JP2010251777A - Copper foil for electronic circuit, and method of forming electronic circuit - Google Patents

Copper foil for electronic circuit, and method of forming electronic circuit Download PDF

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JP2010251777A
JP2010251777A JP2010131709A JP2010131709A JP2010251777A JP 2010251777 A JP2010251777 A JP 2010251777A JP 2010131709 A JP2010131709 A JP 2010131709A JP 2010131709 A JP2010131709 A JP 2010131709A JP 2010251777 A JP2010251777 A JP 2010251777A
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copper foil
etching
circuit
copper
forming
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JP5043154B2 (en
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Kengo Yonezawa
賢吾 米沢
Masaru Sakamoto
勝 坂本
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JX Nippon Mining and Metals Corp
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Abstract

<P>PROBLEM TO BE SOLVED: To form a circuit with a uniform circuit width, each of etched sides of the circuit having a gradient in a range of 80 to 95 degree, by preventing sag of a copper foil in in-plane directions of the copper foil due to etching, upon forming the circuit by etching the copper foil of a copper-clad laminate plate. <P>SOLUTION: For forming the circuit by etching, a resist layer for etching 3 is formed on a surface of a layer 7 of a metal such as cobalt or nickel, or an alloy, with an etching rate smaller than that of copper, the layer 7 being formed on the etching side one of surfaces of the copper foil 1 for the electronic circuit, and the copper foil 1 with the layer 7 is etched by using a cupric chloride aqueous solution. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

本発明は、エッチングにより回路形成を行う電子回路用銅箔及び電子回路の形成方法に関する。   The present invention relates to a copper foil for electronic circuits for forming a circuit by etching and a method for forming an electronic circuit.

電子・電気機器に印刷回路用銅箔が広く使用されているが、この印刷回路用銅箔は、一般に合成樹脂ボードやフイルム等の基材に接着剤を介して、あるいは接着剤を用いずに高温高圧下で接着して銅張り積層板を製造し、その後、目的とする回路を形成するためにレジスト塗布及び露光工程により回路を印刷し、さらに銅箔の不要部分を除去するエッチング処理を経、またさらに各種の素子が半田付けされてエレクトロデバイス用の印刷回路が形成されている。   Copper foil for printed circuits is widely used in electronic and electrical equipment, but this copper foil for printed circuits is generally used with a base material such as a synthetic resin board or film with or without an adhesive. A copper-clad laminate is produced by bonding under high temperature and high pressure, and then a circuit is printed by a resist coating and exposure process to form the desired circuit, followed by an etching process that removes unnecessary portions of the copper foil. Furthermore, various elements are soldered to form a printed circuit for an electro device.

このような印刷回路に使用する銅箔は、その製造方法の種類の違いにより電解銅箔及び圧延銅箔に大別されるが、いずれも印刷回路板の種類や品質要求に応じて使用されている。
これらの銅箔は、樹脂基材と接着される面と非接着面があり、それぞれ特殊な表面処理(トリート処理)が施されている。また、多層プリント配線板の内層に使用する銅箔のように両面に樹脂との接着機能をもつようにされる(ダブルトリート処理)場合もある。
電解銅箔は一般に回転ドラムに銅を電着させ、それを連続的に剥がして銅箔を製造しているが、この製造時点で回転ドラムに接触する面は光沢面で、その反対側の面は多数の凹凸を有している(粗面)。しかし、このような粗面でも樹脂基板との接着性を一層向上させるために、0.2〜3μm程度の銅粒子を付着させるのが一般的である。
さらに、このような凹凸を増強した上に銅粒子の脱落を防止するために薄いめっき層を形成する場合もある。これらの一連の工程を粗化処理と呼んでいる。このような粗化処理は、電解銅箔に限らず圧延銅箔でも要求されることであり、同様な粗化処理が圧延銅箔においても実施されている。
Copper foils used in such printed circuits are broadly divided into electrolytic copper foils and rolled copper foils depending on the type of manufacturing method, both of which are used according to the types of printed circuit boards and quality requirements. Yes.
These copper foils have a surface to be bonded to the resin base material and a non-bonded surface, and are each subjected to a special surface treatment (treating treatment). In some cases, the copper foil used for the inner layer of the multilayer printed wiring board has a function of adhering to the resin on both sides (double treatment).
In general, electrolytic copper foil is produced by electrodepositing copper onto a rotating drum and continuously peeling it to produce a copper foil. At this time, the surface that contacts the rotating drum is a glossy surface and the opposite surface. Has many irregularities (rough surface). However, in order to further improve the adhesion to the resin substrate even on such a rough surface, it is common to deposit copper particles of about 0.2 to 3 μm.
Furthermore, in addition to enhancing such unevenness, a thin plating layer may be formed in order to prevent the copper particles from falling off. A series of these steps is called roughening treatment. Such a roughening treatment is required not only for the electrolytic copper foil but also for the rolled copper foil, and the same roughening treatment is also carried out for the rolled copper foil.

