatment can be applied. The chromate treatment liquid may be any of various treatment liquids currently used, but preferable chromate treatment condition examples are as follows: K 2 Cr 2 O 7 (or Na 2 Cr 2 O 7 , Cr)
O 3 ): 0.2 to 20 g / l Acid: phosphoric acid or sulfuric acid, organic acid pH: 1.0 to 3.5 Bath temperature: 20 to 40 ° C. Current density: 0.1 to 0.5 A / dm 2 hours : 10 to 60 seconds Anode: Lead plate, Pt-Ti plate, stainless steel plate Chromium oxide adhesion amount is 50 μg / dm 2 as chromium amount
The following is sufficient and preferably 15 to 30 μg / dm 2.
It is said that When the amount of chromium exceeds 30 μg / dm 2 , the rust preventive power is improved but the etching property is deteriorated.
【００１９】有用な防錆方法として、本件出願人は、電
解亜鉛・クロム処理による亜鉛及び／又は酸化亜鉛とク
ロム酸化物との混合皮膜処理を提唱し（特公昭５８−７
０７７号）、多くの成果を挙げてきた。更に、特開平２
−２９４４９０号は、長期間高温多湿条件下での黒点発
生を防止することを目的として、浸漬クロメート処理に
よりクロム酸化物皮膜を形成し、続いて電解亜鉛・クロ
ム処理により亜鉛及び／又は酸化亜鉛とクロム酸化物と
の混合皮膜を形成することを開示する。As a useful rust preventive method, the present applicant has proposed a mixed film treatment of zinc and / or zinc oxide and chromium oxide by electrolytic zinc / chromium treatment (Japanese Patent Publication No. 58-7).
No. 077), many achievements have been made. Furthermore, JP-A-2
No. 294490, for the purpose of preventing the generation of black spots under high temperature and high humidity conditions for a long period of time, a chromium oxide film is formed by immersion chromate treatment, and then zinc and / or zinc oxide is formed by electrolytic zinc / chromium treatment. Forming a mixed film with chromium oxide is disclosed.
【００２０】最後に、必要に応じ、銅箔と樹脂基板との
接着力の改善を主目的として、防錆層上にシランカップ
リング剤を塗布するシラン処理が施される。塗布方法
は、シランカップリング剤溶液のスプレーによる吹付
け、コーターでの塗布、浸漬、流しかけ等いずれでもよ
い。例えば、特公昭６０−１５６５４号は、銅箔の粗面
側にクロメート処理を施した後シランカップリング剤処
理を行なうことによって銅箔と樹脂基板との接着力を改
善することを記載している。詳細はこれを参照された
い。Finally, if necessary, a silane treatment for applying a silane coupling agent onto the anticorrosive layer is performed mainly for the purpose of improving the adhesive force between the copper foil and the resin substrate. The coating method may be spraying of a silane coupling agent solution, coating with a coater, dipping, pouring, or the like. For example, Japanese Examined Patent Publication No. 60-15654 describes that the adhesion between the copper foil and the resin substrate is improved by subjecting the rough surface side of the copper foil to a chromate treatment and then a silane coupling agent treatment. . For details, refer to this.
【００２１】こうして粗化面を被膜処理された銅箔は、
光沢面を必要に応じ処理した後、粗化面に接着剤を塗布
して樹脂基板に加熱圧着することにより印刷回路用銅張
り積層板とされ、所定の加工操作を経た後、印刷回路板
として使用に供される。光沢面の処理方法としては、ク
ロメート処理を含む各種化成処理、銅とのキレート化反
応を利用した有機剤処理、銅より卑な金属ないし合金の
被覆処理等その面において要求される特定水準に応じて
適当なものが選ばれる。The copper foil coated on the roughened surface in this way is
After processing the glossy surface as necessary, apply an adhesive to the roughened surface and heat press bond to the resin substrate to make a copper clad laminate for printed circuits, and after a predetermined processing operation, as a printed circuit board Be used. As a treatment method for glossy surface, various chemical conversion treatments including chromate treatment, organic agent treatment utilizing chelation reaction with copper, coating treatment of metals or alloys that are baser than copper, etc. Appropriate one is selected.
【００２２】この後、必要に応じて、銅箔の延性を改善
する目的で焼鈍処理を施すこともある。Thereafter, if necessary, an annealing treatment may be performed for the purpose of improving the ductility of the copper foil.
