JP3113445B2 - Copper foil for printed circuit and manufacturing method thereof - Google Patents
Copper foil for printed circuit and manufacturing method thereofInfo
- Publication number
- JP3113445B2 JP3113445B2 JP05091842A JP9184293A JP3113445B2 JP 3113445 B2 JP3113445 B2 JP 3113445B2 JP 05091842 A JP05091842 A JP 05091842A JP 9184293 A JP9184293 A JP 9184293A JP 3113445 B2 JP3113445 B2 JP 3113445B2
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- JP
- Japan
- Prior art keywords
- copper foil
- copper
- treatment
- plating
- heat
- 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.)
- Expired - Lifetime
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- Electroplating Methods And Accessories (AREA)
- Chemical Treatment Of Metals (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Parts Printed On Printed Circuit Boards (AREA)
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、特には銅箔の光沢面の
耐熱酸化性（プリント基板等の製造時に適用される熱履
歴に対して酸化による変色を起こさないこと）を改善す
るために、耐熱酸化処理を行う前に銅箔の光沢面に銅め
っき層を形成したことを特徴とする印刷回路用銅箔及び
その製造方法に関するものである。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 more particularly to a heat-resistant oxidizing property of a glossy surface of a copper foil (for heat history applied at the time of manufacturing a printed circuit board or the like). A copper plating layer formed on a glossy surface of the copper foil prior to heat-resistant oxidation treatment, and a method for manufacturing the same. It is.
【０００２】[0002]
【従来の技術】銅及び銅合金箔（以下、銅箔と称する）
は、電器・電子関連産業の発展に大きく寄与しており、
特に印刷回路材として不可欠の存在となっている。印刷
回路用銅箔は一般に、合成樹脂ボード、フィルム等の基
材に接着剤を介して或いは接着剤を使用せずに高温高圧
下で熱可塑性樹脂基材に積層接着され、その後目的とす
る回路を形成するべく必要な回路を印刷した後、不要部
を除去する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面（粗化面）と
非接着面（光沢面）とで異なる。2. Description of the Related Art Copper and copper alloy foils (hereinafter referred to as copper foils)
Has contributed greatly to the development of the electrical and electronics related industries,
In particular, it is indispensable as a printed circuit material. Generally, copper foil for printed circuits is laminated and adhered to a thermoplastic resin substrate at a high temperature and a high pressure with or without using an adhesive to a substrate such as a synthetic resin board or film, and then a target circuit is formed. After printing a circuit necessary to form the semiconductor device, an etching process for removing unnecessary portions is performed. Finally, the required elements are soldered to form various printed circuit boards for electronic devices. The quality requirements for the copper foil for printed wiring boards differ between the surface that is bonded to the resin substrate (roughened surface) and the non-bonded surface (glossy surface).
【０００３】粗化面に対する要求としては、主として、 保存時における酸化変色のないこと、 基材との引き剥し強さが高温加熱、湿式処理、半田付
け、薬品処理等の後でも充分なこと、 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 等が挙げられる。The requirements for the roughened surface are mainly that there is no oxidative discoloration during storage, that the peeling strength with the substrate is sufficient even after high-temperature heating, wet processing, soldering, chemical processing, and the like. There is no so-called lamination stain generated after lamination with the base material and etching.
【０００４】他方、光沢面に対しては、 外観が良好なこと及び保存時における酸化変色のない
こと、 半田濡れ性が良好なこと、 高温加熱時に酸化変色がないこと レジストとの密着性が良好なこと 等が要求される。On the other hand, the glossy surface has good appearance, no oxidative discoloration during storage, good solder wettability, no oxidative discoloration at high temperature heating, and good adhesion to resist. Is required.
【０００５】ところで、銅箔の光沢面の耐熱酸化性に関
しては、年々要求が厳しくなっている。一つには、従来
なかった新しい製作方式（２層フレキ：ポリイミドワニ
スを直接銅箔上へ塗布し、フレキシブル基板とする方法
で、ポリイミド層と銅箔層の２層構造となっているた
め、２層フレキと呼ばれている。）及び高耐熱性の新規
樹脂の出現に伴い、銅箔が今までよりも高い温度に曝露
されるようになったためである。また、従来の積層方法
においても、加熱処理を行う積層及びキュアー工程のコ
スト削減のために今までの窒素雰囲気から大気中で行な
う傾向も見られ、この点からも銅箔光沢面の耐熱酸化性
の改善が要求されるようになった。銅箔光沢面は精密な
電気回路が印刷されるので酸化変色等はあってはならな
いとされている。具体的には、現在では、３００℃×３
０分に保持した状態で変色のないことが要求されてい
る。[0005] By the way, with respect to the heat-resistant oxidation resistance of the glossy surface of the copper foil, the requirements are becoming stricter year by year. One is a new manufacturing method that has never existed before (two-layer flexible: a method in which a polyimide varnish is applied directly on a copper foil to form a flexible substrate, and has a two-layer structure of a polyimide layer and a copper foil layer. This is because the copper foil has been exposed to a higher temperature than before with the advent of a new resin having high heat resistance. In addition, in the conventional laminating method, there is a tendency that the heat treatment is performed in the air instead of the nitrogen atmosphere in order to reduce the cost of the laminating process and the curing process. Improvement has been required. The glossy surface of the copper foil is printed with a precise electric circuit, so it should not be oxidized or discolored. Specifically, at present, 300 ° C. × 3
It is required that there be no discoloration in the state where it is kept at 0 minutes.
【０００６】これまでは、光沢面の表面処理法として
は、上述した要件を全般的に満たすものとして亜鉛めっ
き＋クロメート処理の方法が主として採用されてきた。
しかしながら、この方法では、例えば２００℃×３０分
程度しか耐熱酸化性が保持されない。亜鉛めっき量を増
大すれば、耐熱酸化性が向上するが、接着後黄色化（真
ちゅう化）する問題や耐酸性の低下による印刷性の低下
の問題が生じることが知られている。Heretofore, as a surface treatment method for a glossy surface, a method of zinc plating + chromate treatment has been mainly employed as a method satisfying the above requirements in general.