以上のような銅箔を使用してホットプレス法や連続法により銅張り積層板が製造される。この積層板は、例えばホットプレス法を例にとると、エポキシ樹脂の合成、紙基材へのフェノール樹脂の含浸、乾燥を行ってプリプレグを製造し、さらにこのプリプレグと銅箔を組合せプレス機により熱圧成形を行う等の工程を経て製造されている。
このようにして製造された銅張り積層板は、目的とする回路を形成するためにレジスト塗布及び露光工程により回路を印刷し、さらに銅箔の不要部分を除去するエッチング処理を経るが、ここで大きな問題が発生した。
Using the copper foil as described above, a copper-clad laminate is produced by a hot press method or a continuous method. For example, taking the hot press method as an example, this laminated plate is produced by synthesize epoxy resin, impregnate paper substrate with phenol resin, and dry it to produce a prepreg, and further combine this prepreg and copper foil with a combination press. It is manufactured through processes such as hot pressing.
The copper-clad laminate thus manufactured is printed with a resist coating and exposure process to form a desired circuit, and further undergoes an etching process to remove unnecessary portions of the copper foil. A big problem occurred.

それは、図2に示すようにエッチング後の銅箔回路の銅部分2が末広がりにエッチングされる(ダレを発生する)ことである。図2において符号3はレジスト、符号4は樹脂基板を示す。エッチングが十分でなく、このようなダレが発生した場合には、樹脂基板近傍で銅回路が短絡し不良品となる場合もある。
このような末広がりのエッチング不良を防止するために、図3に示すようにエッチング時間を延長してエッチングをより高める方法を採用した。
しかし、この場合は図3の符号5に示すように、銅回路の側面が極端に狭くなり、回路設計上目的とする均一な線幅(回路幅)が得られず、特にその部分(細線化された部分)で発熱し、場合によっては断線するという問題が発生した。
最近では電子回路のファインパターン化が要求されているが、このようなエッチング不良による問題がより強く現れ、回路形成上大きな問題となっている。
That is, as shown in FIG. 2, the copper part 2 of the copper foil circuit after etching is etched in a divergent manner (sagging occurs). In FIG. 2, reference numeral 3 denotes a resist, and reference numeral 4 denotes a resin substrate. If the etching is not sufficient and such sagging occurs, the copper circuit may be short-circuited near the resin substrate, resulting in a defective product.
In order to prevent such a widening etching failure, a method of increasing the etching time by extending the etching time as shown in FIG. 3 was adopted.
However, in this case, as shown by reference numeral 5 in FIG. 3, the side surface of the copper circuit becomes extremely narrow, and a uniform line width (circuit width) intended for circuit design cannot be obtained. Generated heat), and in some cases, there was a problem of disconnection.
Recently, there has been a demand for fine patterning of electronic circuits. However, problems due to such etching defects have become more serious, and this has become a major problem in circuit formation.

以上から、銅箔の上に、該銅箔よりもエッチング速度が遅い金属であるニッケル又はニッケル合金を、35μm銅箔の上に厚く(銅箔の厚さの1〜20%の範囲で)形成し、これによりサイドエッチングを抑制する提案がなされている(特許文献1参照)。この場合のニッケル又はニッケル合金層は0.35〜7μmの範囲でエッチングに要する時間が大となり、またサイドエッチのバランスが取れなくなるという問題が予想された。
下記特許文献2には、銅箔をエッチングする際に、塩化第二鉄溶液でエッチングする技術が、特許文献3には、厚さ1000〜10000Å(100〜1000μm)の銅箔に、厚さ10〜300Å(1〜30μ)のニッケルの被覆層を形成して腐食を抑制する技術が開示されている。しかし、これらは断片的技術であり、また皮膜の膨大な厚さは電子回路のファインパターン化に適合しない厚さである。したがって、従来の問題は未解決で残っているのが現状である。
From the above, on the copper foil, a nickel or nickel alloy, which is a metal whose etching rate is slower than that of the copper foil, is thickly formed on the 35 μm copper foil (in the range of 1 to 20% of the thickness of the copper foil). Thus, a proposal has been made to suppress side etching (see Patent Document 1). In this case, the nickel or nickel alloy layer was expected to have a problem that the time required for etching was increased in the range of 0.35 to 7 μm, and the balance of side etching could not be achieved.
The following Patent Document 2 discloses a technique of etching with a ferric chloride solution when etching a copper foil. Patent Document 3 discloses that a copper foil having a thickness of 1000 to 10000 mm (100 to 1000 μm) has a thickness of 10 A technique for suppressing corrosion by forming a nickel coating layer of ˜300 mm (1-30 μm) is disclosed. However, these are fragmentary technologies, and the enormous thickness of the coating is not suitable for fine patterning of electronic circuits. Therefore, the existing problem remains unsolved.

