JPH07235766A - Method of treating copper circuit on inner layer printed wiring board - Google Patents
Method of treating copper circuit on inner layer printed wiring boardInfo
- Publication number
- JPH07235766A JPH07235766A JP2564794A JP2564794A JPH07235766A JP H07235766 A JPH07235766 A JP H07235766A JP 2564794 A JP2564794 A JP 2564794A JP 2564794 A JP2564794 A JP 2564794A JP H07235766 A JPH07235766 A JP H07235766A
- Authority
- JP
- Japan
- Prior art keywords
- wiring board
- inner layer
- copper circuit
- copper
- aqueous solution
- 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
- Production Of Multi-Layered Print Wiring Board (AREA)
- Manufacturing Of Printed Wiring (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は多層プリント配線板の製
造に用いられる内層用配線板の銅回路の処理方法に関す
るものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for treating a copper circuit of an inner wiring board used for manufacturing a multilayer printed wiring board.
【０００２】[0002]
【従来の技術】電子機器、電気機器に多層プリント配線
板は、例えば、片面乃至両面に銅回路を形成した内層用
配線板にプリプレグを介して外層用配線板、又は銅箔を
重ね、加熱加圧することによって製造される。2. Description of the Related Art A multilayer printed wiring board for electronic equipment and electric equipment is, for example, an inner wiring board having a copper circuit formed on one side or both sides thereof, and an outer wiring board or a copper foil laminated on the wiring board via a prepreg and heated. Manufactured by pressing.
【０００３】この多層プリント配線板にあっては、上記
内層用配線板に形成された銅回路とプリプレグの接着性
を確保する必要性から、銅回路とプリプレグの接着性を
高める種々の方法が検討され、特に内層用配線板の銅回
路の表面に銅酸化物からなる銅酸化膜を形成する方法が
行われている。この方法は銅回路の表面に酸化第二銅を
主成分とした、微細な突起を有する銅酸化膜を形成し
て、プリプレグとの接着性を高めるものである。しか
し、この酸化第二銅は酸に溶解し易いため、多層の銅張
り積層板に形成したスルホールにメッキを施すと、スル
ホールの内壁に露出した銅回路の酸化第二銅が、メッキ
液中の塩酸等の酸に溶解し、内層用配線板の銅回路とプ
リプレグの硬化した接着層との界面に酸が進入し、いわ
ゆるハロー現象を誘起する。このハロー現象が起こると
多層プリント配線板の導通不良を起こし信頼性が低下す
るおそれがある。In this multilayer printed wiring board, it is necessary to secure the adhesiveness between the copper circuit and the prepreg formed on the inner layer wiring board. Therefore, various methods for enhancing the adhesiveness between the copper circuit and the prepreg have been studied. In particular, a method of forming a copper oxide film made of copper oxide on the surface of the copper circuit of the inner layer wiring board is performed. According to this method, a copper oxide film containing fine cupric oxide as a main component and having fine projections is formed on the surface of a copper circuit to enhance the adhesiveness with a prepreg. However, since this cupric oxide is easily dissolved in acid, when plating is applied to the through-holes formed on the multilayer copper-clad laminate, the cupric oxide in the copper circuit exposed on the inner wall of the through-hole is When dissolved in an acid such as hydrochloric acid, the acid enters the interface between the copper circuit of the inner layer wiring board and the cured adhesive layer of the prepreg, and induces a so-called halo phenomenon. When this halo phenomenon occurs, there is a possibility that the multilayer printed wiring board may have poor continuity and the reliability may be reduced.
【０００４】このハロー現象の発生を抑えるために、銅
酸化膜を形成した後に、弱酸性水溶液に浸漬して、銅酸
化膜中の酸化第二銅の皮膜を除去し、酸化第一銅の皮膜
を残す処理が知られている。しかし、近年の高密度化の
要求に伴う、ハロー現象のより完全な防止と内層用配線
板の銅回路の密着性のより良好な多層プリント配線板を
得るには、酸化第二銅のさらに改善された除去が求めら
れている。In order to suppress the occurrence of this halo phenomenon, after forming a copper oxide film, it is immersed in a weakly acidic aqueous solution to remove the cupric oxide film in the copper oxide film, and to remove the cuprous oxide film. The process of leaving is known. However, in order to obtain a multilayer printed wiring board with more complete prevention of the halo phenomenon and better adhesion of the copper circuit of the inner layer wiring board with the recent demand for higher density, further improvement of cupric oxide is required. Required removal.
【０００５】[0005]
【発明が解決しようとする課題】本発明は上記事実に鑑
みてなされたもので、その目的とするところは、ハロー
現象がおきず、銅回路の密着性が良好な多層プリント配
線板を得ることのできる、内層用配線板の銅回路の処理
方法を提供することにある。The present invention has been made in view of the above facts, and an object of the present invention is to obtain a multilayer printed wiring board in which the halo phenomenon does not occur and the adhesion of copper circuits is good. Another object of the present invention is to provide a method of treating a copper circuit of a wiring board for an inner layer, which is capable of performing the above.
