JPH08236930A - Copper foil for printed circuit and its manufacture - Google Patents
Copper foil for printed circuit and its manufactureInfo
- Publication number
- JPH08236930A JPH08236930A JP7058225A JP5822595A JPH08236930A JP H08236930 A JPH08236930 A JP H08236930A JP 7058225 A JP7058225 A JP 7058225A JP 5822595 A JP5822595 A JP 5822595A JP H08236930 A JPH08236930 A JP H08236930A
- Authority
- JP
- Japan
- Prior art keywords
- copper
- group
- layer
- copper foil
- zinc
- 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
Landscapes
- Parts Printed On Printed Circuit Boards (AREA)
- Electroplating Methods And Accessories (AREA)
- Manufacturing Of Printed Wiring (AREA)
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クロム及
びタングステンから成る第１群から選ばれた１種或いは
２種である第１群金属と、バナジウム、ニッケル、鉄、
コバルト、亜鉛、ゲルマニウム及びモリブデンから成る
第２群から選ばれたる１種或いは２種以上である第２群
金属との両者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）銅電着物から成る粗化
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 manufacturing the same, and in particular, chromium and tungsten are provided on the adhered surface of the copper foil in order to enhance the adhesive strength between the copper foil and the resin substrate. Group 1 metal which is one or two selected from the first group consisting of vanadium, nickel, iron,
A large number of protrusions (granular or nodular, hereinafter simply referred to as protrusions) containing both of one or more second group metals selected from the second group consisting of cobalt, zinc, germanium and molybdenum. The present invention relates to a copper foil for a printed circuit on which a roughening treatment layer made of a copper electrodeposit is formed and a method for producing the same.
【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成
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】本発明者等は、課題解決
に向けての検討の結果、（ａ）クロム及びタングステン
から成る第１群から選ばれた１種或いは２種である第１
群金属と（ｂ）バナジウム、ニッケル、鉄、コバルト、
亜鉛、ゲルマニウム及びモリブデンから成る第２群から
選ばれたる１種或いは２種以上である第２群金属との両
者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成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、銅
箔の被接着面に、（ａ）クロム及びタングステンから成
る第１群から選ばれた１種或いは２種である第１群金属
と（ｂ）バナジウム、ニッケル、鉄、コバルト、亜鉛、
ゲルマニウム及びモリブデンから成る第２群から選ばれ
た１種或いは２種以上である第２群金属との両者を含有
する多数の突起状銅電着物から成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。Means for Solving the Problems As a result of studies aimed at solving the problems, the present inventors have found that (a) one or two selected from the first group consisting of chromium and tungsten.
Group metals and (b) vanadium, nickel, iron, cobalt,
Using a copper electrolytic bath containing both one or more second group metals selected from the second group consisting of zinc, germanium and molybdenum, a large number of projecting copper particles are formed on the adhered surface of the copper foil. When a roughening treatment layer made of an electrodeposit is formed, the generation of dendrites (dendritic crystals) is suppressed and the rounded projections are well electrodeposited, and the adhesive strength between the copper foil and the resin substrate is improved, and It came to be found to be useful in avoiding powder drop. Based on this finding, the present invention provides that, on the adhered surface of a copper foil, (a) one or two first group metals selected from the first group consisting of chromium and tungsten, and (b) vanadium, Nickel, iron, cobalt, zinc,
It is characterized by having a roughening treatment layer composed of a large number of protruding copper electrodeposits containing both one type or two or more types of second group metals selected from the second group consisting of germanium and molybdenum. Provided is a copper foil for a printed circuit.
【０００９】この粗化処理層の上に従来通り更にトリー
ト層及び防錆層を形成することができ、この観点から、
本発明は更に、銅箔の被接着面に、（ａ）クロム及びタ
ングステンから成る第１群から選ばれた１種或いは２種
である第１群金属と（ｂ）バナジウム、ニッケル、鉄、
コバルト、亜鉛、ゲルマニウム及びモリブデンから成る
第２群から選ばれたる１種或いは２種以上である第２群
金属との両者を含有する多数の突起状銅電着物から成る
粗化処理層と、前記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成る群から選
択された１種乃至２種以上の金属又は合金から成るトリ
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。突起状銅電
着物の脱落を防止する薄い銅めっき層を前記粗化処理層
とトリート層との間に形成するのが有益である。A treat layer and a rust preventive layer can be further formed on the roughening treatment layer in the conventional manner. From this viewpoint,
The present invention further includes (a) a first group metal which is one or two selected from the first group consisting of chromium and tungsten, and (b) vanadium, nickel, iron, and
A roughening treatment layer comprising a large number of protruding copper electrodeposits containing both one or two or more second group metals selected from the second group consisting of cobalt, zinc, germanium and molybdenum; Treat layer for coating the roughening layer, which is made of one or more metals or alloys selected from the group consisting of copper, chromium, nickel, iron, cobalt and zinc, and rust preventive for coating the treat layer There is provided a copper foil for a printed circuit, which has a layer. It is beneficial to form a thin copper plating layer between the roughened layer and the treat layer to prevent the protruding copper electrodeposits from falling off.