特開平6−81172号公報JP-A-6-81172 特開平7−297544号公報JP-A-7-297544 特開2000−269619号公報JP 2000-269619 A

本発明は、銅張り積層板の銅箔をエッチングにより回路形成を行うに際し、エッチングによるダレを防止し、目的とする回路幅の均一な回路を形成できる電子回路用銅箔及びそのための電子回路の形成方法を課題とする。   The present invention provides a copper foil for an electronic circuit capable of preventing sagging due to etching and forming a circuit having a uniform circuit width when a circuit is formed by etching a copper foil of a copper clad laminate, and an electronic circuit for the same The forming method is an issue.

本発明者らは、銅箔の厚み方向のエッチング速度を制御することにより、ダレのない回路幅の均一な回路を形成できるとの知見を得た。
本発明はこの知見に基づいて、
1 エッチングにより回路形成を行う電子回路用銅箔において、エッチング面側に銅よりエッチングレートの遅い金属又は合金層を形成したことを特徴とする電子回路用銅箔
2 銅張り積層板であることを特徴とする上記1記載の電子回路用銅箔
3 銅よりエッチングレートの遅い金属又は合金層がコバルト、ニッケル又はこれらの合金層であることを特徴とする上記1又は2記載の電子回路用銅箔
4 100〜10000μg/dmの金属又は合金層を形成することを特徴とする上記1〜3記載の電子回路用銅箔
5 銅箔のエッチング側面の傾斜角度が、80〜95度の範囲にあることを特徴とする上記1〜4のそれぞれに記載の電子回路用銅箔
6 銅箔のエッチング側面の傾斜角度が、85〜90度の範囲にあることを特徴とする上記1〜4のそれぞれに記載の電子回路用銅箔、を提供する。
The present inventors have obtained the knowledge that a uniform circuit having a sagging circuit width can be formed by controlling the etching rate in the thickness direction of the copper foil.
The present invention is based on this finding,
1. A copper foil for electronic circuits that forms a circuit by etching, wherein a metal or alloy layer having a slower etching rate than copper is formed on the etched surface side. 3. The copper foil for electronic circuits according to 1 or 2 above, wherein the metal or alloy layer having a slower etching rate than copper is cobalt, nickel or an alloy layer thereof. (4) The copper foil for electronic circuits as described in (1) to (3) above, wherein a metal or alloy layer of 100 to 10,000 μg / dm 2 is formed, and the inclination angle of the etching side surface of the copper foil is in the range of 80 to 95 degrees. The copper foil for electronic circuits 6 according to each of the above 1 to 4, characterized in that the inclination angle of the etching side surface of the copper foil is in the range of 85 to 90 degrees. Providing a copper foil, an electronic circuit according to respectively.

さらに、また
7 銅張り積層板の銅箔をエッチングし電子回路を形成する方法において、銅箔のエッチング面側に銅よりエッチングレートの遅い金属又は合金層を形成した後、塩化第二銅水溶液を用いて該銅箔をエッチングし、回路を形成することを特徴とする電子回路の形成方法
8 銅よりエッチングレートの遅い金属又は合金層がコバルト、ニッケル又はこれらの合金層であることを特徴とする上記7記載の電子回路の形成方法
9 100〜10000μg/dmの金属又は合金層を形成することを特徴とする上記7又は8記載の電子回路の形成方法
10 銅箔のエッチング側面の傾斜角度が、80〜95度の範囲にあることを特徴とする上記7〜9のそれぞれに記載の電子回路の形成方法
11 銅箔のエッチング側面の傾斜角度が、85〜90度の範囲にあることを特徴とする上記7〜9のそれぞれに記載の電子回路の形成方法、を提供するものである。
Furthermore, in the method of forming an electronic circuit by etching a copper foil of a copper-clad laminate, a metal or alloy layer having a slower etching rate than copper is formed on the etched surface side of the copper foil, and then an aqueous cupric chloride solution is added. A method of forming an electronic circuit, wherein the copper foil is etched to form a circuit, wherein the metal or alloy layer having a slower etching rate than copper is cobalt, nickel or an alloy layer thereof. 9. The electronic circuit forming method according to 7 above, wherein the metal or alloy layer of 100 to 10000 μg / dm 2 is formed. 10. The electronic circuit forming method according to 7 or 8 above, wherein the inclination angle of the etching side surface of the copper foil is The method of forming an electronic circuit according to each of 7 to 9 above, wherein the inclination angle of the etching side surface of the copper foil is 85 to 85 degrees. Method of forming an electronic circuit according to each of the above 7-9, characterized in that in the range of 0 degrees, there is provided a.