However, in this method, the thermal oxidation resistance is maintained only at, for example, about 200 ° C. × 30 minutes. It is known that when the amount of zinc plating is increased, the thermal oxidation resistance is improved, but a problem of yellowing (brassing) after bonding and a problem of a decrease in printability due to a decrease in acid resistance are known.
【０００７】上記亜鉛めっきに代えて、耐熱酸化処理層
として亜鉛−ニッケルめっき、亜鉛−コバルトめっき等
の亜鉛合金層を形成したのち、クロメート処理する方法
が考慮されている状況にあるが、これでもせいぜい２４
０℃×３０分或いは２７０℃×１０分の高温条件での変
色に耐える程度であり、３００℃×３０分の耐熱酸化条
件には合格しない。[0007] Instead of the zinc plating, a method of forming a zinc alloy layer such as zinc-nickel plating or zinc-cobalt plating as a heat-resistant oxidation treatment layer and then performing a chromate treatment has been considered. At most 24
It can withstand discoloration under high-temperature conditions of 0 ° C. × 30 minutes or 270 ° C. × 10 minutes, and does not pass the heat-resistant oxidation conditions of 300 ° C. × 30 minutes.
【０００８】[0008]
【発明が解決しようとする課題】本発明の課題は、３０
０℃×３０分の条件下で耐熱酸化性を有して、酸化変色
を生ぜず、また黄色化が生じない銅箔を得るための銅箔
の光沢面の表面処理技術を開発することである。The problem to be solved by the present invention is that
The object of the present invention is to develop a surface treatment technique for a glossy surface of a copper foil to obtain a copper foil having a heat-resistant oxidizing property under a condition of 0 ° C. × 30 minutes, causing no oxidative discoloration and not causing yellowing. .
【０００９】[0009]
【課題を解決するための手段】本発明者等は、従来から
の耐熱酸化処理において３００℃×３０分の条件下で酸
化変色や黄色化が生じる原因を究明した結果、その原因
は耐熱酸化処理前の銅箔光沢面の化学的活性度の不均一
さ及び（又は）平滑性の欠如にあるものと判断した。即
ち、一般に銅箔は平滑な陰極面に銅を電着させ、電着物
を剥離して製造されており、陰極付着面側が光沢面とな
るので充分に平滑であると考えられてきたしまた光沢面
は酸洗い及び水洗を行った後耐熱酸化処理を行うので化
学的活性度は充分に均一であると考えられてきた。その
ために、これまでこの点への問題認識がなされていなか
った。ところが、実際には、こうして製造された銅箔の
光沢面を電子顕微鏡で観察してみるとそこには微小なピ
ットが点在し、化学的活性度も均一ではない。こうした
均一さ及び平滑さを欠如する光沢面に耐熱酸化処理を行
うと、耐熱酸化めっき層に光沢面の欠陥が受け継がれ、
耐熱酸化処理の長所を充分に活用できないのである。本
発明者は、こうした銅箔光沢面自体の化学的活性度の不
均一さ及び（又は）平滑性の欠如を解消する方法として
光沢面に薄い銅めっきを施すのが有効であることを確認
した。The present inventors have investigated the causes of oxidation discoloration and yellowing at 300 ° C. for 30 minutes in the conventional heat-resistant oxidation treatment. It was determined that the previous copper foil glossy surface had non-uniform chemical activity and / or lacked smoothness. That is, copper foil is generally manufactured by electrodepositing copper on a smooth cathode surface and peeling off the electrodeposit, and the cathode-adhering surface side is considered to be sufficiently smooth because it has a glossy surface. It has been considered that the chemical activity is sufficiently uniform because heat-resistant oxidation treatment is performed after acid washing and water washing. For this reason, no problem has been recognized so far. However, actually, when the glossy surface of the copper foil thus manufactured is observed with an electron microscope, minute pits are scattered there and the chemical activity is not uniform. When a heat-resistant oxidation treatment is performed on a glossy surface that lacks such uniformity and smoothness, defects on the glossy surface are inherited by the heat-resistant oxidation plating layer,
The advantage of the heat oxidation treatment cannot be fully utilized. The present inventor has confirmed that it is effective to apply thin copper plating to a glossy surface as a method for solving the unevenness of chemical activity and / or lack of smoothness of the glossy surface of the copper foil itself. .
【００１０】この知見に基づいて、本発明は、（１）銅
箔の光沢面に耐熱酸化処理層と該耐熱酸化処理層上のＣ
ｒ系防錆処理層とを備える印刷回路用銅箔において、前
記銅箔の光沢面と耐熱酸化処理層との間に銅めっき層を
有することを特徴とする印刷回路用銅箔、及び（２）銅
箔の光沢面に耐熱酸化処理を行いそして後Ｃｒ系防錆処
理を行う印刷回路用銅箔の製造方法において、前記耐熱
酸化処理を行う前に前記銅箔の光沢面上に銅めっきを行
うことを特徴とする印刷回路用銅箔の製造方法を提供す
るものである。Based on this finding, the present invention provides (1) a heat-resistant oxidized layer on the glossy surface of a copper foil and C on the heat-resistant oxidized layer.
(2) a copper foil for a printed circuit comprising an r-based rust-proofing layer, wherein a copper plating layer is provided between a glossy surface of the copper foil and a heat-resistant oxidation-treated layer; In a method for producing a copper foil for a printed circuit in which a glossy surface of a copper foil is subjected to a heat-resistant oxidizing treatment and then subjected to a Cr-based rust-proofing treatment, copper plating is performed on the glossy surface of the copper foil before the heat-resistant oxidizing treatment is performed. It is intended to provide a method for producing a copper foil for a printed circuit, which is characterized in that it is performed.