【００１０】更に、印刷回路用銅箔を製造する方法とし
て、本発明は、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
起状銅電着物から成る粗化処理層を形成する印刷回路用
銅箔及びその製造方法において、電解浴中に（ａ）クロ
ム及びタングステンから成る第１群から選ばれた１種或
いは２種である第１群金属：０．０００１〜５ｇ／l
と、（ｂ）バナジウム、ニッケル、鉄、コバルト、亜
鉛、ゲルマニウム及びモリブデンから成る第２群から選
ばれたる１種或いは２種以上である第２群金属：０．０
０１〜５０ｇ／l の両者を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を提供する。更に、粗化処
理層上に、好ましくは形成された粗化処理層上に突起状
銅電着物の脱落を防止する薄い銅めっき層を電解により
形成した後、銅、クロム、ニッケル、鉄、コバルト及び
亜鉛から成る群から選択される１種乃至２種以上の金属
又は合金から成るトリート層を電解により形成し、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
製造方法が提供される。Further, as a method for producing a copper foil for a printed circuit, the present invention uses a copper foil as a cathode in an acidic copper electrolytic bath to electrolyze in the vicinity of a limiting current density to produce a large number of protruding copper on the adhered surface of the copper foil. A copper foil for a printed circuit for forming a roughening treatment layer composed of an electrodeposit and a method for producing the same, wherein the electrolytic bath contains (a) one or two selected from the first group consisting of chromium and tungsten. Group metal: 0.0001 to 5 g / l
And (b) one or more second group metals selected from the second group consisting of vanadium, nickel, iron, cobalt, zinc, germanium, and molybdenum: 0.0
Provided is a method for producing a copper foil for a printed circuit, characterized in that both 01 to 50 g / l are present. Furthermore, on the roughening treatment layer, preferably, after forming a thin copper plating layer by electrolysis to prevent the dropout of the protruding copper electrodeposit on the roughening treatment layer formed, copper, chromium, nickel, iron, cobalt 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 selected from the group consisting of zinc and zinc is formed by electrolysis and further subjected to rust prevention treatment. Provided.
【００１１】[0011]
【作用】本発明に従えば、電解浴中に（ａ）クロム及び
タングステンから成る第１群から選ばれた１種或いは２
種である第１群金属：０．０００１〜５ｇ／l と、
（ｂ）バナジウム、ニッケル、鉄、コバルト、亜鉛、ゲ
ルマニウム及びモリブデンから成る第２群から選ばれた
る１種或いは２種以上である第２群金属：０．００１〜
５０ｇ／l の両者を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第１群金属と第２
群金属とを併有することになる。クロム及び（又は）タ
ングステンの第１群金属成分が存在することにより、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。クロム又
はタングステン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。また、バナジウム、ニッケル、
鉄、コバルト、亜鉛、ゲルマニウム及びモリブデンから
選ばれる１種或いは２種以上の第２群金属成分の存在
は、粗化粒子の異方性成長を促し、接着強度の向上に寄
与する。According to the present invention, in the electrolytic bath, (a) one or two selected from the first group consisting of chromium and tungsten.
Group 1 metal as a seed: 0.0001 to 5 g / l,
(B) One or two or more second group metals selected from the second group consisting of vanadium, nickel, iron, cobalt, zinc, germanium and molybdenum: 0.001 to 1
By forming the roughening treatment layer in the presence of both of 50 g / l, the protruding copper electrodeposit has a very small amount of the first group metal and the second group metal.
It will have a group metal together. The presence of the first group metal component of chromium and / or tungsten suppresses the generation of nuclei during electrodeposition of copper, suppresses the formation of dendrites, and rounds the electrodeposited projection particles to improve the adhesive strength. It is useful and prevents powder from falling off during etching. In the absence of chromium or tungsten ions in the electrolytic bath, electrolysis near the limiting current causes the copper electrodeposits to become dendritic and impair rather than improve the bond strength. When powder is removed, fine copper powder remains after the etching process, which may impair the electrical characteristics. Also, vanadium, nickel,
The presence of one or more second group metal components selected from iron, cobalt, zinc, germanium, and molybdenum promotes anisotropic growth of roughened particles and contributes to improvement of adhesive strength.