本発明は、銅張り積層板の銅箔をエッチングにより回路形成を行うに際し、銅箔の厚み方向のエッチング速度を制御することにより、ダレのない回路幅の均一な回路を形成できるという優れた効果を有する。   The present invention has an excellent effect that a uniform circuit having a sagging circuit width can be formed by controlling the etching rate in the thickness direction of the copper foil when forming a circuit by etching the copper foil of the copper clad laminate. Have

本発明の実施例で得られた良好な矩形の銅箔回路が形成された様子を示す説明図である。It is explanatory drawing which shows a mode that the favorable rectangular copper foil circuit obtained in the Example of this invention was formed. 比較例2に示すようなダレが大きく、台形状の不良な銅箔回路が形成された様子を示す説明図である。It is explanatory drawing which shows a mode that the sagging as shown in the comparative example 2 was large, and the copper foil circuit with a trapezoid defect was formed. エッチング速度を高めた例であり、エッチングが強すぎて銅箔回路が細くなり、不良な回路が形成された様子を示す説明図である。It is an example which increased the etching rate, and is an explanatory view showing a state in which the etching is too strong, the copper foil circuit becomes thin, and a defective circuit is formed.

本発明は、エッチングにより回路形成を行う電子回路用銅箔のエッチング面側に、銅よりエッチングレートの遅い金属又は合金層を形成し、銅張り積層板とする。この銅箔は、電解銅箔及び圧延銅箔のいずれにも適用できる。また、粗化面(M面)又は光沢面(S面)にも同様に適用できる。
圧延銅箔の中には高純度銅箔又は強度を向上させた合金銅箔も存在するが、本件発明はこれらの銅箔の全てを包含する。
銅よりエッチングレートの遅い金属又は合金層を形成する材料としては、コバルト、ニッケル又はこれらの合金が使用できるが、特にコバルト、ニッケル又はこれらの合金が好適である。合金層としては、Co−P、Ni−P、Co−Ni、Co−Zn、Ni−Znが使用できる。
The present invention forms a copper-clad laminate by forming a metal or alloy layer having a slower etching rate than copper on the etched surface side of the copper foil for electronic circuits that forms a circuit by etching. This copper foil can be applied to both electrolytic copper foil and rolled copper foil. Further, the present invention can be similarly applied to a roughened surface (M surface) or a glossy surface (S surface).
Among the rolled copper foils, there are high-purity copper foils or alloy copper foils with improved strength, but the present invention encompasses all these copper foils.
As a material for forming a metal or alloy layer having a slower etching rate than copper, cobalt, nickel, or an alloy thereof can be used, but cobalt, nickel, or an alloy thereof is particularly preferable. As the alloy layer, Co—P, Ni—P, Co—Ni, Co—Zn, or Ni—Zn can be used.

コバルト又はニッケル等のエッチングを抑制する金属又は合金は、図1の符号1示すように銅箔1上のレジスト部分3に近い位置にあり、レジスト3側の銅箔1のエッチング速度は、このコバルト、ニッケル等の層7により抑制され、逆にコバルト、ニッケル等の層から遠ざかるに従いエッチングは通常の速度で進行する。
これによって、銅回路の側面6のレジスト3側から樹脂基板4側に向かってほぼ垂直にエッチングが進行し、矩形の銅箔回路が形成される。
The metal or alloy that suppresses etching such as cobalt or nickel is located near the resist portion 3 on the copper foil 1 as shown by reference numeral 1 in FIG. 1, and the etching rate of the copper foil 1 on the resist 3 side is the cobalt. Etching proceeds at a normal rate as it is suppressed by the layer 7 of nickel or the like and conversely away from the layer of cobalt or nickel.
As a result, etching proceeds substantially perpendicularly from the resist 3 side of the side surface 6 of the copper circuit toward the resin substrate 4 side, and a rectangular copper foil circuit is formed.

コバルト又はニッケル等の銅よりエッチングレートの遅い金属又は合金層の厚さは、100〜10000μg/dmとするのが良い。100μg/dm未満であると、銅箔の厚み方向のエッチング速度を効果的に制御することができず、ダレのない回路幅の均一な回路を形成することが難しくなる。また、10000μg/dmを超えると、レジスト側のエッチングが抑制され過ぎて銅箔回路のエッチング部がいびつになるので好ましくない。 The thickness of the metal or alloy layer whose etching rate is slower than that of copper such as cobalt or nickel is preferably 100 to 10,000 μg / dm 2 . If it is less than 100 μg / dm 2 , the etching rate in the thickness direction of the copper foil cannot be controlled effectively, and it becomes difficult to form a uniform circuit with no circuit sagging. On the other hand, if it exceeds 10,000 μg / dm 2 , etching on the resist side is excessively suppressed and the etched portion of the copper foil circuit becomes distorted.