【０００６】[0006]
【課題を解決するための手段】本発明の請求項１に係る
内層用配線板の銅回路の処理方法は、内層用配線板を
亜塩素酸ナトリウム水溶液に浸漬して、内層用配線板の
銅回路に銅酸化膜を形成し、その後弱酸性水溶液に浸漬
する内層用配線板の銅回路の処理方法であって、亜塩
素酸ナトリウムの濃度が９２〜１１２ｇ／リットル、水
酸化ナトリウムの濃度が３５〜４５ｇ／リットル、水酸
化ナトリウムに対する亜塩素酸ナトリウムの重量比が
２．０〜３．２の配合からなる亜塩素酸ナトリウム水溶
液に内層用配線板を浸漬し、上記内層用配線板の金属
銅からなる銅回路に銅酸化膜を８０〜１６０ｍｇ／ｄｍ
2 形成した後に、弱酸性水溶液に浸漬して、内層用配
線板の金属銅からなる銅回路の膜厚を３．２〜３３．６
ｍｇ／ｄｍ2 とし、且つ、上記亜塩素酸ナトリウム水溶
液浸漬後の銅酸化膜に対し、上記弱酸性水溶液浸漬後の
上記膜厚が重量比で０．０４〜０．２１の範囲とするこ
とを特徴とする。According to a first aspect of the present invention, there is provided a method for treating a copper circuit of an inner layer wiring board by immersing the inner layer wiring board in an aqueous sodium chlorite solution to form a copper layer of the inner layer wiring board. A method for treating a copper circuit of a wiring board for an inner layer, which comprises forming a copper oxide film on a circuit and then immersing it in a weakly acidic aqueous solution, wherein the concentration of sodium chlorite is 92 to 112 g / liter and the concentration of sodium hydroxide is 35. ˜45 g / liter, the inner layer wiring board is immersed in an aqueous solution of sodium chlorite having a weight ratio of sodium chlorite to sodium hydroxide of 2.0 to 3.2, and metal copper of the inner layer wiring board 80-160mg / dm2 of copper oxide film on the copper circuit consisting of
2 After forming, dip it in a weakly acidic aqueous solution to make the thickness of the copper circuit made of metallic copper of the inner layer wiring board 3.2 to 33.6.
mg / dm 2 , and the weight ratio of the film thickness after immersion in the weakly acidic aqueous solution to the copper oxide film after immersion in the sodium chlorite aqueous solution is 0.04 to 0.21. Characterize.
【０００７】本発明の請求項２に係る内層用配線板の銅
回路の処理方法は、請求項１記載の内層用配線板の銅回
路の処理方法において、上記亜塩素酸ナトリウム水溶液
に内層用配線板を浸漬した際に亜塩素酸ナトリウム水溶
液中に蓄積される塩化ナトリウムの濃度を４０ｇ／リッ
トル以下、酸化第二銅の濃度を６ｇ／リットル以下、炭
酸ナトリウムの濃度を４０ｇ／リットル以下に保持する
ことを特徴とする。A method for treating a copper circuit of an inner layer wiring board according to a second aspect of the present invention is the method for treating a copper circuit of the inner layer wiring board according to the first aspect, wherein the inner layer wiring is added to the sodium chlorite aqueous solution. The concentration of sodium chloride accumulated in the aqueous solution of sodium chlorite when the plate is immersed is kept at 40 g / liter or less, the concentration of cupric oxide is kept at 6 g / liter or less, and the concentration of sodium carbonate is kept at 40 g / liter or less. It is characterized by
【０００８】以下、本発明を詳細に説明する。本発明に
用いる内層用配線板は、表面に銅回路が形成されてい
る。上記内層用配線板としては、例えば、銅箔を張った
ガラス基材のエポキシ樹脂積層板、ガラスポリイミド樹
脂積層板、不飽和ポリエステル樹脂積層板、フッ素樹脂
積層板、及びこれら樹脂の変性樹脂積層板等が用いら
れ、上記積層板の銅箔にエッチングを施すと片面もしく
は両面に銅回路が形成される。The present invention will be described in detail below. The inner layer wiring board used in the present invention has a copper circuit formed on its surface. Examples of the inner layer wiring board include, for example, a copper-clad glass-based epoxy resin laminate, a glass polyimide resin laminate, an unsaturated polyester resin laminate, a fluororesin laminate, and a modified resin laminate of these resins. Etc. are used, and a copper circuit is formed on one side or both sides by etching the copper foil of the above laminated plate.