【００１２】[0012]
【発明の具体的な説明】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。DETAILED DESCRIPTION OF THE INVENTION 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
（ａ）クロム及びタングステンから成る第１群から選ば
れた１種或いは２種である第１群金属と（ｂ）バナジウ
ム、ニッケル、鉄、コバルト、亜鉛、ゲルマニウム及び
モリブデンから成る第２群から選ばれたる１種或いは２
種以上である第２群金属とを同時に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, the first group metal which is one or two kinds selected from the first group consisting of (a) chromium and tungsten, and (b) vanadium, mainly in the vicinity of the top of the convex portion 2, One or two selected from the second group consisting of nickel, iron, cobalt, zinc, germanium and molybdenum
The roughening treatment layer 3 composed of a large number of protruding copper electrodeposits simultaneously containing the second group metal of at least one kind is formed, and the convex portions are strengthened. 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, although 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 to give post heat resistance and other properties,
A metal or alloy such as nickel, 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： （粗化処理用銅電解浴めっき条件） Ｃｕイオン：５〜５０ｇ／ｌ Ｈ2 ＳＯ4 ：１０〜１００ｇ／ｌ 第１群金属（Ｃｒ、Ｗの１種又は２種）イオン：０．０
００１〜５ｇ／ｌ 第２群金属（Ｖ、Ｎｉ、Ｆｅ、Ｃｏ、Ｚｎ、Ｇｅ、Ｍｏ
の１種或いは２種以上） イオン：０．００１〜５０ｇ／ｌ 温 度：室温〜５０℃ Ｄk ：５〜８０Ａ／ｄｍ2 時間：１〜３０秒The plating conditions of the roughening treatment copper electrolytic bath according to the present invention are as follows: (Roughening treatment copper electrolytic bath plating condition) Cu ion: 5 to 50 g / l H 2 SO 4 : 10 to 100 g / L Group 1 metal (one or two of Cr and W) ions: 0.0
001 to 5 g / l Group 2 metals (V, Ni, Fe, Co, Zn, Ge, Mo
Ion: 0.001 to 50 g / l Temperature: Room temperature to 50 ° C. D k : 5 to 80 A / dm 2 hours: 1 to 30 seconds
【００１５】銅電解浴中に存在させるクロム又はタング
ステンの濃度或いは両者の組合せの濃度は０．０００１
〜５ｇ／ｌが適当であり、好ましくは０．０００２〜１
ｇ／ｌである。添加量が０．０００１ｇ／ｌ未満では接
着強度を増すのに充分な効果はなく、他方５ｇ／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。クロム又はタングステンの供給源として、ナ
トリウム塩、カリウム塩、酸化物等の使用が可能であ
る。例えば、無水クロム酸（ＶＩ）やタングステン酸ナ
トリウム（２水塩）等が使用される。また、銅電解浴中
に存在させるバナジウム、ニッケル、鉄、コバルト、亜
鉛、ゲルマニウム及びモリブデンから選ばれる１種或い
は２種以上の組合わせの濃度は、０．００１〜５０ｇ／
ｌが適当であり、好ましくは０．０１〜２０ｇ／ｌであ
る。添加量が０．００１ｇ／ｌ未満では接着強度を増す
べく粗化粒子の異方性成長を促すのに十分な効果はな
く、他方５０ｇ／ｌを超えてもその効果に顕著な向上は
ない。むしろ、表面の処理ムラが目立つようになる。ニ
ッケル、鉄、コバルト及び亜鉛の供給源としては、それ
らの硫酸塩、酸化物、水酸化物等が使用できる。また、
バナジウムの供給源としては、酸化物、硫酸バナジル、
酸素酸塩のナトリウム塩、カリウム塩、アンモニウム塩
等が使用できる。ゲルマニウム及びモリブデンの供給源
としては、酸化物或いは酸素酸塩のナトリウム塩、カリ
ウム塩、アンモニウム塩等が使用できる。The concentration of chromium or tungsten or the combination of both present in the copper electrolytic bath is 0.0001.