【００２３】本発明による鉄、ニッケル又はコバルトイ
オン或いはその組合せを含有する銅電解浴で粗化した銅
箔は、その処理は均一であり、ムラもなく優秀な基板特
性を示した。即ち、銅箔とガラス布基材エポキシ樹脂で
積層板を作製した場合、良好な接着性及び耐熱性を示
し、デンドライトの発達を抑えた丸みのある銅電着物が
形成されるので、接着強度は高くまたエッチング後の基
板の電気的特性や粉落ちの問題がなく良好な性状を示し
た。２．４ｋｇ／ｃｍ以上の引きはがし強さが得られ、
特にＮｉ，Ｃｏについては２．６０〜２．７８ｋｇ／ｃ
ｍもの高水準の引きはがし強さが得られた。The copper foil roughened with a copper electrolytic bath containing iron, nickel or cobalt ions or a combination thereof according to the present invention was uniformly treated and showed excellent substrate characteristics without unevenness. That is, when a laminate is prepared from a copper foil and a glass cloth-based epoxy resin, it shows good adhesiveness and heat resistance, and a rounded copper electrodeposit with suppressed dendrite development is formed. It was high and showed good properties without problems such as electrical characteristics of the substrate after etching and powder falling off. A peeling strength of 2.4 kg / cm or more is obtained,
Especially for Ni and Co, 2.60 to 2.78 kg / c
A high level of peel strength was obtained.
【００２４】以下、実施例及び比較例を示す。Examples and comparative examples will be shown below.
【００２５】（実施例１）硫酸銅（５水塩）１００ｇ／
ｌ、硫酸１００ｇ／ｌ及び硫酸ニッケル（７水塩）１０
ｇ／ｌを含む水溶液を３０℃で電解浴として使用し、厚
さ７０μｍの電解銅箔の被接着面に電流密度２０Ａ／ｄ
ｍ２で１０秒間めっきした。このようにして得られた銅
箔を分析したところ、箔全体に対するニッケルの含有料
は約２ｐｐｍ（突起状銅電着物中のＮｉ含有量は、約
０．０２ｗｔ％）であった。得られた銅箔の粗化面の突
起状銅電着物の電着状況を示す電子顕微鏡写真を図２に
示す。また、ガラス布基材エポキシ樹脂で加熱・加圧し
て銅張り積層板を作製し、引きはがし強さ及び粉落ち特
性を測定した。結果を表１に示す。(Example 1) 100 g of copper sulfate (pentahydrate) /
1, sulfuric acid 100 g / l and nickel sulfate (heptahydrate) 10
An aqueous solution containing g / l was used as an electrolytic bath at 30 ° C., and a current density of 20 A / d was applied to the adhered surface of an electrolytic copper foil having a thickness of 70 μm.
Plated at m 2 for 10 seconds. When the copper foil thus obtained was analyzed, the content of nickel in the entire foil was about 2 ppm (the Ni content in the protruding copper electrodeposit was about 0.02 wt%). An electron micrograph showing the electrodeposition state of the protruding copper electrodeposit on the roughened surface of the obtained copper foil is shown in FIG. Further, a copper-clad laminate was prepared by heating and pressurizing with a glass cloth base epoxy resin, and peeling strength and powder falling property were measured. The results are shown in Table 1.
【００２６】（実施例２）硫酸銅（５水塩）１００ｇ／
ｌ、硫酸１００ｇ／ｌ及び硫酸コバルト（７水塩）５ｇ
／ｌを含む水溶液を３０℃で電解浴として使用し、厚さ
７０μｍの電解銅箔の被接着面に電流密度１０Ａ／ｄｍ
２で２０秒間めっきした。このようにして得られた銅箔
を分折したところ、箔全体に対するコバルトの含有量は
約１ｐｐｍ（突起状銅電着物中のＣｏ含有量は、約０．
０１ｗｔ％）であった。得られた銅箔の粗化面の突起状
銅電着物の電着状況を示す電子顕微鏡写真を図３に示
す。また、ガラス布基材エポキシ樹脂で加熱・加圧して
銅張り積層板を作製し、引きはがし強さ及び粉落ち特性
を測定した。結果を表１に示す。(Example 2) 100 g of copper sulfate (pentahydrate) /
1, sulfuric acid 100 g / l and cobalt sulfate (heptahydrate) 5 g
An aqueous solution containing 1 / l was used as an electrolytic bath at 30 ° C., and the current density was 10 A / dm on the adhered surface of an electrolytic copper foil having a thickness of 70 μm.