【０００９】本発明は、この内層用配線板を亜塩素酸ナ
トリウム水溶液に浸漬して、銅回路に銅酸化膜を形成す
る。この方法は銅回路の表面に酸化第二銅を主成分とし
た、微細な突起を有する銅酸化膜を形成して、プリプレ
グとの接着性を高めるものである。本発明においては、
上記亜塩素酸ナトリウム水溶液の成分として、亜塩素酸
ナトリウム（ＮａＣｌＯ2 ）が９２〜１１２ｇ／リット
ル範囲の濃度であり、水酸化ナトリウム（ＮａＯＨ）が
３５〜４５ｇ／リットルの範囲の濃度で含有する水溶液
である。さらに、水酸化ナトリウムに対する亜塩素酸ナ
トリウムの比（ＮａＣｌＯ2 ／ＮａＯＨ）が重量比で
２．０〜３．２の範囲に制限される。水酸化ナトリウム
に対する亜塩素酸ナトリウムの重量比（ＮａＣｌＯ2 ／
ＮａＯＨ）が２．０未満であると、この内層用配線板を
用いた多層プリント配線板にハロー現象が起きやすく、
重量比（ＮａＣｌＯ2 ／ＮａＯＨ）が３．２を越えると
銅回路の密着力が低下する。また、上記亜塩素酸ナトリ
ウム水溶液にリン酸・１２水和物（Ｈ3 ＰＯ4 ・１２Ｈ
2 Ｏ）が５〜２５ｇ／リットルの濃度の範囲で含まれる
と、緩衝液として作用するので好ましい。In the present invention, this inner layer wiring board is immersed in an aqueous sodium chlorite solution to form a copper oxide film on the copper circuit. According to this method, a copper oxide film containing fine cupric oxide as a main component and having fine projections is formed on the surface of a copper circuit to enhance the adhesiveness with a prepreg. In the present invention,
An aqueous solution containing sodium chlorite (NaClO 2 ) in a concentration range of 92 to 112 g / liter and sodium hydroxide (NaOH) in a concentration range of 35 to 45 g / liter as components of the sodium chlorite aqueous solution. Is. Furthermore, the ratio of sodium chlorite to sodium hydroxide (NaClO 2 / NaOH) is limited to a weight ratio range of 2.0 to 3.2. Weight ratio of sodium chlorite to sodium hydroxide (NaClO 2 /
If the (NaOH) is less than 2.0, a halo phenomenon easily occurs in a multilayer printed wiring board using this inner layer wiring board,
If the weight ratio (NaClO 2 / NaOH) exceeds 3.2, the adhesion of the copper circuit will be reduced. In addition, phosphoric acid dodecahydrate (H 3 PO 4 12H
2 O) is preferably contained in a concentration range of 5 to 25 g / liter because it acts as a buffer solution.
【００１０】本発明は上記亜塩素酸ナトリウム水溶液に
内層用配線板を浸漬し、銅回路に銅酸化膜を８０〜１６
０ｍｇ／ｄｍ2 の範囲で形成する。この銅酸化膜は酸化
第二銅を主成分とするものである。上記銅酸化膜が８０
ｍｇ／ｄｍ2 未満であると、次の工程の弱酸性水溶液に
浸漬した後に、所望の膜厚が確保されにくく、銅酸化膜
が１６０ｍｇ／ｄｍ2 を越えると、ハロー現象が起きや
すい。In the present invention, the inner layer wiring board is dipped in the above-mentioned sodium chlorite aqueous solution, and a copper oxide film is formed on the copper circuit at 80-16
It is formed in the range of 0 mg / dm 2 . This copper oxide film contains cupric oxide as a main component. The copper oxide film is 80
If it is less than mg / dm 2, it is difficult to secure a desired film thickness after immersion in the weakly acidic aqueous solution in the next step, and if the copper oxide film exceeds 160 mg / dm 2 , the halo phenomenon is likely to occur.
【００１１】上記亜塩素酸ナトリウム水溶液で数多く内
層用配線板を浸漬処理を行うと、塩化ナトリウム（Ｎａ
Ｃｌ）、酸化第二銅（ＣｕＯ）、炭酸ナトリウム（Ｎａ
2 ＣＯ3 ）が不純物として蓄積され、この不純物が多く
なると銅回路に８０ｍｇ／ｄｍ2 以上の銅酸化膜を確保
しにくくなる。８０ｍｇ／ｄｍ2 以上の銅酸化膜を確保
するため、亜塩素酸ナトリウム水溶液内の塩化ナトリウ
ムの濃度は４０ｇ／リットル以下、酸化第二銅の濃度は
６ｇ／リットル以下、炭酸ナトリウムの濃度は４０ｇ／
リットル以下に保持することが望ましい。When many inner layer wiring boards are immersed in the above-mentioned sodium chlorite aqueous solution, sodium chloride (Na
Cl), cupric oxide (CuO), sodium carbonate (Na
2 CO 3 ) is accumulated as an impurity, and if the amount of this impurity increases, it becomes difficult to secure a copper oxide film of 80 mg / dm 2 or more in the copper circuit. In order to secure a copper oxide film of 80 mg / dm 2 or more, the concentration of sodium chloride in the aqueous solution of sodium chlorite is 40 g / liter or less, the concentration of cupric oxide is 6 g / liter or less, and the concentration of sodium carbonate is 40 g / liter.