~ 5 g / l is suitable, preferably 0.0002 to 1
g / l. If the amount added is less than 0.0001 g / l, the effect is not sufficient to increase the adhesive strength, while if it exceeds 5 g / l, the effect is not significantly improved and the economic burden increases. As a source of chromium or tungsten, it is possible to use sodium salts, potassium salts, oxides and the like. For example, chromic anhydride (VI), sodium tungstate (dihydrate) or the like is used. Further, the concentration of one kind or a combination of two or more kinds selected from vanadium, nickel, iron, cobalt, zinc, germanium and molybdenum to be present in the copper electrolytic bath is 0.001 to 50 g /
1 is suitable, and preferably 0.01 to 20 g / l. If the amount added is less than 0.001 g / l, there is no sufficient effect to promote anisotropic growth of roughened particles in order to increase the adhesive strength, while if it exceeds 50 g / l, there is no significant improvement in that effect. Rather, uneven treatment on the surface becomes noticeable. As a supply source of nickel, iron, cobalt, and zinc, their sulfates, oxides, hydroxides, etc. can be used. Also,
Sources of vanadium include oxides, vanadyl sulfate,
Oxygen acid salts such as sodium salt, potassium salt and ammonium salt can be used. As the source of germanium and molybdenum, sodium salts, potassium salts, ammonium salts of oxides or oxygenates can be used.
【００１６】上記のような粗化処理後、必要に応じ公知
の処理、例えば薄い銅めっき層を形成し、突起状電着物
の脱落を防止することが好ましい。この薄い銅層の被覆
として、もっとも一般的な、硫酸銅浴を使用した場合の
好ましい銅電解条件は下記の通りである。 （薄い銅めっき層電解条件） Ｃｕイオン：５〜５０ｇ／ｌ Ｈ2 ＳＯ4 ：１０〜１００ｇ／ｌ 温度：室温〜５０℃ Ｄk ：５〜８０Ａ／ｄｍ2 時間：１〜３０秒After the roughening treatment as described above, it is preferable that a known treatment, for example, a thin copper plating layer is formed as necessary to prevent the protruding electrodeposits from falling off. The most common copper electrolysis conditions when a copper sulfate bath is used as the coating of this thin copper layer are as follows. (Thin copper-plated layer electrolysis conditions) Cu ion: 5~50g / l H 2 SO 4 : 10~100g / l Temperature: room temperature ~50 ℃ D k: 5~80A / dm 2 Time: 1-30 seconds
【００１７】粗化面に、好ましくは上記の薄い銅めっき
を施した後、銅、クロム、ニッケル、鉄、コバルト及び
亜鉛から成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、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５６−９０２
８号、特開昭５４−１３９７１号、特開平２−２９２８
９４号、特開平２−２９２８９５号、特公昭５１−３５
７１１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。The roughened surface is preferably subjected to the above thin copper plating, and then one or more metal layers or alloy layers selected from the group consisting of copper, chromium, nickel, iron, cobalt and zinc. Is preferably performed. For example, a metal layer of copper, chromium, nickel, iron, cobalt, or zinc, or an alloy layer represented by copper-nickel, copper-cobalt, copper-nickel-cobalt, copper-zinc, or the like can be formed (for example, a special Kosho 56-902
No. 8, JP-A-54-13971, JP-A-2-2928.
94, JP-A-2-292895, JP-B-51-35.
711, Japanese Patent Publication No. 54-6701). Such treated layers serve as determinants of the final properties of the copper foil and as barrier layers.
【００１８】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。 （亜鉛トリート処理電解条件） 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、１５〜６０
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６０〜４００
μｇ／ｄｍ2 とする。Taking the zinc coating as an example, either zinc electroplating or electroless plating can be performed, but zinc electrolytic operation is more convenient for forming the 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. The zinc electrolysis operation can be performed using an acidic zinc plating bath typified 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. (Zinc Treat process electrolysis conditions) ZnSO 4 · 7H 2 O: 50~350g / l pH ( sulfate): 2.5-4.5 bath temperature: 40 to 60 ° C. Cathode: copper anode: zinc or insoluble anode Cathode current density: 0.05~0.4A / dm 2 Time: 10-30 seconds 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 and 60 for glass epoxy resin substrate
˜1500 μg / dm 2 , particularly preferably 60 to 400
μg / dm 2 .
【００１９】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： （Ｃｕ−Ｚｎトリート処理電解条件） 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 of Cu-Zn treat treatment will be described: (Cu-Zn treat treatment electrolysis conditions) NaCN: 10 to 30 g / l NaOH: 40 to 100 g / l CuCN: 60~120g / l Zn (CN) 2 : 1~10g / l pH: 10~13 temperature: 60~80 ℃ D k: 1~10A / dm 2
【００２０】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： （クロメート処理条件電解条件） Ｋ2 Ｃｒ2 Ｏ7(或いはＮａ2 Ｃｒ2 Ｏ7 、ＣｒＯ3)：
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. As the chromate treatment liquid, any of various treatment liquids currently used can be used, but preferable chromate treatment condition examples are as follows: (Chromate treatment condition Electrolytic condition) 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 to 60 Second 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. When the amount of chromium exceeds 30 μg / dm 2 , the rust preventive power is improved but the etching property is deteriorated.