【００１１】[0011]
【作用】銅箔の光沢面に薄い銅めっきを付着することに
より、全面がめっき操作によって生成した微粒銅で覆わ
れ、微粒銅面の均一性がその後の耐熱酸化処理による耐
熱酸化めっき層の均一性及び完全性を高め、その長所を
充分に活用することを可能ならしめる。[Function] By applying thin copper plating on the glossy surface of copper foil, the whole surface is covered with fine copper generated by the plating operation, and the uniformity of the fine copper surface is uniformed by the subsequent heat resistant oxidation treatment. Enhance gender and integrity and make full use of its strengths.
【００１２】本発明において使用する銅箔は、電解銅箔
或いは圧延銅箔いずれでもよい。本発明自体は銅箔の光
沢面に関与するが、参考までに銅箔粗化面についても述
べておく。通常、銅箔の、樹脂基材と接着する面即ち粗
化面には積層後の銅箔の引き剥し強さを向上させること
を目的として、脱脂後の銅箔の表面に例えば銅のふしこ
ぶ状の電着を行なう銅粗化処理が施される。こうした銅
のふしこぶ状の電着はいわゆるヤケ電着により容易にも
たらされる。粗化前の前処理として通常の銅めっき等が
そして粗化後の仕上げ処理として通常の銅めっき等が行
なわれることもある。銅粗化処理の例としては、例えば
次の条件が採用され得る。 銅粗化処理条件： Cu ： １０〜２５g/l H2SO4 ： ２０〜１００g/l 温度 ： ２０〜４０℃ Ｄk ： ３０〜７０A/dm2 時間 ： １〜５秒The copper foil used in the present invention may be either an electrolytic copper foil or a rolled copper foil. Although the present invention pertains to the glossy surface of the copper foil, the roughened surface of the copper foil will be described for reference. Normally, for the purpose of improving the peeling strength of the copper foil after lamination on the surface of the copper foil that adheres to the resin substrate, that is, the roughened surface, for example, copper bumps on the surface of the degreased copper foil. A copper roughening treatment for performing electrodeposition in a shape is performed. Such a bumpy electrodeposition of copper is easily provided by so-called burnt electrodeposition. Ordinary copper plating or the like may be performed as pretreatment before roughening, and ordinary copper plating or the like may be performed as finishing treatment after roughening. As an example of the copper roughening treatment, for example, the following conditions can be adopted. Doaraka treatment conditions: Cu: 10~25g / l H 2 SO 4: 20~100g / l Temperature: 20~40 ℃ D k: 30~70A / dm 2 Time: 1 to 5 seconds
【００１３】粗化処理後に、該粗化面にＣｕ、Ｃｒ、Ｎ
ｉ、Ｆｅ、Ｃｏ及びＺｎから選択される１種乃至２種以
上の単一金属層又は合金層を形成するトリート処理を行
なうことが好ましい。合金めっきの例としては、Ｃｕ−
Ｎｉ、Ｃｕ−Ｃｏ、Ｃｕ−Ｎｉ−Ｃｏ、Ｃｕ−Ｚｎその
他を挙げることが出来る（詳細は、特公昭５６−９０２
８号、特開昭５４−１３９７１号、特開平２−２９２８
９５号、特開平２−２９２８９４号、特公昭５１−３５
７１１号、特公昭５４−６７０１号等を参照のこと）。
こうしたトリート処理は、銅箔の最終性状を決定するも
のとしてまた障壁としての役割を果たす。After the roughening treatment, Cu, Cr, N
It is preferable to perform a treatment for forming one or more single metal layers or alloy layers selected from i, Fe, Co and Zn. An example of alloy plating is Cu-
Ni, Cu-Co, Cu-Ni-Co, Cu-Zn and others (for details, see JP-B-56-902).
8, JP-A-54-13971, JP-A-2-2928
No. 95, JP-A-2-292894, JP-B-51-35
711, JP-B-54-6701, etc.).
Such a treatment serves as a final property of the copper foil and as a barrier.
【００１４】さて、本発明に従えば、銅箔の粗化面にト
リート処理を伴って或いは伴わずして、酸洗い、水洗等
の通常の予備処理を施された銅箔の光沢面に銅めっきが
施される。この銅めっきにおいては、新鮮な微粒銅が全
面に付着しさえすれば良いので、浴種を限定するもので
はなく、取扱の面から、一般的な硫酸銅−硫酸浴が最も
便宜である。めっき液組成及びめっき条件についても厳
しく限定するものではない。めっき液組成範囲は、Ｃｕ
2+：２０〜４０ｇ／ｌそしてＨ2 ＳＯ4 ：５０〜１００
ｇ／ｌが好ましい。めっき条件に関しては、浴温は高い
方がよいが、３０〜６０℃の範囲であれば満足しうる結
果が得られる。電流密度は通電電気量との関連があるの
で、一義的に定義できないが、１〜８０Ａ／ｄｍ2 の範
囲で有効であり、好ましくは２０±５Ａ／ｄｍ2 であ
る。めっき時間は０．１〜１０秒程度で充分である。こ
うして付着される銅めっき量は、高いほど耐熱酸化性を
向上させるが、多量のめっきは銅箔自体の機械的特性を
変化させる可能性があることや処理速度を低下させるこ
となどから、好ましい範囲は１〜２０ｍｇ／ｄｍ2 であ
る。According to the present invention, the glossy surface of a copper foil which has been subjected to a usual pretreatment such as pickling or washing with water, with or without a treatment on the roughened surface of the copper foil, may be used. Plating is applied. In this copper plating, the type of bath is not limited since fresh fine-grained copper only needs to adhere to the entire surface, and a general copper sulfate-sulfuric acid bath is most convenient from the viewpoint of handling. The composition of the plating solution and the plating conditions are not strictly limited. The plating solution composition range is Cu
2+: 20 to 40 g / l and H 2 SO 4: 50~100
g / l is preferred. Regarding the plating conditions, the higher the bath temperature, the better, but a satisfactory result can be obtained in the range of 30 to 60 ° C. The current density cannot be unambiguously defined because it has a relationship with the amount of electricity passed, but it is effective in the range of 1 to 80 A / dm 2 , preferably 20 ± 5 A / dm 2 . A plating time of about 0.1 to 10 seconds is sufficient. The higher the amount of copper plating thus attached, the higher the thermal oxidation resistance. However, a large amount of plating may change the mechanical properties of the copper foil itself or reduce the processing speed. Is 1 to 20 mg / dm 2 .