2 for 20 seconds. When the copper foil thus obtained was broken, the content of cobalt in the entire foil was about 1 ppm (the Co content in the protruding copper electrodeposit was about 0.
It was 01 wt%). An electron micrograph showing the electrodeposition state of the protruding copper electrodeposit on the roughened surface of the obtained copper foil is shown in FIG. Further, a copper-clad laminate was prepared by heating and pressurizing with a glass cloth base epoxy resin, and peeling strength and powder falling property were measured. The results are shown in Table 1.
【００２７】（実施例３）硫酸銅（５水塩）１００ｇ／
ｌ、硫酸１００ｇ／１及び硫酸第１鉄（７水塩）２０ｇ
／ｌを含む水溶液を３０℃で電解浴として使用し、厚さ
７０μｍの電解銅箔の被接着面に電流密度２０Ａ／ｄｍ
２で１０秒間めっきした。このようにして得られた銅箔
を分析したところ、箔全体に対する鉄の含有量は約４ｐ
ｐｍ（突起状銅電着物中のＦｅ含有量は、約０．０３ｗ
ｔ％）であった。得られた銅箔の粗化面の突起状銅電着
物の電着状況を示す電子顕微鏡写真を図４に示す。ま
た、ガラス布基材エポキシ樹脂で加熱・加圧して銅張り
積層板を作製し、引きはがし強さ及び粉落ち特性を測定
した。結果を表１に示す。(Example 3) 100 g of copper sulfate (pentahydrate) /
1, sulfuric acid 100g / 1 and ferrous sulfate (heptahydrate) 20g
An aqueous solution containing 1 / l was used as an electrolytic bath at 30 ° C., and a current density of 20 A / dm was applied to the adhered surface of an electrolytic copper foil having a thickness of 70 μm.
Plated at 2 for 10 seconds. When the copper foil thus obtained was analyzed, the iron content in the entire foil was about 4 p.
pm (Fe content in the protruding copper electrodeposition is about 0.03w
t%). An electron micrograph showing the electrodeposition state of the protruding copper electrodeposit on the roughened surface of the obtained copper foil is shown in FIG. Further, a copper-clad laminate was prepared by heating and pressurizing with a glass cloth base epoxy resin, and peeling strength and powder falling property were measured. The results are shown in Table 1.
【００２８】（実施例４）硫酸銅（５水塩）１００ｇ／
ｌ、硫酸１００ｇ／ｌ、硫酸ニッケル（７水塩）５ｇ／
ｌ及び硫酸コバルト（７水塩）５ｇ／ｌを含む水溶液を
３０℃で電解浴として使用し、厚さ７０μｍの電解銅箔
の被接着面に電流密度１０Ａ／ｄｍ２で２０秒間めっき
した。このようにして得られた銅箔を分析したところ、
箔全体に対するニッケル及びコバルトの含有量はそれぞ
れ約１ｐｐｍ（突起状銅電着物中のＮｉ及びＣｏの含有
量は、それぞれ約０．０１ｗｔ％）であった。得られた
銅箔の粗化面の突起状銅電着物の電着状況を示す電子顕
微鏡写真を図５に示す。また、ガラス布基材エポキシ樹
脂で加熱・加圧して銅張り積層板を作製し、引きはがし
強さ及び粉落ち特性を測定した。結果を表１に示す。Example 4 Copper sulfate (pentahydrate) 100 g /
1, sulfuric acid 100 g / l, nickel sulfate (heptahydrate) 5 g /
1 and an aqueous solution containing 5 g / l of cobalt sulfate (heptahydrate) were used as an electrolytic bath at 30 ° C., and a surface to be adhered of an electrolytic copper foil having a thickness of 70 μm was plated at a current density of 10 A / dm 2 for 20 seconds. When the copper foil thus obtained was analyzed,
The contents of nickel and cobalt with respect to the entire foil were each about 1 ppm (the contents of Ni and Co in the protruding copper electrodeposition were each about 0.01 wt%). An electron micrograph showing the electrodeposition state of the protruding copper electrodeposit on the roughened surface of the obtained copper foil is shown in FIG. Further, a copper-clad laminate was prepared by heating and pressurizing with a glass cloth base epoxy resin, and peeling strength and powder falling property were measured. The results are shown in Table 1.