【００２１】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 electrolytic zinc-chromium mixed film treatment of zinc and / or zinc oxide and chromium oxide (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.
【００２２】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 anticorrosion 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.
【００２３】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 having the roughened surface thus coated 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.
【００２４】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.
【００２５】本発明による第１群金属としてクロム又は
タングステンイオン或いはその組合せそして第２群金属
としてバナジウム、ニッケル、鉄、コバルト、亜鉛、ゲ
ルマニウム及びモリブデンから選ばれる１種或いは２種
以上のイオン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。The first group metal according to the present invention contains chromium or tungsten ions or a combination thereof, and the second group metal contains one or more ions selected from vanadium, nickel, iron, cobalt, zinc, germanium and molybdenum. The copper foil roughened in the copper electrolytic bath 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.
【００２６】[0026]
【実施例】以下、実施例及び比較例を示す。EXAMPLES Examples and comparative examples will be described below.
【００２７】（実施例１）硫酸銅（５水塩）１００ｇ／
ｌ、硫酸１００ｇ／ｌ、無水クロム酸（ＶＩ）１ｇ／
ｌ、硫酸ニッケル６水和物１３ｇ／ｌ、及び硫酸コバル
ト７水和物１４ｇ／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秒間めっきして突起状銅電着
物を形成した後、銅イオン４５ｇ／ｌ及び硫酸１００ｇ
／ｌを含む銅電解液（４０℃）を用いて、３０Ａ／ｄｍ
2 で４秒間銅めっきした。このようにして得られた銅箔
を分析したところ、箔全体に対するクロム、ニッケル及
びコバルトの含有量は、クロム：約１ｐｐｍ、ニッケ
ル：約２ｐｐｍそしてコバルト：０．５ｐｐｍ（突起状
銅電着物中のＣｒ、Ｎｉ及びＣｏの含有量は、Ｃｒ：約
０．０１ｗｔ％、Ｎｉ：約０．０２ｗｔ％そしてＣｏ：
約０．００５ｗｔ％）であった。得られた銅箔をガラス
布基材エポキシ樹脂に加熱・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。更に、粗化処理層上に亜鉛によるトリー
ト処理層及び防錆層を形成した銅箔は一層良好な耐熱性
と耐酸化性を示した。(Example 1) 100 g of copper sulfate (pentahydrate) /
1, sulfuric acid 100 g / l, chromic anhydride (VI) 1 g /
1, an aqueous solution containing 13 g / l of nickel sulfate hexahydrate and 14 g / l of cobalt sulfate heptahydrate was used as an electrolytic bath at 30 ° C., and a current density of 20 A was applied to an adhered surface of an electrolytic copper foil having a thickness of 70 μm. / Dm 2 for 10 seconds to form a protruding copper electrodeposit, and then copper ion 45 g / l and sulfuric acid 100 g
30 A / dm using a copper electrolyte solution (40 ° C.) containing 1 / l
Copper plated at 2 for 4 seconds. When the copper foil thus obtained was analyzed, the contents of chromium, nickel and cobalt with respect to the entire foil were as follows: chromium: about 1 ppm, nickel: about 2 ppm and cobalt: 0.5 ppm (in the protruding copper electrodeposit) The contents of Cr, Ni and Co are as follows: Cr: about 0.01 wt%, Ni: about 0.02 wt% and Co:
It was about 0.005 wt%). The copper foil thus obtained was heated and pressed against a glass cloth-based epoxy resin to prepare a copper-clad laminate, and the peel strength and powder falling characteristics were measured. The results are shown in Table 1. Further, the copper foil having a zinc treated layer and a rust preventive layer formed on the roughened layer exhibited better heat resistance and oxidation resistance.
【００２８】（実施例２）硫酸銅（５水塩）１００ｇ／
ｌ、硫酸１００ｇ／ｌ、タングステン酸ナトリウム（２
水塩）０．０２ｇ／ｌ、硫酸ニッケル６水和物１３ｇ／
ｌ、硫酸コバルト７水和物１４ｇ／ｌを含む水溶液を３
０℃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
て突起状銅電着物を形成した後、銅イオン４５ｇ／ｌ、
硫酸１００ｇ／ｌを含む電解液（４０℃）を用い、３０
Ａ／ｄｍ2 で４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、箔全体に対するタングステ
ン、ニッケル及びコバルトの含有量はそれぞれ約１ｐｐ
ｍ、約２ｐｐｍそして約０．６ｐｐｍ（突起状銅電着物
中のＷ、Ｎｉ及びＣｏの含有量は、それぞれ約０．０１
ｗｔ％、約０．０２ｗｔ％そして約０．００６ｗｔ％）
であった。得られた銅箔をガラス布基材エポキシ樹脂に
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。更に、
粗化処理層上に亜鉛によるトリート処理層及び防錆層を
形成した銅箔は一層良好な耐熱性と耐酸化性を示した。Example 2 Copper sulfate (pentahydrate) 100 g /
1, sulfuric acid 100 g / l, sodium tungstate (2
Water salt) 0.02 g / l, nickel sulfate hexahydrate 13 g /
1 and 3 g of an aqueous solution containing 14 g of cobalt sulfate heptahydrate / l.