It is desirable to keep it below liter.
【００１２】なお、上記内層用配線板を亜塩素酸ナトリ
ウム水溶液に浸漬する前にソフトエッチングを施こすこ
とが好ましく、このソフトエッチングを施して銅回路を
１〜４．５μｍ程エッチングをし、上記銅回路の表面粗
度を２．０〜４．０μｍとすると、銅酸化膜の密着がよ
くなり好ましい。[0012] It is preferable that the inner layer wiring board is soft-etched before being dipped in an aqueous solution of sodium chlorite, and the copper circuit is etched by about 1 to 4.5 µm by performing the soft etching. When the surface roughness of the copper circuit is 2.0 to 4.0 μm, the adhesion of the copper oxide film is improved, which is preferable.
【００１３】本発明は、銅回路に銅酸化膜を８０〜１６
０ｍｇ／ｄｍ2 形成した後に、弱酸性水溶液に浸漬す
る。この弱酸性水溶液に浸漬すると、銅酸化膜中の酸化
第二銅が除去され、酸化第一銅が残る。上記弱酸性水溶
液としては、例えば、希硫酸を含有し、さらにキレー
ト、ほう酸、ぎ酸、カルボン酸等の有機酸を含むＰＨ
３．３〜４．１の水溶液が挙げられる。このキレート、
ほう酸、ぎ酸、カルボン酸を含んでいると、除去した第
二銅の銅イオンが銅回路に再付着するのを防ぐ効果があ
る。The present invention provides a copper circuit with a copper oxide film in the range of 80 to 16
After forming 0 mg / dm 2 , it is immersed in a weakly acidic aqueous solution. When immersed in this weakly acidic aqueous solution, cupric oxide in the copper oxide film is removed and cuprous oxide remains. As the weakly acidic aqueous solution, for example, PH containing dilute sulfuric acid and further containing an organic acid such as chelate, boric acid, formic acid, and carboxylic acid.
An aqueous solution of 3.3 to 4.1 can be mentioned. This chelate,
When boric acid, formic acid and carboxylic acid are contained, it is effective to prevent the copper ions of the removed cupric acid from reattaching to the copper circuit.
【００１４】本発明においては、上記弱酸性水溶液に浸
漬して、内層用配線板の金属銅からなる銅回路の膜厚を
３．２〜３３．６ｍｇ／ｄｍ2 の範囲に形成し、且つ、
上記亜塩素酸ナトリウム水溶液浸漬後の銅酸化膜に対
し、上記弱酸性水溶液浸漬後の上記膜厚が重量比で０．
０４〜０．２１の範囲とする。上記重量比で０．２１を
越えるとハロー現象が起きやすく、重量比で０．０４未
満であると内層用配線板の金属銅からなる銅回路の密着
力が低下する。In the present invention, the inner circuit wiring board is immersed in the weakly acidic aqueous solution to form a copper circuit having a thickness of 3.2 to 33.6 mg / dm 2 on the copper circuit made of metallic copper, and
The above-mentioned film thickness after immersion in the weakly acidic aqueous solution was 0.
The range is from 04 to 0.21. If the weight ratio exceeds 0.21, the halo phenomenon is likely to occur, and if the weight ratio is less than 0.04, the adhesion of the copper circuit made of metallic copper of the inner layer wiring board deteriorates.
【００１５】なお、上記弱酸性水溶液は数多く処理を施
すとＣｕ2+、ＳＯ4 2- が蓄積され、多層プリント配線板
の半田耐熱性が劣りふくれやミーズリングが生じやすく
なる。従って、Ｃｕ2+は１３ｇ／リットル以下、ＳＯ4
2- は７０ｇ／リットル以下に保持することが好まし
い。When the weakly acidic aqueous solution is subjected to a large number of treatments, Cu 2+ and SO 4 2− are accumulated, the solder heat resistance of the multilayer printed wiring board is poor, and blistering and measling are likely to occur. Therefore, Cu 2+ is 13 g / liter or less, SO 4
2- is preferably maintained at 70 g / liter or less.
【００１６】また、上記弱酸性水溶液に浸漬した後の銅
回路に形成させた膜厚を外観の色調で判定する方法も検
討されている。例えば、日本電色工業株式会社製の色差
計（ＳＺ−Σ８０）を用いる場合、銅回路の外観を明度
指数（Ｌ）を１６．４〜２５．２とすることが好まし
い。Further, a method of judging the film thickness formed on the copper circuit after the immersion in the weakly acidic aqueous solution by the color tone of the appearance is also being studied. For example, when using a color difference meter (SZ-Σ80) manufactured by Nippon Denshoku Industries Co., Ltd., it is preferable that the appearance of the copper circuit has a lightness index (L) of 16.4 to 25.2.