【００１５】この銅めっきによって元の銅箔光沢面に点
在した０．１〜０．３μｍ範囲のピットは完全に消失
し、全面がめっき操作によって生成した微粒銅で覆われ
ていることが３０，０００倍の走査電子顕微鏡（ＳＥ
Ｍ）像で確認された。Due to this copper plating, pits in the range of 0.1 to 0.3 μm scattered on the glossy surface of the original copper foil are completely disappeared, and the entire surface is covered with fine copper generated by the plating operation. 2,000 × scanning electron microscope (SE
M) Confirmed by image.
【００１６】この後、銅めっき光沢面に従来通り耐熱酸
化処理を行いそして後Ｃｒ系防錆処理が行われる。Thereafter, the glossy surface of the copper plating is subjected to a conventional heat-resistant oxidation treatment, and a post-Cr-based rust prevention treatment is performed.
【００１７】耐熱酸化処理は、公知の方法のいずれをも
使用することができる。例えば、Ｚｎ−Ｎｉ合金処理、
Ｚｎ−Ｃｏ合金処理のような亜鉛合金めっき処理が実施
される。本発明において、耐熱酸化処理は、大気中、１
００℃以上×３０分、好ましくは２００℃以上×３０
分、特に好ましくは２４０℃以上×３０分の条件の下で
酸化等の変色を防止するための処理として定義する。具
体的には、Ｚｎ又はＺｎとＮｉ、Ｃｏ、Ｖ、Ｗ、Ｍｏ、
Ｓｎ、Ｃｒ等から選択される１種以上の金属よりなるＺ
ｎ合金めっき処理等が例示される。For the heat-resistant oxidation treatment, any of known methods can be used. For example, Zn-Ni alloy processing,
A zinc alloy plating process such as a Zn-Co alloy process is performed. In the present invention, the heat-resistant oxidation treatment is performed in air at 1
00 ° C. or more × 30 minutes, preferably 200 ° C. or more × 30 minutes
Min, particularly preferably a treatment for preventing discoloration such as oxidation under conditions of 240 ° C. or more × 30 minutes. Specifically, Zn or Zn and Ni, Co, V, W, Mo,
Z made of at least one metal selected from Sn, Cr, etc.
An n-alloy plating process is exemplified.
【００１８】例えば、Ｚｎ−Ｎｉ合金処理を例にとる
と、これは、好ましくはＺｎ−Ｎｉ電解めっき浴を使用
して、好ましくは５０〜９７重量％Ｚｎ及び３〜５０重
量％Ｎｉの組成のＺｎ−Ｎｉ合金層を１００〜５００μ
ｇ／ｄｍ2 の付着量でごく薄く形成するようにして実施
される。Ｎｉ量が３重量％未満では耐熱酸化性の所要の
向上が得られない。他方Ｎｉ量が５０重量％を超える
と、半田濡れ性が悪化すると共に、耐熱酸化性もまた悪
化する。Ｚｎ−Ｎｉ合金層の付着量が１００μｇ／ｄｍ
2 未満では、耐熱酸化性の向上が得られない。他方５０
０μｇ／ｄｍ2 を超えると、Ｚｎ等の拡散により導電性
が悪化する。Ｚｎ−Ｎｉ合金層は銅箔光沢面の耐熱酸化
性を高め、しかも半田濡れ性、レジスト密着性といった
他の特性を損なうことはない。付着量は外観が銅色とあ
まり変わらないようにするためにも上記のような薄いも
のとされる。For example, taking Zn-Ni alloy treatment as an example, this is preferably done using a Zn-Ni electroplating bath, preferably with a composition of 50-97 wt% Zn and 3-50 wt% Ni. Zn-Ni alloy layer 100-500μ
It is carried out so as to form a very thin film with an adhesion amount of g / dm 2 . If the Ni content is less than 3% by weight, the required improvement in thermal oxidation resistance cannot be obtained. On the other hand, if the Ni content exceeds 50% by weight, the solder wettability deteriorates, and the thermal oxidation resistance also deteriorates. The adhesion amount of the Zn—Ni alloy layer is 100 μg / dm.
If it is less than 2 , improvement in thermal oxidation resistance cannot be obtained. The other 50
If it exceeds 0 μg / dm 2 , the conductivity will deteriorate due to the diffusion of Zn or the like. The Zn-Ni alloy layer enhances the thermal oxidation resistance of the glossy surface of the copper foil, and does not impair other properties such as solder wettability and resist adhesion. The amount of adhesion is made thin as described above so that the appearance is not so different from the copper color.
【００１９】Ｚｎ−Ｃｏ合金処理についても同じく、好
ましくはＺｎ−Ｃｏ電解めっき浴を使用して５０〜９７
重量％Ｚｎ及び３〜５０重量％Ｃｏを含むＺｎ−Ｃｏ合
金層を１００〜５００μｇ／ｄｍ2 の付着量でごく薄く
形成するように実施される。Ｃｏ量が３重量％未満では
耐熱酸化性の所要の向上が得られない。他方Ｃｏ量が５
０重量％を超えると、半田濡れ性が悪化すると共に、耐
熱酸化性も悪化する。Ｚｎ−Ｃｏ合金層の付着量が１０
０μｇ／ｄｍ2 未満では、耐熱酸化性の向上が得られな
い。他方５００μｇ／ｄｍ2 を超えると、Ｚｎ等の拡散
により導電性が悪化する。また、フラックスを使用しな
い工程では、半田濡れ性を悪化することも予想される。
付着量は外観が銅色とあまり変わらないようにするため
にも上記のような薄いものとされる。Similarly, the Zn-Co alloy treatment is preferably carried out using a Zn-Co electrolytic plating bath for 50 to 97 days.