It is used as an electrolytic bath at 0 ° C., and the surface to be adhered of an electrolytic copper foil having a thickness of 70 μm is plated at a current density of 10 A / dm 2 for 20 seconds to form a protruding copper electrodeposit, and then copper ions are added at 45 g / l,
Using an electrolytic solution (40 ° C.) containing 100 g / l of sulfuric acid, 30
Plated at A / dm 2 for 4 seconds. When the copper foil thus obtained was analyzed, the content of tungsten, nickel and cobalt in the entire foil was about 1 pp each.
m, about 2 ppm and about 0.6 ppm (the content of W, Ni and Co in the protruding copper electrodeposition is about 0.01 respectively)
wt%, about 0.02 wt% and about 0.006 wt%)
Met. The copper foil thus obtained was heated and pressed against a glass cloth-based epoxy resin to prepare a copper-clad laminate, and the peel strength and powder falling characteristics were measured. The results are shown in Table 1. Furthermore,
The copper foil having a zinc treated layer and a rust preventive layer formed on the roughened layer showed better heat resistance and oxidation resistance.
【００２９】（実施例３）硫酸銅（５水塩）１００ｇ／
ｌ、硫酸１００ｇ／ｌ、無水クロム酸（ＶＩ）０．１ｇ
／ｌ、タングステン酸ナトリウム（２水塩）０．０１ｇ
／ｌ、硫酸ニッケル６水和物１３ｇ／ｌ、及び硫酸コバ
ルト７水和物１４ｇ／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秒間めっきして突起状銅電
着物を形成した後、銅イオン４５ｇ／ｌ、硫酸１００ｇ
／ｌを含む電解液（４０℃）を用い、３０Ａ／ｄｍ2 で
４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、箔全体に対するクロム及びタングステン、
ニッケル及びコバルトの含有量は、クロム：約０．１ｐ
ｐｍ、タングステン：約０．７ｐｐｍ、ニッケル：約２
ｐｐｍそしてコバルト：約０．６ｐｐｍ（突起状銅電着
物中の含有量は、Ｃｒ：約０．００１ｗｔ％、Ｗ：約
０．００７ｗｔ％、Ｎｉ：約０．０２ｗｔ％そしてＣ
ｏ：約０．００６ｗｔ％）であった。得られた銅箔をガ
ラス布基材エポキシ樹脂に加熱・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。更に、粗化処理層上に亜鉛によるト
リート処理層及び防錆層を形成した銅箔は一層良好な耐
熱性と耐酸化性を示した。Example 3 Copper sulfate (pentahydrate) 100 g /
1, sulfuric acid 100g / l, chromic anhydride (VI) 0.1g
/ L, sodium tungstate (dihydrate) 0.01g
/ L, 13 g / l of nickel sulfate hexahydrate, and 14 g / l of cobalt sulfate heptahydrate were used as an electrolytic bath at 30 ° C., and a current density was applied to the adhered surface of an electrolytic copper foil having a thickness of 70 μm. After plating with 20 A / dm 2 for 10 seconds to form a protruding copper electrodeposit, copper ion 45 g / l, sulfuric acid 100 g
Using an electrolytic solution (40 ° C.) containing 1 / l, plating was performed at 30 A / dm 2 for 4 seconds. When the copper foil thus obtained was analyzed, chromium and tungsten for the entire foil,
The content of nickel and cobalt is chromium: about 0.1p
pm, tungsten: about 0.7 ppm, nickel: about 2
ppm and cobalt: about 0.6 ppm (contents in the protruding copper electrodeposit are Cr: about 0.001 wt%, W: about 0.007 wt%, Ni: about 0.02 wt% and C
o: about 0.006 wt%). The copper foil thus obtained was heated and pressed against a glass cloth-based epoxy resin to prepare a copper-clad laminate, and the peel strength and powder falling characteristics were measured.
The results are shown in Table 1. Further, the copper foil having a zinc treated layer and a rust preventive layer formed on the roughened layer exhibited better heat resistance and oxidation resistance.