【００２９】（比較例１）添加物を含まない例として、
硫酸銅（５水塩）１００ｇ／ｌ及び硫酸１００ｇ／ｌを
含む水溶液を３０℃で電解浴として使用し、厚さ７０μ
ｍの電解銅箔の被接着面に電流密度２０Ａ／ｄｍ２で１
０秒間めっきした。得られた銅箔の粗化面の突起状銅電
着物の電着状況を示す電子顕微鏡写真を図６に示す。ま
た、ガラス布基材エポキシ樹脂で加熱・加圧して銅張り
積層板を作製し、引きはがし強さ及び粉落ち特性を測定
した。結果を表１に示す。図６には、樹枝状電着物が観
察される。(Comparative Example 1) As an example containing no additives,
An aqueous solution containing 100 g / l of copper sulfate (pentahydrate) and 100 g / l of sulfuric acid was used as an electrolytic bath at 30 ° C. and had a thickness of 70 μm.
1 with a current density of 20 A / dm 2 on the surface to be adhered of electrolytic copper foil of m
Plated for 0 seconds. An electron micrograph showing the electrodeposition state of the protruding copper electrodeposit on the roughened surface of the obtained copper foil is shown in FIG. Further, a copper-clad laminate was prepared by heating and pressurizing with a glass cloth base epoxy resin, and peeling strength and powder falling property were measured. The results are shown in Table 1. In FIG. 6, a dendritic electrodeposit is observed.
【００３０】（比較例２）従来からの砒素を含む例とし
て、硫酸銅（５水塩）１００ｇ／ｌ、硫酸１００ｇ／ｌ
及び砒酸３ｇ／ｌを含む水溶液を３０℃で電解浴として
使用し、厚さ７０μｍの電解銅箔の被接着面に電流密度
２０Ａ／ｄｍ２で１０秒間めっきした。このようにして
得られた銅箔を分折したところ、箔全体に対する砒素の
含有量は約２００ｐｐｍ（突起状銅電着物中のＡｓ含有
量は、約１．２ｗｔ％）であった。得られた銅箔の粗化
面の突起状銅電着物の電着状況を示す電子顕微鏡写真を
図７に示す。また、ガラス布基材エポキシ樹脂で加熱・
加圧して銅張り積層板を作製し、引きはがし強さ及び粉
落ち特性を測定した。結果を表１に示す。Comparative Example 2 As an example containing conventional arsenic, copper sulfate (pentahydrate) 100 g / l, sulfuric acid 100 g / l
And an aqueous solution containing 3 g / l of arsenic acid was used as an electrolytic bath at 30 ° C., and the adhered surface of an electrolytic copper foil having a thickness of 70 μm was plated at a current density of 20 A / dm 2 for 10 seconds. When the copper foil thus obtained was broken, the content of arsenic with respect to the entire foil was about 200 ppm (the As content in the protruding copper electrodeposit was about 1.2 wt%). An electron micrograph showing the electrodeposition state of the protruding copper electrodeposit on the roughened surface of the obtained copper foil is shown in FIG. 7. Also, heating with glass cloth base epoxy resin
A copper-clad laminate was prepared by pressurizing, and the peel strength and the powder falling property were measured. The results are shown in Table 1.
【００３１】[0031]
【表１】 [Table 1]
【００３２】[0032]
【発明の効果】本発明による鉄、ニッケル又はコバルト
イオン或いはその組合せを含有する銅電解浴で粗化した
銅箔は、その処理は均一であり、ムラもなく優秀な基板
特性を示す。銅箔とガラス布基材エポキシ樹脂で積層板
を作製した場合、良好な接着性及び耐熱性を示し、デン
ドライトの発達を抑えた丸みのある電着物が形成される
ので、接着強度は非常に高くまたエッチング後の基板の
電気的特性や粉落ちの問題がない。The copper foil roughened with the copper electrolytic bath containing iron, nickel or cobalt ions or the combination thereof according to the present invention has a uniform treatment and shows excellent substrate characteristics without unevenness. When a laminate is made of copper foil and glass cloth-based epoxy resin, it shows good adhesiveness and heat resistance, and a rounded electrodeposit with suppressed dendrite formation is formed, so the adhesive strength is very high. Further, there is no problem of electrical characteristics of the substrate after etching and powder drop.