This is performed so that a Zn—Co alloy layer containing wt% Zn and 3 to 50 wt% Co is formed very thin with an adhesion amount of 100 to 500 μg / dm 2 . If the Co content is less than 3% by weight, the required improvement in thermal oxidation resistance cannot be obtained. On the other hand, when the Co amount is 5
If it exceeds 0% by weight, the solder wettability will deteriorate and the thermal oxidation resistance will also deteriorate. The adhesion amount of the Zn—Co alloy layer is 10
If it is less than 0 μg / dm 2 , improvement in thermal oxidation resistance cannot be obtained. On the other hand, if it exceeds 500 μg / dm 2 , the conductivity will deteriorate due to the diffusion of Zn and the like. Further, in a step where no flux is used, it is expected that the solder wettability will be deteriorated.
The amount of adhesion is made thin as described above so that the appearance is not so different from the copper color.
【００２０】Ｚｎ−Ｎｉめっき浴及びＺｎ−Ｃｏめっき
浴の組成及び条件例は次の通りである： Ｚｎ−Ｎｉ（乃至Ｚｎ−Ｃｏ）めっき浴条件： Ｚｎ：５〜５０g/l Ｎｉ（乃至Ｃｏ）：１〜５０g/l ｐＨ：２．５〜４ 温度：３０〜６０℃ 電流密度：０．５〜５A/dm2 めっき時間：０．１〜１０秒Examples of compositions and conditions of the Zn—Ni plating bath and the Zn—Co plating bath are as follows: Zn—Ni (or Zn—Co) plating bath conditions: Zn: 5 to 50 g / l Ni (or Co) ): 1 to 50 g / l pH: 2.5 to 4 Temperature: 30 to 60 ° C Current density: 0.5 to 5 A / dm 2 Plating time: 0.1 to 10 seconds
【００２１】水洗後、こうした耐熱酸化処理層の上にＣ
ｒ系防錆処理が施される。Ｃｒ系防錆層とは、（１）ク
ロム酸化物の単独皮膜処理或いは（２）クロム酸化物と
亜鉛及び（又は）亜鉛酸化物との混合皮膜処理或いは
（３）それらの組合せにより形成されたクロム酸化物を
主体とする防錆層を云う。After washing with water, C
An r-based rust prevention treatment is performed. The Cr-based rust-preventive layer is formed by (1) a single film treatment of chromium oxide, (2) a mixed film treatment of chromium oxide and zinc and / or zinc oxide, or (3) a combination thereof. Rust prevention layer mainly composed of chromium oxide.
【００２２】クロム酸化物の単独皮膜処理に関しては、
浸漬クロメート又は電解クロメートいずれでも良い。耐
候性が要求されるときには、電解クロメートが好まし
い。浸漬クロメート或いは電解クロメートの条件は斯界
で確立されている条件に従う。例えば、浸漬クロメート
及び電解クロメート処理の条件例は次の通りである： （Ａ）浸漬クロメート処理： K2Cr2O7 ：０．５〜１．５g/l ｐＨ ：１．４〜５．０ 温度 ：２０〜６０℃ 時間 ：３〜１０秒 （Ｂ）電解クロメート処理： K2Cr2O7 （Na2Cr2O7或いはCrO3）：２〜１０g/l NaOH或いはKOH ：１０〜５０g/l ｐＨ ：７〜１３ 浴温 ：２０〜８０℃ 電流密度 ：０．０５〜５ A/dm2 時間 ：５〜３０秒 アノード ：Pt-Ti 板、ステンレス鋼板等Regarding the single coating treatment of chromium oxide,
Either immersion chromate or electrolytic chromate may be used. When weather resistance is required, electrolytic chromate is preferred. The conditions of immersion chromate or electrolytic chromate follow those established in the art. For example, conditions for immersion chromate and electrolytic chromate treatment are as follows: (A) Immersion chromate treatment: K 2 Cr 2 O 7 : 0.5 to 1.5 g / l pH: 1.4 to 5.0 Temperature: 20 to 60 ° C. Time: 3 to 10 seconds (B) Electrolytic chromate treatment: K 2 Cr 2 O 7 (Na 2 Cr 2 O 7 or CrO 3 ): 2 to 10 g / l NaOH or KOH: 10 to 50 g / l pH: 7-13 Bath temperature: 20-80 ° C Current density: 0.05-5 A / dm 2 hours: 5-30 seconds Anode: Pt-Ti plate, stainless steel plate, etc.