下記に好適なめっき条件の例を示す。
(コバルトめっき)
Co:1〜20g/L
pH:1〜4
温度:常温〜60°C
電流密度Dk:1〜15A/dm
時間:1〜10秒
Examples of suitable plating conditions are shown below.
(Cobalt plating)
Co: 1-20 g / L
pH: 1-4
Temperature: normal temperature to 60 ° C
Current density Dk: 1 to 15 A / dm 2
Time: 1-10 seconds

(ニッケルめっき)
Ni:1〜20g/L
pH:1〜4
温度:常温〜60°C
電流密度Dk:1〜15A/dm
時間:1〜10秒
(Nickel plating)
Ni: 1 to 20 g / L
pH: 1-4
Temperature: normal temperature to 60 ° C
Current density Dk: 1 to 15 A / dm 2
Time: 1-10 seconds

(Co−Ni合金めっき)
Co:1〜20g/L
Ni:1〜20g/L
温度:常温〜60°C
電流密度Dk:1〜15A/dm
時間:1〜10秒
(Co-Ni alloy plating)
Co: 1-20 g / L
Ni: 1 to 20 g / L
Temperature: normal temperature to 60 ° C
Current density Dk: 1 to 15 A / dm 2
Time: 1-10 seconds

銅張り積層板の銅箔のエッチングに際しては、銅箔のエッチング面側に銅よりエッチングレートの遅い金属又は合金層を形成した後、塩化第二銅水溶液を用いて該銅箔をエッチングする。
上記の条件でエッチングすることにより、銅箔回路のエッチング側面と樹脂基板との間の傾斜角度が80〜95度の範囲にすることができる。特に望ましい傾斜角度は85〜90度の範囲である。これによって、ダレのない矩形のエッチング回路が形成できる。
In etching the copper foil of the copper-clad laminate, a metal or alloy layer having a slower etching rate than copper is formed on the etching surface side of the copper foil, and then the copper foil is etched using a cupric chloride aqueous solution.
By etching under the above conditions, the inclination angle between the etching side surface of the copper foil circuit and the resin substrate can be in the range of 80 to 95 degrees. A particularly desirable inclination angle is in the range of 85 to 90 degrees. Thereby, a rectangular etching circuit without sagging can be formed.

次に、本発明の実施例、参考例及び比較例について説明する。なお、本実施例はあくまで1例であり、この例に制限されるものではない。すなわち、本発明の技術思想の範囲内で、実施例以外の態様あるいは変形を全て包含するものである。 Next, examples, reference examples and comparative examples of the present invention will be described. In addition, a present Example is an example to the last, and is not restrict | limited to this example. That is, all aspects or modifications other than the embodiments are included within the scope of the technical idea of the present invention.

参考例1
12μm電解銅箔の光沢(S)面に、コバルトめっきを施した。
めっき条件は次の通りである。
Co:10g/L
pH:2.5
温度:50°C
電流密度Dk:5A/dm
時間:2秒
( Reference Example 1 )
Cobalt plating was performed on the gloss (S) surface of the 12 μm electrolytic copper foil.
The plating conditions are as follows.
Co: 10 g / L
pH: 2.5
Temperature: 50 ° C
Current density Dk: 5 A / dm 2
Time: 2 seconds

このコバルトめっき層の厚さは2500μg/dmであった。
このコバルトめっき層を設けた銅箔をエッチング側とし、樹脂基板に接着して銅張り積層板とした。その後、レジスト塗布及び露光工程により10本の回路を印刷し、さらに銅箔の不要部分を除去するエッチング処理を実施した。
エッチング液は塩化第二銅水溶液を用いた。エッチング条件は次の通りである。
水溶液組成:CuCl、CuO、HCl(3.5M/L)
S.G.(比重):1.26
温度:50°C
搬送スピード:0.77m/min(槽長770mm)
上面回路幅:0.222mm
The cobalt plating layer had a thickness of 2500 μg / dm 2 .
The copper foil provided with this cobalt plating layer was used as the etching side, and was bonded to a resin substrate to obtain a copper-clad laminate. Then, 10 circuits were printed by the resist coating and exposure process, and an etching process for removing unnecessary portions of the copper foil was performed.
An aqueous solution of cupric chloride was used as the etching solution. Etching conditions are as follows.
Aqueous solution composition: CuCl 2 , CuO, HCl (3.5 M / L)
S. G. (Specific gravity): 1.26
Temperature: 50 ° C
Conveying speed: 0.77m / min (tank length 770mm)
Top circuit width: 0.222 mm

これによって、図1に示すように銅回路の側面6のレジスト3側から樹脂基板4側に向かってほぼ垂直にエッチングが進行し、矩形の銅箔回路が形成された。
次に、エッチングした銅箔の傾斜角度を測定した(なお、この測定値は、エッチング回路10の平均値である)。その結果左傾斜角91.8度であり、右傾斜角89.4°であり、ほぼ矩形の銅箔回路が形成され、極めて良好なエッチング回路が得られた。
As a result, as shown in FIG. 1, the etching progressed almost vertically from the resist 3 side to the resin substrate 4 side of the side surface 6 of the copper circuit, and a rectangular copper foil circuit was formed.
Next, the tilt angle of the etched copper foil was measured (note that this measured value is an average value of the etching circuit 10). As a result, the left inclination angle was 91.8 degrees, the right inclination angle was 89.4 °, and a substantially rectangular copper foil circuit was formed, and an extremely good etching circuit was obtained.