【図面の簡単な説明】[Brief description of drawings]
【図１】電解銅箔の被接着面側の処理層の例を概略的に
示す断面図である。FIG. 1 is a cross-sectional view schematically showing an example of a treatment layer on a surface to be adhered of an electrolytic copper foil.
【図２】実施例１において得られた銅箔の粗化面の粒子
構造を示す電子顕微鏡写真である（倍率：３０００
倍）。FIG. 2 is an electron micrograph showing the grain structure of the roughened surface of the copper foil obtained in Example 1 (magnification: 3000).
Times).
【図３】実施例２において得られた銅箔の粗化面の粒子
構造を示す電子顕微鏡写真である（倍率：３０００
倍）。FIG. 3 is an electron micrograph showing the grain structure of the roughened surface of the copper foil obtained in Example 2 (magnification: 3000).
Times).
【図４】実施例３において得られた銅箔の粗化面の粒子
構造を示す電子顕微鏡写真である（倍率：３０００
倍）。FIG. 4 is an electron micrograph showing a grain structure of a roughened surface of a copper foil obtained in Example 3 (magnification: 3000).
Times).
【図５】実施例４において得られた銅箔の粗化面の粒子
構造を示す電子顕微鏡写真である（倍率：３０００
倍）。5 is an electron micrograph showing the grain structure of the roughened surface of the copper foil obtained in Example 4 (magnification: 3000).
Times).
【図６】比較例１において得られた銅箔の粗化面の粒子
構造を示す電子顕微鏡写真である（倍率：３０００
倍）。FIG. 6 is an electron micrograph showing a grain structure of a roughened surface of a copper foil obtained in Comparative Example 1 (magnification: 3000).
Times).
【図７】比較例２において得られた銅箔の粗化面の粒子
構造を示す電子顕微鏡写真である（倍率：３０００
倍）。7 is an electron micrograph showing the grain structure of the roughened surface of the copper foil obtained in Comparative Example 2 (magnification: 3000).
Times).
【符号の説明】 １ 生箔 ２ 凸部 ３ 粗化処理層 ４ 銅めっき層 ５ トリート処理めっき層 ６ 防錆層[Explanation of symbols] 1 Raw foil 2 Convex portion 3 Roughening treatment layer 4 Copper plating layer 5 Treat treatment plating layer 6 Anticorrosion layer
Claims (5)
ルトの１種或いは２種以上を含有する多数の突起状銅電
着物からなる粗化処理層を有することを特徴とする印刷
回路用銅箔。1. A printed circuit having a roughening treatment layer comprising a large number of protruding copper electrodeposits containing one or more of iron, nickel and cobalt on the adhered surface of a copper foil. Copper foil.
ルトの１種或いは２種以上を含有する多数の突起状銅電
着物からなる粗化処理層と、該粗化処理層を被覆する
銅、クロム、ニッケル、鉄、コバルト及び亜鉛からなる
群から選択される１種乃至２種以上の金属または合金か
らなるトリート層とを有することを特徴とする印刷回路
用銅箔。2. A surface to be adhered of a copper foil is coated with a roughening treatment layer comprising a large number of protruding copper electrodeposits containing one or more of iron, nickel and cobalt, and the roughening treatment layer. A copper foil for a printed circuit, comprising a treat layer comprising one or more metals or alloys selected from the group consisting of copper, chromium, nickel, iron, cobalt and zinc.
ルトの１種或いは２種以上を含有する多数の突起状銅電
着物からなる粗化処理層と、該粗化処理層を被覆する
銅、クロム、ニッケル、鉄、コバルト及び亜鉛からなる
群から選択される１種乃至２種以上の金属または合金か
らなるトリート層と、該トリート層を被覆する防錆層と
を有することを特徴とする印刷回路用銅箔。3. A surface to be adhered of a copper foil is coated with a roughening treatment layer comprising a large number of protruding copper electrodeposits containing one or more of iron, nickel and cobalt, and the roughening treatment layer. A treat layer comprising one or more metals or alloys selected from the group consisting of copper, chromium, nickel, iron, cobalt, and zinc; and a rust preventive layer covering the treat layer. Copper foil for printed circuits.