【００２３】クロム酸化物と亜鉛／亜鉛酸化物との混合
物皮膜処理とは、亜鉛塩または酸化亜鉛とクロム酸塩と
を含むめっき浴を用いて電気めっきにより亜鉛または酸
化亜鉛とクロム酸化物とより成る亜鉛−クロム基混合物
の防錆層を被覆する処理であり、電解亜鉛・クロム処理
と呼ばれる。めっき浴としては代表的には、K2Cr2O7、N
a2Cr2O7等の重クロム酸塩やCrO3等の少なくとも一種
と、水溶性亜鉛塩、例えばZnO 、ZnSO4 ・7H2O等少なく
とも一種と、水酸化アルカリとの混合水溶液が用いられ
る。代表的なめっき浴組成と電解条件例は次の通りであ
る： （Ｃ）電解亜鉛・クロム処理 K2Cr2O7 （Na2Cr2O7或いはCrO3）：２〜１０g/l NaOH或いはKOH ：１０〜５０g/l ZnO 或いはZnSO4 ・7H2O：０．０５〜１０g/l ｐＨ ：７〜１３ 浴温 ：２０〜８０℃ 電流密度 ：０．０５〜５ A/dm2 時間 ：５〜３０秒 アノード ：Pt-Ti 板、ステンレス鋼板等 クロム酸化物はクロム量として１５μg/dm2 以上そして
亜鉛は３０μg/dm2 以上の被覆量が要求される。粗面側
と光沢面側とで厚さを異ならしめても良い。こうした防
錆方法は、特公昭５８−７０７７、６１−３３９０８、
６２−１４０４０等に記載されている。クロム酸化物単
独の皮膜処理及びクロム酸化物と亜鉛／亜鉛酸化物との
混合物皮膜処理の組合せも有効である。The coating treatment of a mixture of chromium oxide and zinc / zinc oxide means that zinc or zinc oxide is mixed with chromium oxide by electroplating using a plating bath containing zinc salt or zinc oxide and chromate. This is a process for coating the anticorrosive layer of the zinc-chromium group mixture thus formed, and is called electrolytic zinc-chromium treatment. As a plating bath, typically, K 2 Cr 2 O 7 , N
At least one and, water-soluble zinc salt of 3 such dichromate or CrO such a 2 Cr 2 O 7, for example ZnO, and at least one ZnSO 4 · 7H 2 O, etc., a mixed aqueous solution of alkali hydroxide is used . Typical plating bath compositions and examples of electrolysis conditions are as follows: (C) Electrolytic zinc / chromium treatment K 2 Cr 2 O 7 (Na 2 Cr 2 O 7 or CrO 3 ): 2 to 10 g / l NaOH or KOH: 10 to 50 g / l ZnO or ZnSO 4 · 7H 2 O: 0.05~10g / l pH: 7~13 bath temperature: 20 to 80 ° C. current density: 0.05 to 5 A / dm 2 Time: 5 Anode: Pt-Ti plate, stainless steel plate, etc. Chromium oxide requires a coating amount of 15 μg / dm 2 or more in terms of chromium and zinc requires a coating amount of 30 μg / dm 2 or more. The thickness may be different between the rough side and the gloss side. Such rust prevention methods are disclosed in JP-B-58-7077, 61-33908,
62-14040 and the like. It is also effective to combine chromium oxide alone and a mixture of chromium oxide and zinc / zinc oxide.
【００２４】水洗及び乾燥後得られた銅箔は、従来の亜
鉛めっき＋クロメート処理の方法では、例えば２００℃
×３０分程度しか耐熱酸化性がなくまたこれまでの銅め
っきを行わずに直接耐熱酸化処理を行う場合には２４０
℃×３０分或いは２７０℃×１０分の高温条件での変色
に耐える程度であったのに対して、３００℃×３０分の
耐熱酸化条件に耐えることができる。しかも、半田濡れ
性、レジスト密着性といった他の特性を損なうものでは
ない。The copper foil obtained after rinsing and drying is treated, for example, at 200 ° C. by a conventional zinc plating + chromate treatment method.
When the heat-resistant oxidation treatment is performed only for about 30 minutes and the heat-resistant oxidation treatment is directly performed without performing the conventional copper plating, 240
While it was able to withstand discoloration under a high temperature condition of 30 ° C. × 30 minutes or 270 ° C. × 10 minutes, it can withstand heat-resistant oxidation conditions of 300 ° C. × 30 minutes. In addition, other characteristics such as solder wettability and resist adhesion are not impaired.
【００２５】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、防錆層上の少なくとも粗
化面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 of applying a silane coupling agent to at least the roughened surface on the rust-preventive layer is performed mainly for the purpose of improving the adhesive strength between the copper foil and the resin substrate. The application method may be any of spraying of a silane coupling agent solution, application with a coater, immersion, and pouring. For example, Japanese Patent Publication No. 60-15654 describes that the adhesive strength between a copper foil and a resin substrate is improved by performing a silane coupling agent treatment after performing a chromate treatment on a rough surface side of the copper foil. . Please refer to this for details.
【００２６】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.
【００２７】[0027]
【実施例】本発明を例示する目的で以下に実施例及び比
較例を呈示する。得られた銅箔の光沢面について、表面
付着量、ベーキングテスト及び半田濡れ性について試験
を行なった。尚、表面分析は、粗化面をＦＲ−４等の基
板材料でプレスしてマスキングし、酸に浸漬して光沢面
のみのＺｎ及びＮｉ又はＣｏを溶解させ、原子吸光法に
より分析した。ベーキングテストは、銅箔６００ｍｍ巾
×１００ｍｍ長さの試片を所定のオーブン中に３００℃
×３０分の加熱条件において投入し、取り出した後、光
沢面の変色の様相を観察した。半田濡れ性については、
フラックスとして山栄化学株式会社製ＪＳ６４を使用し
て半田槽にプレスした基板を垂直に浸漬し、基板表面に
沿って吸い上げられた半田の濡れ角度を求めた。角度が
小さい程半田濡れ性が良い。EXAMPLES Examples and comparative examples are presented below for the purpose of illustrating the present invention. With respect to the glossy surface of the obtained copper foil, a test was conducted on the amount of surface adhesion, a baking test, and solder wettability. In the surface analysis, the roughened surface was pressed and masked with a substrate material such as FR-4, immersed in an acid to dissolve Zn, Ni, or Co only on the glossy surface, and analyzed by an atomic absorption method. The baking test was conducted by placing a copper foil 600 mm wide × 100 mm long in a predetermined oven at 300 ° C.
After throwing in under heating conditions of × 30 minutes and taking out, the appearance of discoloration on the glossy surface was observed. Regarding solder wettability,
The pressed substrate was vertically immersed in a solder bath using JS64 manufactured by Yamaei Chemical Co., Ltd. as a flux, and the wetting angle of the solder sucked up along the substrate surface was determined. The smaller the angle, the better the solder wettability.