【００３０】（実施例４）硫酸銅（５水塩）１００ｇ／
ｌ、硫酸１００ｇ／ｌ、タングステン酸ナトリウム（２
水塩）０．０１ｇ／ｌ、及び硫酸コバルト７水和物１４
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秒間めっきして突起状銅電着物を形成した
後、銅イオン４５ｇ／ｌ、硫酸１００ｇ／ｌを含む電解
液（４０℃）を用い、３０Ａ／ｄｍ2で４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
全体に対するタングステン及びコバルトの含有量は、タ
ングステン：約０．７ｐｐｍそしてコバルト：約１ｐｐ
ｍ（突起状銅電着物中の含有量は、Ｗ：約０．００７ｗ
ｔ％そしてＣｏ：約０．０１ｗｔ％）であった。得られ
た銅箔をガラス布基材エポキシ樹脂に加熱・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。更に、粗化処理層上に亜
鉛によるトリート処理層及び防錆層を形成した銅箔は一
層良好な耐熱性と耐酸化性を示した。Example 4 Copper sulfate (pentahydrate) 100 g /
1, sulfuric acid 100 g / l, sodium tungstate (2
Water salt) 0.01 g / l, and cobalt sulfate heptahydrate 14
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.
After plating with m 2 for 10 seconds to form a protruding copper electrodeposit, it was plated with 30 A / dm 2 for 4 seconds using an electrolytic solution (40 ° C.) containing 45 g / l of copper ions and 100 g / l of sulfuric acid. When the copper foil thus obtained was analyzed, the content of tungsten and cobalt in the entire foil was found to be about 0.7 ppm for tungsten and about 1 pp for cobalt.
m (content in the protruding copper electrodeposition is W: about 0.007w
t% and Co: about 0.01 wt%). The copper foil thus obtained was heated and pressed against a glass cloth-based epoxy resin to prepare a copper-clad laminate, and the peel strength and powder falling characteristics were measured. The results are shown in Table 1. Further, the copper foil having a zinc treated layer and a rust preventive layer formed on the roughened layer exhibited better heat resistance and oxidation resistance.
【００３１】（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秒間めっきした後、銅イオン４５ｇ／ｌ、硫酸１００
ｇ／ｌを含む電解液（４０℃）を用い、３０Ａ／ｄｍ2
で４秒間めっきした。得られた銅箔をガラス布基材エポ
キシ樹脂に加熱・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 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
After plating for 0 seconds, copper ion 45g / l, sulfuric acid 100
Using an electrolytic solution (40 ° C.) containing g / l, 30 A / dm 2
For 4 seconds. The copper foil thus obtained was heated and pressed against a glass cloth-based epoxy resin to prepare a copper-clad laminate, and the peel strength and powder falling characteristics were measured. The results are shown in Table 1.
【００３２】（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秒間めっきした後、銅イオン４５
ｇ／ｌ、硫酸１００ｇ／ｌを含む電解液（４０℃）を用
い、３０Ａ／ｄｍ2 で４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の
含有量は、約１．２ｗｔ％）であった。得られた銅箔を
ガラス布基材エポキシ樹脂に加熱・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
Then, 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, and then copper ions 45
Using an electrolytic solution (40 ° C.) containing g / l and 100 g / l of sulfuric acid, plating was performed at 30 A / dm 2 for 4 seconds. When the copper foil thus obtained was analyzed, the content of arsenic in the entire foil was about 200 ppm (the content of As in the protruding copper electrodeposit was about 1.2 wt%). The copper foil thus obtained was heated and pressed against a glass cloth-based epoxy resin to prepare a copper-clad laminate, and the peel strength and powder falling characteristics were measured. The results are shown in Table 1.
【００３３】[0033]
【表１】 [Table 1]
【００３４】[0034]
【発明の効果】本発明によるクロム又はタングステン或
いは両者から成る第１群金属成分と、バナジウム、ニッ
ケル、鉄、コバルト、亜鉛、ゲルマニウム及びモリブデ
ンから選ばれる１種或いは２種以上から成る第２群金属
成分と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
向上し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 first group metal component of chromium or tungsten or both according to the present invention and the second group metal of one or more selected from vanadium, nickel, iron, cobalt, zinc, germanium and molybdenum. The copper foil roughened in the copper electrolytic bath containing the components is uniformly treated and shows excellent substrate characteristics without unevenness. When a laminated board is made of copper foil and glass cloth base epoxy resin,
Since a rounded electrodeposit having good adhesiveness and heat resistance and suppressing the development of dendrites is formed, the adhesive strength is improved, and there is no problem of electrical characteristics of the substrate after etching or powder falling off.