【００１７】なお、上記弱酸性水溶液に浸漬した後の水
洗は、多段式が望ましく、ＰＨの変化による衝撃を緩和
するために、最初の水洗はＰＨ４．２〜６．５の範囲で
水洗することが好ましい。The washing with water after the immersion in the weakly acidic aqueous solution is preferably a multi-stage washing, and in order to reduce the impact due to the change of PH, the first washing should be performed with washing within the range of PH 4.2 to 6.5. Is preferred.
【００１８】上記処理を施した内層用配線板は、通常の
工程で多層プリント配線板に用いられる。The inner layer wiring board subjected to the above-mentioned treatment is used for a multilayer printed wiring board in a usual process.
【００１９】[0019]
実施例１ 内層用配線板として、３５μｍ厚さの銅箔を両面に配設
した厚み０．８ｍｍ、サイズ５００×５００ｍｍ角のガ
ラス布基材エポキシ樹脂積層板を用い、この積層板に銅
回路を両表面に作製した。その後、銅回路にソフトエッ
チングを施し、銅回路の表面粗度を３．０μｍとした内
層用配線板を亜塩素酸ナトリウム水溶液に浸漬した。亜
塩素酸ナトリウム水溶液は、亜塩素酸ナトリウム（Ｎａ
ＣｌＯ2）の濃度が１００ｇ／リットル、水酸化ナトリ
ウム（ＮａＯＨ）の濃度が４２ｇ／リットル、リン酸・
１２水和物（Ｈ3 ＰＯ4 ・１２Ｈ2 Ｏ）の濃度が１５ｇ
／リットル、水酸化ナトリウム（ＮａＯＨ）に対する亜
塩素酸ナトリウム（ＮａＣｌＯ2 ）の重量比（ＮａＣｌ
Ｏ2 ／ＮａＯＨ）が２．４であった。なお、不純物とし
て亜塩素酸ナトリウム水溶液中に残留していた塩化ナト
リウム（ＮａＣｌ）の濃度は２０ｇ／リットル、酸化第
二銅（ＣｕＯ）の濃度は２ｇ／リットル、炭酸ナトリウ
ム（Ｎａ2 ＣＯ3 ）の濃度は２０ｇ／リットルであっ
た。亜塩素酸ナトリウム水溶液に浸漬して、銅回路に１
００ｍｇ／ｄｍ2 の銅酸化膜を形成した。Example 1 As a wiring board for the inner layer, a glass cloth base material epoxy resin laminated board having a thickness of 0.8 mm and a size of 500 × 500 mm in which a copper foil having a thickness of 35 μm is arranged on both sides was used, and a copper circuit was formed on the laminated board. It was prepared on both surfaces. Then, the copper circuit was soft-etched, and the inner layer wiring board having a surface roughness of the copper circuit of 3.0 μm was dipped in a sodium chlorite aqueous solution. The sodium chlorite aqueous solution is sodium chlorite (Na
ClO 2 ) concentration is 100 g / liter, sodium hydroxide (NaOH) concentration is 42 g / liter, phosphoric acid.
The concentration of dodecahydrate (H 3 PO 4 · 12H 2 O) is 15g
/ Liter, the weight ratio of sodium chlorite (NaClO 2 ) to sodium hydroxide (NaOH) (NaCl
O 2 / NaOH) it was 2.4. As impurities, the concentration of sodium chloride (NaCl) remaining in the aqueous solution of sodium chlorite was 20 g / liter, the concentration of cupric oxide (CuO) was 2 g / liter, and sodium carbonate (Na 2 CO 3 ) The concentration was 20 g / liter. Immerse it in an aqueous solution of sodium chlorite and apply 1 to the copper circuit.
A copper oxide film of 00 mg / dm 2 was formed.
【００２０】次に、希硫酸、キレート、ほう酸、ぎ酸、
カルボン酸を成分とするＰＨ３．７の弱酸性水溶液に浸
漬した。弱酸性水溶液に浸漬して金属銅からなる銅回路
に１０ｍｇ／ｄｍ2 の膜厚を形成した。上記亜塩素酸ナ
トリウム水溶液に浸漬後の銅酸化膜に対し、上記弱酸性
水溶液に浸漬後の膜厚は重量比で０．１０となった。こ
の際の弱酸性水溶液内のＣｕ2+は５ｇ／リットル、ＳＯ
4 2- は２７ｇ／リットルであった。その後、水洗し乾燥
した。Next, dilute sulfuric acid, chelate, boric acid, formic acid,
It was immersed in a weakly acidic aqueous solution of PH 3.7 containing a carboxylic acid as a component. A copper circuit made of metallic copper was immersed in a weakly acidic aqueous solution to form a film thickness of 10 mg / dm 2 . The weight ratio of the copper oxide film dipped in the sodium chlorite aqueous solution to the copper oxide film dipped in the weak acidic aqueous solution was 0.10. At this time, Cu 2+ in the weakly acidic aqueous solution was 5 g / liter, SO
4 2- was 27g / liter. Then, it was washed with water and dried.