【００２８】（実施例１）厚さ３５μｍの電解銅箔の光
沢面を酸洗い及び水洗を行った後陰極としそして銅板を
陽極として、浴組成はＣｕ2+：３５ｇ／ｌそしてＨ2 Ｓ
Ｏ4 ：１００ｇ／ｌにおいてそしてめっき条件は浴温：
４０℃、陰極電流密度：２０Ａ／ｄｍ2 そして通電時
間：０．４秒において銅めっきを行った。電着銅量は約
２．６ｍｇ／ｄｍ2 であった。この銅めっきは、光沢面
をＳＥＭ観察した結果、微粒の電析銅が均一に付着した
平滑面であった。Example 1 A glossy surface of a 35 μm thick electrolytic copper foil was pickled and washed with water and then used as a cathode and a copper plate was used as an anode. The bath composition was Cu 2+ : 35 g / l and H 2 S.
O 4 : at 100 g / l and the plating conditions were bath temperature:
Copper plating was performed at 40 ° C., a cathode current density of 20 A / dm 2 and a conduction time of 0.4 second. The amount of electrodeposited copper was about 2.6 mg / dm 2 . As a result of SEM observation of the glossy surface, the copper plating was a smooth surface on which finely-deposited copper was uniformly adhered.
【００２９】引き続き、得られた光沢面を陰極としそし
て亜鉛板を陽極として、浴組成：２０ｇ／ｌＺｎ−５ｇ
／ｌＮｉのＺｎ−Ｎｉ浴において、ｐＨ：３．５、浴
温：４０℃、陰極電流密度：２．０Ａ／ｄｍ2 及び通電
時間：０．６秒の条件でＺｎ−Ｎｉ合金めっきを行っ
た。得られためっき面を浴組成：ＣｒＯ3 ３．５ｇ／
ｌ、ｐＨ：４．８及び浴温：５０℃のクロメート処理液
に浸漬することによりクロメート処理した。その後、直
ちに、水洗及び乾燥を行って耐熱酸化及び防錆処理光沢
表面を得た。この光沢表面は、Ｚｎ：２００μｇ／ｄｍ
2 、Ｎｉ：２５μｇ／ｄｍ2 そしてＣｒ：１５μｇ／ｄ
ｍ2 を有するものであった。半田濡れ角度は４２．７度
であり、濡れ性１００％と良好であった。Subsequently, using the resulting glossy surface as a cathode and a zinc plate as an anode, bath composition: 20 g / l Zn-5 g
In a Zn / Ni bath of / lNi, Zn-Ni alloy plating was performed under the conditions of pH: 3.5, bath temperature: 40 ° C, cathode current density: 2.0 A / dm 2, and energization time: 0.6 second. . Bath composition: CrO 3 3.5 g /
l, pH: 4.8 and bath temperature: 50 ° C. Immediately thereafter, washing and drying were performed to obtain a heat-resistant oxidized and rust-proof glossy surface. This glossy surface has a Zn content of 200 μg / dm.
2 , Ni: 25 μg / dm 2 and Cr: 15 μg / d
m 2 . The solder wetting angle was 42.7 degrees, and the wettability was 100%, which was good.
【００３０】得られた耐熱酸化銅箔は、３００℃×３０
分の加熱条件のベーキングテストで酸化変色や黄色化は
まったく認められなかった。The obtained heat-resistant copper oxide foil was heated at 300 ° C. × 30.
No oxidation discoloration or yellowing was observed in the baking test under the heating condition for one minute.
【００３１】（比較例１）電解銅箔に銅めっきなしでＺ
ｎ−Ｎｉ合金めっき及びクロメート処理を実施例１と同
様に行って耐熱酸化及び防錆処理光沢表面を得た。得ら
れた光沢面はこの光沢表面は、Ｚｎ：２００μｇ／ｄｍ
2 、Ｎｉ：２５μｇ／ｄｍ2 そしてＣｒ：１５μｇ／ｄ
ｍ2 を有するものであった。得られた原電解銅箔の光沢
面に見られる０．１〜０．３μｍのピットがそのままに
近い状態で点在する面であった。得られた耐熱酸化銅箔
は、３００℃×３０分の加熱条件で島状ないし斑点状の
酸化変色が発生した。(Comparative Example 1) Z without copper plating on electrolytic copper foil
N-Ni alloy plating and chromate treatment were performed in the same manner as in Example 1 to obtain a heat-resistant oxidized and rust-proof glossy surface. The obtained glossy surface was Zn: 200 μg / dm.
2 , Ni: 25 μg / dm 2 and Cr: 15 μg / d
m 2 . The pits of 0.1 to 0.3 μm observed on the glossy surface of the obtained electro-deposited copper foil were scattered in a state close to the pits. In the obtained heat-resistant copper oxide foil, island-like or spot-like oxidative discoloration occurred under heating conditions of 300 ° C. × 30 minutes.
【００３２】（実施例２）厚さ３５μｍの電解銅箔の光
沢面を実施例１と同様にして銅めっきし、引き続き、得
られた光沢面を陰極としそして亜鉛板を陽極として、浴
組成：２０ｇ／ｌＺｎ−１０ｇ／ｌＣｏのＺｎ−Ｃｏ浴
において、ｐＨ：３、浴温：４０℃、陰極電流密度：
２．０Ａ／ｄｍ2 及び通電時間：０．７秒の条件でＺｎ
−Ｃｏ合金めっきを行った。得られためっき面を実施例
１と同じクロメート処理液に浸漬することによりクロメ
ート処理した。その後、直ちに、水洗及び乾燥を行って
耐熱酸化及び防錆処理光沢表面を得た。光沢表面は、Ｚ
ｎ：２３０μｇ／ｄｍ2 、Ｃｏ：２３μｇ／ｄｍ2 そし
てＣｒ：３０μｇ／ｄｍ2 を有するものであった。得ら
れた耐熱酸化銅箔は、３００℃×３０分の加熱条件で酸
化変色や黄色化はまったく認められなかった。半田濡れ
角度は４１．６度であり、濡れ性１００％と良好であっ
た。Example 2 A glossy surface of a 35 μm-thick electrolytic copper foil was copper-plated in the same manner as in Example 1, followed by bath composition using the glossy surface as a cathode and a zinc plate as an anode: In a Zn-Co bath of 20 g / l Zn-10 g / l Co, pH: 3, bath temperature: 40 ° C, cathode current density:
2.0 A / dm 2 and energization time: 0.7 seconds
-Co alloy plating was performed. Chromate treatment was performed by immersing the obtained plated surface in the same chromate treatment solution as in Example 1. Immediately thereafter, washing and drying were performed to obtain a heat-resistant oxidized and rust-proof glossy surface. The glossy surface is Z
n: 230μg / dm 2, Co : 23μg / dm 2 and Cr: had a 30 [mu] g / dm 2. The heat-resistant copper oxide foil obtained did not show any oxidation discoloration or yellowing under heating conditions of 300 ° C. × 30 minutes. The solder wetting angle was 41.6 degrees, and the wettability was 100%, which was good.