限界電流密度付近で電解して銅箔の被接着面に多数の突
起状銅電着物からなる粗化処理層を形成する印刷回路用
銅箔の製造方法において、電解浴中に鉄、ニッケル及び
コバルトイオンの１種或いは２種以上を０．１〜５０ｇ
／ｌ存在せしめることを特徴とする印刷回路用銅箔の製
造方法。4. A copper for a printed circuit, wherein a copper foil is used as a cathode in an acidic copper electrolytic bath to electrolyze in the vicinity of a limiting current density to form a roughening treatment layer composed of a large number of protruding copper electrodeposits on the adhered surface of the copper foil. In the method for producing a foil, 0.1 to 50 g of one or more of iron, nickel and cobalt ions is added to the electrolytic bath.
The method for producing a copper foil for a printed circuit, characterized in that the copper foil for a printed circuit is present.
ニッケル、鉄、コバルト及び亜鉛からなる群から選択さ
れる１種乃至２種以上の金属または合金からなるトリー
ト層を電解により形成し、必要に応じ更に防錆処理する
ことを特徴とする請求項４の印刷回路用銅箔の製造方
法。5. Copper, chromium, on the roughening layer thus formed
5. A treat layer comprising one or more metals or alloys selected from the group consisting of nickel, iron, cobalt and zinc is formed by electrolysis and further rustproofed if necessary. Manufacturing method of copper foil for printed circuit.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4332219A JP2717910B2 (en) | 1992-11-19 | 1992-11-19 | Copper foil for printed circuit and manufacturing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4332219A JP2717910B2 (en) | 1992-11-19 | 1992-11-19 | Copper foil for printed circuit and manufacturing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06169168A true JPH06169168A (en) | 1994-06-14 |
| JP2717910B2 JP2717910B2 (en) | 1998-02-25 |
Family
ID=18252509
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4332219A Expired - Lifetime JP2717910B2 (en) | 1992-11-19 | 1992-11-19 | Copper foil for printed circuit and manufacturing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2717910B2 (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2285813A (en) * | 1994-01-21 | 1995-07-26 | Olin Corp | Electrolytic treatment of copper foil to deposit a dark-coloured,nodular layer of copper-nickel alloy to improve bond strength to dielectric substrate |
| WO2001077420A1 (en) * | 2000-04-05 | 2001-10-18 | Nikko Materials Company, Limited | Laser hole drilling copper foil |
| JP2005139544A (en) * | 2003-07-28 | 2005-06-02 | Mitsui Mining & Smelting Co Ltd | Surface-treated copper foil having blackening-treated surface, process for producing the surface-treated copper foil and, using the surface-treated copper foil, electromagnetic wave shielding conductive mesh for front panel of plasma display |
| US6902824B2 (en) | 2000-04-28 | 2005-06-07 | Mitsui Mining & Smelting Co., Ltd. | Copper foil and metal foil with carrier foil for printed wiring board, and semi-additive process for producing printed wiring board using the same |
| WO2005083157A1 (en) * | 2004-03-02 | 2005-09-09 | Mitsui Mining & Smelting Co., Ltd. | Surface-treated copper foil having grayed surface, process for producing the same and electromagnetic wave shielding conductive mesh for front panel of plasma display wherein use is made of the surface-treated copper foil |
| US7455533B2 (en) | 2004-11-19 | 2008-11-25 | Sharp Kabushiki Kaisha | Method for producing printed wiring board |
| JP2009242945A (en) * | 2008-03-31 | 2009-10-22 | Ls Mtron Ltd | Surface treating method of copper foil for printed circuit, copper foil produced by the same, and plating apparatus |
| KR20120112216A (en) | 2011-03-31 | 2012-10-11 | 신닛테츠가가쿠 가부시키가이샤 | Metal-clad laminate |
| JP2013174017A (en) * | 2008-11-25 | 2013-09-05 | Jx Nippon Mining & Metals Corp | Copper foil for printed circuit |
| JP2014019914A (en) * | 2012-07-19 | 2014-02-03 | Fukuda Metal Foil & Powder Co Ltd | High emissivity metal foil |
| KR20150077944A (en) * | 2013-12-30 | 2015-07-08 | 일진머티리얼즈 주식회사 | Copper foil, electric component and battery comprising the foil |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63500250A (en) * | 1985-06-28 | 1988-01-28 | サーキット フォイル ユー．エス．エイ．インコーポレイテッド | Treatment for copper foil |