【００２１】得た内層用配線板のハロー現象、及び銅回
路の密着力の評価を行った。ハロー現象は次の様にして
測定した。ガラス布基材エポキシ樹脂プリプレグを上記
内層用配線板の上下に２枚重ね、さらに３５μｍ厚さの
銅箔を重ね、加熱加圧して多層の銅張り積層板を作製し
た。次に直径０．４のスルホールをドリルで明けた。こ
のスルホールを明けた積層板を１．２Ｎの２０℃の塩酸
中に１０分間浸漬した後に、水洗いする。その後、外側
の銅箔、及びプリプレグが硬化した接着層を剥がし、内
層用配線板の銅回路を露出させ、ハロー現象がスルホー
ルの外周からどのくらい長く発生しているかを顕微鏡で
観察した。一番長くハロー現象の起きている所を測定し
た。The halo phenomenon of the obtained inner layer wiring board and the adhesion of the copper circuit were evaluated. The halo phenomenon was measured as follows. Two glass cloth base epoxy resin prepregs were stacked on the upper and lower sides of the inner layer wiring board, copper foil having a thickness of 35 μm was further stacked, and heated and pressed to produce a multilayer copper-clad laminate. Next, a through hole having a diameter of 0.4 was drilled. The laminated plate having the through holes is immersed in 1.2N hydrochloric acid at 20 ° C. for 10 minutes and then washed with water. Then, the outer copper foil and the adhesive layer where the prepreg was cured were peeled off to expose the copper circuit of the inner layer wiring board, and how long the halo phenomenon occurred from the outer periphery of the through hole was observed with a microscope. The longest halo phenomenon was measured.
【００２２】銅回路の密着力は上記プリプレグが硬化し
た接着層を剥がして露出させた内層用配線板の銅回路の
剥離強度をＪＩＳに基づいて測定した。The adhesive strength of the copper circuit was measured by peeling the adhesive layer on which the prepreg was hardened and peeling off the exposed copper circuit of the wiring board for the inner layer based on JIS.
【００２３】結果は、ハロー現象の発生はなく、銅回路
の剥離強度は１．０５ｋｇ／ｃｍ2で良好とあった。As a result, the halo phenomenon did not occur, and the peel strength of the copper circuit was 1.05 kg / cm 2 , which was good.
【００２４】実施例２ 実施例１の亜塩素酸ナトリウム水溶液において、亜塩素
酸ナトリウム（ＮａＣｌＯ2 ）の濃度が１１０ｇ／リッ
トル、水酸化ナトリウム（ＮａＯＨ）の濃度が３５ｇ／
リットル、リン酸・１２水和物（Ｈ3 ＰＯ4 ・１２Ｈ2
Ｏ）の濃度が１５ｇ／リットル、水酸化ナトリウムに対
する亜塩素酸ナトリウムの重量比（ＮａＣｌＯ2 ／Ｎａ
ＯＨ）が３．１とした以外は実施例１と同様にして、内
層用配線板を亜塩素酸ナトリウム水溶液及び弱酸性水溶
液に浸漬した。亜塩素酸ナトリウム水溶液浸漬後は、銅
回路に１００ｍｇ／ｄｍ2 の銅酸化膜を形成し、弱酸性
水溶液に浸漬後は、金属銅からなる銅回路に１０ｍｇ／
ｄｍ2 の膜厚を形成した。Example 2 In the aqueous sodium chlorite solution of Example 1, the concentration of sodium chlorite (NaClO 2 ) was 110 g / liter and the concentration of sodium hydroxide (NaOH) was 35 g / l.
L, phosphoric acid dodecahydrate (H 3 PO 4 12H 2
O) concentration is 15 g / liter, and the weight ratio of sodium chlorite to sodium hydroxide (NaClO 2 / Na
The inner layer wiring board was immersed in an aqueous sodium chlorite solution and a weakly acidic aqueous solution in the same manner as in Example 1 except that the OH) was 3.1. After immersion in the sodium chlorite aqueous solution, a copper oxide film of 100 mg / dm 2 is formed on the copper circuit, and after immersion in the weakly acidic aqueous solution, 10 mg / dm 2 is applied to the copper circuit made of metallic copper.
A film thickness of dm 2 was formed.
【００２５】得た内層用配線板のハロー現象、及び銅回
路の密着力の評価を実施例１と同様に行った。結果は、
表１のとおり、ハロー現象の発生はなく、銅回路の剥離
強度は１．０２ｋｇ／ｃｍ2 と良好であった。The halo phenomenon of the obtained inner layer wiring board and the adhesion of the copper circuit were evaluated in the same manner as in Example 1. Result is,
As shown in Table 1, the halo phenomenon did not occur, and the peel strength of the copper circuit was as good as 1.02 kg / cm 2 .