【００３３】（比較例２）電解銅箔に銅めっきを施さな
かったことを除いて実施例２と同様の処理を行った。得
られた耐熱酸化銅箔は、３００℃×３０分の加熱条件で
島状ないし斑点状の酸化変色が発生した。(Comparative Example 2) The same treatment as in Example 2 was performed except that no copper plating was applied to the electrolytic copper foil. In the obtained heat-resistant copper oxide foil, island-like or spot-like oxidative discoloration occurred under heating conditions of 300 ° C. × 30 minutes.
【００３４】[0034]
【発明の効果】本発明によりこれまで得られなかった３
００℃×３０分の加熱条件で酸化変色や黄色化が生じな
い優れた耐熱酸化性を備える光沢面を有する銅箔が得ら
れ、今後のプリント基板製造時の熱履歴に対しても銅箔
光沢面の変色を防止し、しかも半田濡れ性、レジスト密
着性といった他の特性を損なうことがなく、今後のプリ
ント基板用銅箔の要求に対処しうる。According to the present invention, 3 which has not been obtained before can be obtained.
A copper foil having a glossy surface with excellent heat-resistant oxidation resistance that does not cause oxidative discoloration or yellowing under heating conditions of 00 ° C. for 30 minutes can be obtained. This prevents the discoloration of the surface, and does not impair other properties such as solder wettability and resist adhesion, and can cope with future requirements for copper foil for printed circuit boards.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ Ｈ０５Ｋ 1/09 Ｈ０５Ｋ 1/09 Ａ ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification code FI H05K 1/09 H05K 1/09 A
Claims (2)
酸化処理層上のＣｒ系防錆処理層とを備える印刷回路用
銅箔において、前記銅箔の光沢面と耐熱酸化処理層との
間に銅めっき層を有することを特徴とする印刷回路用銅
箔。1. A printed circuit copper foil comprising a heat-resistant oxidation treatment layer on a glossy surface of a copper foil and a Cr-based rust-proof treatment layer on the heat-resistance oxidation treatment layer, wherein the glossy surface of the copper foil and the heat-resistance oxidation treatment layer Characterized by having a copper plating layer between the copper foil and the printed circuit board.
て後Ｃｒ系防錆処理を行う印刷回路用銅箔の製造方法に
おいて、前記耐熱酸化処理を行う前に前記銅箔の光沢面
上に銅めっきを行うことを特徴とする印刷回路用銅箔の
製造方法。2. A method for producing a copper foil for a printed circuit in which a glossy surface of a copper foil is subjected to a heat-resistant oxidizing treatment and then subjected to a post-Cr-based rust-proofing treatment. A method for producing a copper foil for a printed circuit, wherein copper plating is performed on a copper foil.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05091842A JP3113445B2 (en) | 1993-03-29 | 1993-03-29 | Copper foil for printed circuit and manufacturing method thereof |
| US08/217,263 US5552234A (en) | 1993-03-29 | 1994-03-24 | Copper foil for printed circuits |
| DE69408189T DE69408189T2 (en) | 1993-03-29 | 1994-03-29 | Copper foil for printed circuit boards and process for their manufacture |
| EP94302237A EP0618755B1 (en) | 1993-03-29 | 1994-03-29 | Copper foil for printed circuits and process for producing the same |
| CN94103182A CN1067120C (en) | 1993-03-29 | 1994-03-29 | Copper foil used for printed circuit |
| CNB00128973XA CN1173612C (en) | 1993-03-29 | 2000-09-14 | Copper foil for printed circuit and its manufacture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05091842A JP3113445B2 (en) | 1993-03-29 | 1993-03-29 | Copper foil for printed circuit and manufacturing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06280047A JPH06280047A (en) | 1994-10-04 |
| JP3113445B2 true JP3113445B2 (en) | 2000-11-27 |
Family
ID=14037844
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP05091842A Expired - Lifetime JP3113445B2 (en) | 1993-03-29 | 1993-03-29 | Copper foil for printed circuit and manufacturing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3113445B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5151761B2 (en) * | 2008-01-10 | 2013-02-27 | 日立電線株式会社 | Method for producing rolled copper foil for printed wiring board |
| US8580390B2 (en) | 2008-12-26 | 2013-11-12 | Jx Nippon Mining & Metals Corporation | Rolled copper foil or electrolytic copper foil for electronic circuit, and method of forming electronic circuit using same |
| JP4955105B2 (en) | 2008-12-26 | 2012-06-20 | Ｊｘ日鉱日石金属株式会社 | Rolled copper foil or electrolytic copper foil for electronic circuit and method for forming electronic circuit using these |
| EP2371995A1 (en) | 2008-12-26 | 2011-10-05 | JX Nippon Mining & Metals Corporation | Rolled copper foil or electrolytic copper foil for electronic circuit and method of forming electronic circuit using same |
-
1993
- 1993-03-29 JP JP05091842A patent/JP3113445B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06280047A (en) | 1994-10-04 |
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