実施例1
12μm電解銅箔の粗化(M)面に、ニッケルめっきを施した。
めっき条件は次の通りである。
Ni:10g/L
pH:2.5
温度:50°C
電流密度Dk:5A/dm
時間:8秒
( Example 1 )
Nickel plating was applied to the roughened (M) surface of the 12 μm electrolytic copper foil.
The plating conditions are as follows.
Ni: 10 g / L
pH: 2.5
Temperature: 50 ° C
Current density Dk: 5 A / dm 2
Time: 8 seconds

このニッケルめっき層の厚さは6600μg/dmであった。
このニッケルめっき層を設けた銅箔をエッチング側として樹脂基板に接着し、銅張り積層板とした。その後、レジスト塗布及び露光工程により10本の回路を印刷し、さらに銅箔の不要部分を除去するエッチング処理を実施した。
エッチング液は塩化第二銅水溶液を用いた。エッチング条件は次の通りである。
水溶液組成:CuCl、CuO、HCl(3.5M/L)
S.G.(比重):1.26
温度:50°C
搬送スピード:0.77m/min(槽長770mm)
上面回路幅:0.232mm
The nickel plating layer had a thickness of 6600 μg / dm 2 .
The copper foil provided with the nickel plating layer was bonded to the resin substrate as an etching side to obtain a copper-clad laminate. Then, 10 circuits were printed by the resist coating and exposure process, and an etching process for removing unnecessary portions of the copper foil was performed.
An aqueous solution of cupric chloride was used as the etching solution. Etching conditions are as follows.
Aqueous solution composition: CuCl 2 , CuO, HCl (3.5 M / L)
S. G. (Specific gravity): 1.26
Temperature: 50 ° C
Conveying speed: 0.77m / min (tank length 770mm)
Top circuit width: 0.232 mm

これによって、図1に示すように銅回路の側面6のレジスト3側から樹脂基板4側に向かってほぼ垂直にエッチングが進行し、矩形の銅箔回路が形成された。
次に、エッチングした銅箔の傾斜角度を測定した(なお、この測定値は、エッチング回路10の平均値である)。その結果左傾斜角81.5度であり、右傾斜角82.5°であり、図1に示すような、ほぼ矩形の銅箔回路が形成され、良好なエッチング回路が得られた。
As a result, as shown in FIG. 1, the etching progressed almost vertically from the resist 3 side to the resin substrate 4 side of the side surface 6 of the copper circuit, and a rectangular copper foil circuit was formed.
Next, the tilt angle of the etched copper foil was measured (note that this measured value is an average value of the etching circuit 10). As a result, the left inclination angle was 81.5 degrees and the right inclination angle was 82.5 degrees. As shown in FIG. 1, a substantially rectangular copper foil circuit was formed, and a good etching circuit was obtained.

(比較例1)
12μm電解銅箔の光沢(S)面に、コバルトめっきを施した。
めっき条件は次の通りである。
Co:10g/L
pH:2.5
温度:50°C
電流密度Dk:5A/dm
時間:14秒
(Comparative Example 1)
Cobalt plating was performed on the gloss (S) surface of the 12 μm electrolytic copper foil.
The plating conditions are as follows.
Co: 10 g / L
pH: 2.5
Temperature: 50 ° C
Current density Dk: 5 A / dm 2
Time: 14 seconds

このコバルトめっき層の厚さは13000μg/dmであった。
このコバルトめっき層を設けた銅箔をエッチング面側として樹脂基板に接着し、エッチング側とし、銅張り積層板とした。その後、レジスト塗布及び露光工程により10本の回路を印刷し、さらに銅箔の不要部分を除去するエッチング処理を実施した。
The thickness of this cobalt plating layer was 13000 μg / dm 2 .
The copper foil provided with the cobalt plating layer was adhered to the resin substrate as the etching surface side, and the etching side was used as a copper-clad laminate. Then, 10 circuits were printed by the resist coating and exposure process, and an etching process for removing unnecessary portions of the copper foil was performed.