【００２６】実施例３ 実施例１の亜塩素酸ナトリウム水溶液において、亜塩素
酸ナトリウム（ＮａＣｌＯ2 ）の濃度が９３ｇ／リット
ル、水酸化ナトリウム（ＮａＯＨ）の濃度が４４ｇ／リ
ットル、リン酸・１２水和物（Ｈ3 ＰＯ4 ・１２Ｈ
2 Ｏ）の濃度が１５ｇ／リットル、水酸化ナトリウムに
対する亜塩素酸ナトリウムの重量比（ＮａＣｌＯ2 ／Ｎ
ａＯＨ）が２．１とした以外は実施例１と同様にして、
内層用配線板を亜塩素酸ナトリウム水溶液及び弱酸性水
溶液に浸漬した。亜塩素酸ナトリウム水溶液浸漬後は、
銅回路に１００ｍｇ／ｄｍ2 の銅酸化膜を形成し、弱酸
性水溶液に浸漬後は、金属銅からなる銅回路に１０ｍｇ
／ｄｍ2 の膜厚を形成した。Example 3 In the aqueous sodium chlorite solution of Example 1, the concentration of sodium chlorite (NaClO 2 ) was 93 g / liter, the concentration of sodium hydroxide (NaOH) was 44 g / liter, and phosphoric acid / 12 water. Japanese products (H 3 PO 4・ 12H
2 O) concentration is 15 g / liter, and the weight ratio of sodium chlorite to sodium hydroxide (NaClO 2 / N
aOH) was 2.1 but in the same manner as in Example 1,
The inner layer wiring board was immersed in an aqueous sodium chlorite solution and a weakly acidic aqueous solution. After immersion in an aqueous solution of sodium chlorite,
After forming a 100 mg / dm 2 copper oxide film on the copper circuit and immersing it in a weakly acidic aqueous solution, 10 mg on the copper circuit made of metallic copper.
A film thickness of / dm 2 was formed.
【００２７】得た内層用配線板のハロー現象、及び銅回
路の密着力の評価を実施例１と同様に行った。結果は、
表１のとおり、ハロー現象の発生はなく、銅回路の剥離
強度は１．０９ｋｇ／ｃｍ2 と良好であった。The halo phenomenon of the obtained inner layer wiring board and the adhesion of the copper circuit were evaluated in the same manner as in Example 1. Result is,
As shown in Table 1, the halo phenomenon did not occur, and the peel strength of the copper circuit was as good as 1.09 kg / cm 2 .
【００２８】比較例１ 実施例１の亜塩素酸ナトリウム水溶液において、亜塩素
酸ナトリウム（ＮａＣｌＯ2 ）の濃度が１１０ｇ／リッ
トル、水酸化ナトリウム（ＮａＯＨ）の濃度が３３ｇ／
リットル、リン酸・１２水和物（Ｈ3 ＰＯ4 ・１２Ｈ2
Ｏ）の濃度が１５ｇ／リットル、水酸化ナトリウムに対
する亜塩素酸ナトリウムの重量比（ＮａＣｌＯ2 ／Ｎａ
ＯＨ）が３．３とした以外は実施例１と同様にして、内
層用配線板を亜塩素酸ナトリウム水溶液及び弱酸性水溶
液に浸漬した。亜塩素酸ナトリウム水溶液浸漬後は、銅
回路に１００ｍｇ／ｄｍ2 の銅酸化膜を形成し、弱酸性
水溶液に浸漬後は、金属銅からなる銅回路に１０ｍｇ／
ｄｍ2 の膜厚を形成した。Comparative Example 1 In the aqueous sodium chlorite solution of Example 1, the concentration of sodium chlorite (NaClO 2 ) was 110 g / liter and the concentration of sodium hydroxide (NaOH) was 33 g / l.
L, phosphoric acid dodecahydrate (H 3 PO 4 12H 2
O) concentration is 15 g / liter, and the weight ratio of sodium chlorite to sodium hydroxide (NaClO 2 / Na
The inner layer wiring board was immersed in an aqueous sodium chlorite solution and a weakly acidic aqueous solution in the same manner as in Example 1 except that the OH) was 3.3. After immersion in the sodium chlorite aqueous solution, a copper oxide film of 100 mg / dm 2 is formed on the copper circuit, and after immersion in the weakly acidic aqueous solution, 10 mg / dm 2 is applied to the copper circuit made of metallic copper.
A film thickness of dm 2 was formed.
【００２９】得た内層用配線板のハロー現象、及び銅回
路の密着力の評価を実施例１と同様に行った。結果は、
表１のとおり、ハロー現象の発生はなかったが、銅回路
の剥離強度は０．４０ｋｇ／ｃｍ2 と低下していた。The halo phenomenon of the obtained inner layer wiring board and the adhesion of the copper circuit were evaluated in the same manner as in Example 1. Result is,
As shown in Table 1, the halo phenomenon did not occur, but the peel strength of the copper circuit was lowered to 0.40 kg / cm 2 .