【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.
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 part 3 Roughening treatment layer 4 Copper plating layer 5 Treat treatment plating layer 6 Rust preventive layer
Claims (6)
ングステンから成る第１群から選ばれた１種或いは２種
である第１群金属と（ｂ）バナジウム、ニッケル、鉄、
コバルト、亜鉛、ゲルマニウム及びモリブデンから成る
第２群から選ばれた１種或いは２種以上である第２群金
属との両者を含有する多数の突起状銅電着物から成る粗
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 first group metal, which is one or two selected from the first group consisting of chromium and tungsten, and (b) vanadium, nickel, iron,
To have a roughening treatment layer composed of a large number of protruding copper electrodeposits containing both of one or more second group metals selected from the second group consisting of cobalt, zinc, germanium and molybdenum. Copper foil for printed circuits characterized by.
ングステンから成る第１群から選ばれた１種或いは２種
である第１群金属と（ｂ）バナジウム、ニッケル、鉄、
コバルト、亜鉛、ゲルマニウム及びモリブデンから成る
第２群から選ばれた１種或いは２種以上である第２群金
属との両者を含有する多数の突起状銅電着物から成る粗
化処理層と、前記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成る群から選択さ
れた１種乃至２種以上の金属又は合金から成るトリート
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。2. A first group metal, which is one or two selected from the first group consisting of chromium and tungsten, and (b) vanadium, nickel, iron, and
A roughening treatment layer comprising a large number of protruding copper electrodeposits containing both one or two or more second group metals selected from the second group consisting of cobalt, zinc, germanium and molybdenum; Copper, chromium, which coats the roughened layer,
A printed circuit having a treat layer composed of one or more kinds of metals or alloys selected from the group consisting of nickel, iron, cobalt and zinc, and a rust preventive layer covering the treat layer. Copper foil.
めっき層を前記粗化処理層とトリート層との間に形成し
たことを特徴とする請求項２の印刷回路用銅箔。3. The copper foil for a printed circuit according to claim 2, wherein a thin copper plating layer that prevents the protruding copper electrodeposits from falling off is formed between the roughening treatment layer and the treat layer.
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
起状銅電着物から成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（ａ）クロム及び
タングステンから成る第１群から選ばれた１種或いは２
種である第１群金属：０．０００１〜５ｇ／l と、
（ｂ）バナジウム、ニッケル、鉄、コバルト、亜鉛、ゲ
ルマニウム及びモリブデンから成る第２群から選ばれた
１種或いは２種以上である第２群金属：０．００１〜５
０ｇ／l の両者を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 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, in the electrolytic bath, (a) one or two selected from the first group consisting of chromium and tungsten.
Group 1 metal as a seed: 0.0001 to 5 g / l,
(B) One or two or more second group metals selected from the second group consisting of vanadium, nickel, iron, cobalt, zinc, germanium and molybdenum: 0.001 to 5
A method for producing a copper foil for a printed circuit, characterized in that both 0 g / l are present.
ニッケル、鉄、コバルト及び亜鉛から成る群から選択さ
れる１種乃至２種以上の金属又は合金から成るトリート
層を電解により形成し、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. The printed circuit according to claim 4, wherein a treat layer made of one or more kinds of metals or alloys selected from the group consisting of nickel, iron, cobalt and zinc is formed by electrolysis, and further treated for rust prevention. Method for manufacturing copper foil.
物の脱落を防止する薄い銅めっき層を電解により形成
し、形成された銅めっき層上に銅、クロム、ニッケル、
鉄、コバルト及び亜鉛から成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成るトリート層を電解
により形成し、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。6. A thin copper plating layer for preventing drop-out of protruding copper electrodeposits from being electrolytically formed on the roughening treatment layer formed, and copper, chromium, nickel, and the like on the formed copper plating layer.
The copper for printed circuit according to claim 4, wherein a treat layer made of one or more kinds of metals or alloys selected from the group consisting of iron, cobalt and zinc is formed by electrolysis, and further treated for rust prevention. Method of manufacturing foil.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7058225A JP2920083B2 (en) | 1995-02-23 | 1995-02-23 | Copper foil for printed circuit and manufacturing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7058225A JP2920083B2 (en) | 1995-02-23 | 1995-02-23 | Copper foil for printed circuit and manufacturing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08236930A true JPH08236930A (en) | 1996-09-13 |
| JP2920083B2 JP2920083B2 (en) | 1999-07-19 |
Family
ID=13078148
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7058225A Expired - Fee Related JP2920083B2 (en) | 1995-02-23 | 1995-02-23 | Copper foil for printed circuit and manufacturing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2920083B2 (en) |
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