エッチング液は塩化第二銅水溶液を用いた。エッチング条件は次の通りである。
水溶液組成:CuCl、CuO、HCl(3.5M/L)
S.G.(比重):1.26
温度:50°C
搬送スピード:0.77m/min(槽長770mm)
上面回路幅:0.220mm
An aqueous solution of cupric chloride was used as the etching solution. Etching conditions are as follows.
Aqueous solution composition: CuCl 2 , CuO, HCl (3.5 M / L)
S. G. (Specific gravity): 1.26
Temperature: 50 ° C
Conveying speed: 0.77m / min (tank length 770mm)
Top circuit width: 0.220 mm

次に、エッチングした銅箔の傾斜角度を測定した(なお、この測定値は、エッチング回路10の平均値である)。その結果左傾斜角101.3度であり、右傾斜角108.0°であり、図3に示すような、レジスト側に比べて樹脂基板側が過度にエッチングされ、逆台形状の銅箔回路が形成され、エッチング不良の回路が形成された。   Next, the tilt angle of the etched copper foil was measured (note that this measured value is an average value of the etching circuit 10). As a result, the left tilt angle is 101.3 degrees, the right tilt angle is 108.0 °, and the resin substrate side is excessively etched compared to the resist side as shown in FIG. As a result, a circuit with poor etching was formed.

(比較例2)
12μm電解銅箔を、粗化(M)面側をエッチング面として、樹脂基板に接着して銅張り積層板とした後、レジスト塗布及び露光工程により10本の回路を印刷し、さらに銅箔の不要部分を除去するエッチング処理を実施した。
エッチング液は塩化第二銅水溶液を用いた。エッチング条件は次の通りである。
水溶液組成:CuCl、CuO、HCl(3.5M/L)
S.G.(比重):1.26
温度:50°C
搬送スピード:0.77m/min(槽長770mm)
上面回路幅:0.233mm
(Comparative Example 2)
After 12 μm electrolytic copper foil is bonded to a resin substrate with the roughened (M) surface side as an etching surface to form a copper-clad laminate, 10 circuits are printed by resist coating and exposure processes, An etching process for removing unnecessary portions was performed.
An aqueous solution of cupric chloride was used as the etching solution. Etching conditions are as follows.
Aqueous solution composition: CuCl 2 , CuO, HCl (3.5 M / L)
S. G. (Specific gravity): 1.26
Temperature: 50 ° C
Conveying speed: 0.77m / min (tank length 770mm)
Top circuit width: 0.233 mm

次に、エッチングした銅箔の傾斜角度を測定した(なお、この測定値は、エッチング回路10の平均値である)。その結果、左傾斜角73.5度であり、右傾斜角76.3°であり、図2に示すような、ダレが大きく台形状の銅箔回路が形成され、エッチング不良であった。   Next, the tilt angle of the etched copper foil was measured (note that this measured value is an average value of the etching circuit 10). As a result, the left tilt angle was 73.5 degrees, the right tilt angle was 76.3 °, a trapezoidal copper foil circuit having a large sag as shown in FIG. 2 was formed, and the etching was defective.

以上の結果を表1に示す。
表1から明らかなように、100〜10000μg/dmの範囲にあるコバルトめっき及びニッケルめっきは、ほぼ矩形の銅箔回路が形成され、極めて良好なエッチング回路が得られた。特にコバルトめっき層は少量でも優れたエッチング性が得られた。
これに対して、めっき層を設けていないものは、ダレが大きく台形状の銅箔回路が形成され、エッチング不良であった。また、逆にめっき層が多すぎると、レジスト側に比べて樹脂基板側が過度にエッチングされ、逆台形状の銅箔回路が形成されて、エッチング不良の回路が形成された。
The results are shown in Table 1.
As is apparent from Table 1, cobalt plating and nickel plating in the range of 100 to 10000 μg / dm 2 formed a substantially rectangular copper foil circuit, and an extremely good etching circuit was obtained. In particular, excellent etching properties were obtained even with a small amount of the cobalt plating layer.
On the other hand, when the plating layer was not provided, the sagging was large and a trapezoidal copper foil circuit was formed, resulting in poor etching. On the other hand, when there are too many plating layers, the resin substrate side is excessively etched as compared with the resist side, an inverted trapezoidal copper foil circuit is formed, and a circuit with poor etching is formed.

以上の実施例、参考例及び比較例以外に、多くの実験を繰り返し行ったところ、100〜10000μg/dmの金属又は合金層を形成することが望ましいことが分かった。
実施例では、コバルト層及びニッケル層を形成した場合について説明したが、これらの合金層でも同様な効果があることを確認した。しかし、合金めっきに比べ,コバルトめっき及びニッケルめっきの単独層はめっき液及びめっき条件の管理が容易なので、めっき処理操作上より効果的である。
In addition to the above examples , reference examples and comparative examples, many experiments were repeated, and it was found that it is desirable to form a metal or alloy layer of 100 to 10000 μg / dm 2 .
In the examples, the case where the cobalt layer and the nickel layer are formed has been described, but it was confirmed that these alloy layers have the same effect. However, compared to alloy plating, a single layer of cobalt plating and nickel plating is more effective in plating processing operations because it is easier to manage the plating solution and plating conditions.