| JPH0496395A (en) * | 1990-08-14 | 1992-03-27 | Nikko Kyodo Co Ltd | Processing method for copper foil for printed circuit |
| JPH0496394A (en) * | 1990-08-14 | 1992-03-27 | Nikko Kyodo Co Ltd | Processing method for copper foil for printed circuit |
-
1992
- 1992-11-19 JP JP4332219A patent/JP2717910B2/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63500250A (en) * | 1985-06-28 | 1988-01-28 | サーキット フォイル ユー．エス．エイ．インコーポレイテッド | Treatment for copper foil |
| JPH0496395A (en) * | 1990-08-14 | 1992-03-27 | Nikko Kyodo Co Ltd | Processing method for copper foil for printed circuit |
| JPH0496394A (en) * | 1990-08-14 | 1992-03-27 | Nikko Kyodo Co Ltd | Processing method for copper foil for printed circuit |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2285813A (en) * | 1994-01-21 | 1995-07-26 | Olin Corp | Electrolytic treatment of copper foil to deposit a dark-coloured,nodular layer of copper-nickel alloy to improve bond strength to dielectric substrate |
| GB2285813B (en) * | 1994-01-21 | 1997-12-10 | Olin Corp | Nodular copper/nickel alloy treatment for copper foil |
| WO2001077420A1 (en) * | 2000-04-05 | 2001-10-18 | Nikko Materials Company, Limited | Laser hole drilling copper foil |
| US6902824B2 (en) | 2000-04-28 | 2005-06-07 | Mitsui Mining & Smelting Co., Ltd. | Copper foil and metal foil with carrier foil for printed wiring board, and semi-additive process for producing printed wiring board using the same |
| JP2005139544A (en) * | 2003-07-28 | 2005-06-02 | Mitsui Mining & Smelting Co Ltd | Surface-treated copper foil having blackening-treated surface, process for producing the surface-treated copper foil and, using the surface-treated copper foil, electromagnetic wave shielding conductive mesh for front panel of plasma display |
| JP2005248221A (en) * | 2004-03-02 | 2005-09-15 | Mitsui Mining & Smelting Co Ltd | Surface-treated copper foil having grayish-treated surface, method for manufacturing the copper foil, and electromagnetic wave shielding conductive mesh for front panel of plasma display using the copper foil |
| WO2005083157A1 (en) * | 2004-03-02 | 2005-09-09 | Mitsui Mining & Smelting Co., Ltd. | Surface-treated copper foil having grayed surface, process for producing the same and electromagnetic wave shielding conductive mesh for front panel of plasma display wherein use is made of the surface-treated copper foil |
| KR100869196B1 (en) * | 2004-03-02 | 2008-11-18 | 미쓰이 긴조꾸 고교 가부시키가이샤 | Surface-treated copper foil having grayed surface, process for producing the same and electromagnetic wave shielding conductive mesh for front panel of plasma display wherein use is made of the surface-treated copper foil |
| US7455533B2 (en) | 2004-11-19 | 2008-11-25 | Sharp Kabushiki Kaisha | Method for producing printed wiring board |
| JP2009242945A (en) * | 2008-03-31 | 2009-10-22 | Ls Mtron Ltd | Surface treating method of copper foil for printed circuit, copper foil produced by the same, and plating apparatus |
| JP2013174017A (en) * | 2008-11-25 | 2013-09-05 | Jx Nippon Mining & Metals Corp | Copper foil for printed circuit |
| KR20120112216A (en) | 2011-03-31 | 2012-10-11 | 신닛테츠가가쿠 가부시키가이샤 | Metal-clad laminate |
| JP2014019914A (en) * | 2012-07-19 | 2014-02-03 | Fukuda Metal Foil & Powder Co Ltd | High emissivity metal foil |
| KR20150077944A (en) * | 2013-12-30 | 2015-07-08 | 일진머티리얼즈 주식회사 | Copper foil, electric component and battery comprising the foil |
| JP2017508890A (en) * | 2013-12-30 | 2017-03-30 | イルジン マテリアルズ カンパニー リミテッドＩｌｊｉｎ Ｍａｔｅｒｉａｌｓ Ｃｏ．， Ｌｔｄ． | Copper foil, electrical parts including the same, and battery |
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|---|---|
| JP2717910B2 (en) | 1998-02-25 |
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