Figure 2010251777
Figure 2010251777

本発明は、銅張り積層板の銅箔をエッチングにより回路形成を行うに際し、銅箔の厚み方向のエッチング速度を制御することにより、ダレのない回路幅の均一な回路を形成できるという優れた効果を有するので、回路幅の均一な回路を形成できる電子回路用銅箔として有用である。   The present invention has an excellent effect that a uniform circuit having a sagging circuit width can be formed by controlling the etching rate in the thickness direction of the copper foil when forming a circuit by etching the copper foil of the copper clad laminate. Therefore, it is useful as a copper foil for electronic circuits that can form a circuit having a uniform circuit width.

1: 銅箔
2:ダレが発生した銅箔エッチング面
3:レジスト
4:樹脂基板
5:過度にエッチングされた銅箔エッチング面
6:基板に対してほぼ垂直である銅箔エッチング面
7:コバルト又はニッケル等の金属又は合金層
1: Copper foil 2: Copper foil etched surface where sagging occurred 3: Resist 4: Resin substrate 5: Overetched copper foil etched surface 6: Copper foil etched surface that is substantially perpendicular to the substrate 7: Cobalt or Metal or alloy layer such as nickel

Claims (11)

エッチングにより回路形成を行う電子回路用銅箔において、エッチング面側に銅よりエッチングレートの遅い金属又は合金層を形成したことを特徴とする電子回路用銅箔。   An electronic circuit copper foil for forming a circuit by etching, wherein a metal or alloy layer having a slower etching rate than copper is formed on the etched surface side. 銅張り積層板であることを特徴とする請求項1記載の電子回路用銅箔。   2. The copper foil for electronic circuits according to claim 1, which is a copper-clad laminate. 銅よりエッチングレートの遅い金属又は合金層がコバルト、ニッケル又はこれらの合金層であることを特徴とする請求項1又は2記載の電子回路用銅箔。   3. The copper foil for electronic circuits according to claim 1, wherein the metal or alloy layer having a slower etching rate than copper is cobalt, nickel, or an alloy layer thereof. 100〜10000μg/dmの金属又は合金層を形成することを特徴とする請求項1〜3のそれぞれに記載の電子回路用銅箔。 The copper foil for electronic circuits according to each of claims 1 to 3, wherein a metal or alloy layer of 100 to 10000 µg / dm 2 is formed. 銅箔のエッチング側面の傾斜角度が、80〜95度の範囲にあることを特徴とする請求項1〜4のそれぞれに記載の電子回路用銅箔。   The copper foil for electronic circuits according to each of claims 1 to 4, wherein the inclination angle of the etching side surface of the copper foil is in the range of 80 to 95 degrees. 銅箔のエッチング側面の傾斜角度が、85〜90度の範囲にあることを特徴とする請求項1〜4のそれぞれに記載の電子回路用銅箔。   The copper foil for electronic circuits according to each of claims 1 to 4, wherein the inclination angle of the etching side surface of the copper foil is in the range of 85 to 90 degrees. 銅張り積層板の銅箔をエッチングし電子回路を形成する方法において、銅箔のエッチング面側に銅よりエッチングレートの遅い金属又は合金層を形成した後、塩化第二銅水溶液を用いて該銅箔をエッチングし、回路を形成することを特徴とする電子回路の形成方法。   In a method of forming an electronic circuit by etching a copper foil of a copper-clad laminate, after forming a metal or alloy layer having a slower etching rate than copper on the etched surface side of the copper foil, the copper foil is used with a cupric chloride aqueous solution. A method of forming an electronic circuit, comprising etching a foil to form a circuit. 銅よりエッチングレートの遅い金属又は合金層がコバルト、ニッケル又はこれらの合金層であることを特徴とする請求項7記載の電子回路の形成方法。   8. The method for forming an electronic circuit according to claim 7, wherein the metal or alloy layer whose etching rate is slower than that of copper is cobalt, nickel or an alloy layer thereof. 100〜10000μg/dmの金属又は合金層を形成することを特徴とする請求項7又は8記載の電子回路の形成方法。 9. The method for forming an electronic circuit according to claim 7, wherein a metal or alloy layer of 100 to 10,000 [mu] g / dm < 2 > is formed. 銅箔のエッチング側面の傾斜角度が、80〜95度の範囲にあることを特徴とする請求項7〜9のそれぞれに記載の電子回路の形成方法。   The method for forming an electronic circuit according to claim 7, wherein an inclination angle of the etched side surface of the copper foil is in a range of 80 to 95 degrees. 銅箔のエッチング側面の傾斜角度が、85〜90度の範囲にあることを特徴とする請求項7〜9のそれぞれに記載の電子回路の形成方法。   The method for forming an electronic circuit according to claim 7, wherein an inclination angle of an etching side surface of the copper foil is in a range of 85 to 90 degrees.
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