【００３０】比較例２ 実施例１の亜塩素酸ナトリウム水溶液において、亜塩素
酸ナトリウム（ＮａＣｌＯ2 ）の濃度が８７ｇ／リット
ル、水酸化ナトリウム（ＮａＯＨ）の濃度が４５ｇ／リ
ットル、リン酸・１２水和物（Ｈ3 ＰＯ4 ・１２Ｈ
2 Ｏ）の濃度が１５ｇ／リットル、水酸化ナトリウムに
対する亜塩素酸ナトリウムの重量比（ＮａＣｌＯ2 ／Ｎ
ａＯＨ）が１．９とした以外は実施例１と同様にして、
内層用配線板を亜塩素酸ナトリウム水溶液及び弱酸性水
溶液に浸漬した。亜塩素酸ナトリウム水溶液浸漬後は、
銅回路に１００ｍｇ／ｄｍ2 の銅酸化膜を形成し、弱酸
性水溶液に浸漬後は、金属銅からなる銅回路に１０ｍｇ
／ｄｍ2 の膜厚を形成した。Comparative Example 2 In the sodium chlorite aqueous solution of Example 1, the concentration of sodium chlorite (NaClO 2 ) was 87 g / liter, the concentration of sodium hydroxide (NaOH) was 45 g / liter, and phosphoric acid / 12 water. Japanese products (H 3 PO 4・ 12H
2 O) concentration is 15 g / liter, and the weight ratio of sodium chlorite to sodium hydroxide (NaClO 2 / N
aOH) in the same manner as in Example 1 except that it was 1.9,
The inner layer wiring board was immersed in an aqueous sodium chlorite solution and a weakly acidic aqueous solution. After immersion in an aqueous solution of sodium chlorite,
After forming a 100 mg / dm 2 copper oxide film on the copper circuit and immersing it in a weakly acidic aqueous solution, 10 mg on the copper circuit made of metallic copper.
A film thickness of / dm 2 was formed.
【００３１】得た内層用配線板のハロー現象、及び銅回
路の密着力の評価を実施例１と同様に行った。結果は、
表１のとおり、ハロー現象が２３５μｍ発生し、銅回路
の剥離強度は０．５３ｋｇ／ｃｍ2 と低下していた。The halo phenomenon of the obtained wiring board for inner layer and the adhesion of the copper circuit were evaluated in the same manner as in Example 1. Result is,
As shown in Table 1, the halo phenomenon occurred at 235 μm, and the peel strength of the copper circuit was lowered to 0.53 kg / cm 2 .
【００３２】[0032]
【表１】 [Table 1]
【００３３】実施例４ 実施例１と同様にして亜塩素酸ナトリウム水溶液に浸漬
し、銅回路に１４８ｍｇ／ｄｍ2 の銅酸化膜を形成し
た。Example 4 As in Example 1, it was immersed in an aqueous sodium chlorite solution to form a 148 mg / dm 2 copper oxide film on the copper circuit.
【００３４】次に、実施例１と同様の弱酸性水溶液に浸
漬し、銅回路に１３ｍｇ／ｄｍ2 の膜厚を形成した。Next, the film was immersed in the same weakly acidic aqueous solution as in Example 1 to form a film thickness of 13 mg / dm 2 on the copper circuit.
【００３５】得た内層用配線板のハロー現象、及び銅回
路の密着力の評価を実施例１と同様に行った。結果は、
表２のとおり、ハロー現象の発生はなく、銅回路の剥離
強度は１．０３ｋｇ／ｃｍ2 と良好であった。The halo phenomenon of the obtained inner layer wiring board and the adhesion of the copper circuit were evaluated in the same manner as in Example 1. Result is,
As shown in Table 2, the halo phenomenon did not occur, and the peel strength of the copper circuit was as good as 1.03 kg / cm 2 .
【００３６】実施例５ 実施例１と同様にして亜塩素酸ナトリウム水溶液に浸漬
し、銅回路に１００ｍｇ／ｄｍ2 の銅酸化膜を形成し
た。Example 5 A copper oxide film of 100 mg / dm 2 was formed on a copper circuit by immersing it in an aqueous solution of sodium chlorite in the same manner as in Example 1.
【００３７】次に、実施例１と同様の弱酸性水溶液に浸
漬し、銅回路に２０ｍｇ／ｄｍ2 の膜厚を形成した。Next, the film was immersed in the same weakly acidic aqueous solution as in Example 1 to form a film thickness of 20 mg / dm 2 on the copper circuit.
【００３８】得た内層用配線板のハロー現象、及び銅回
路の密着力の評価を実施例１と同様に行った。結果は、
表２のとおり、ハロー現象の発生はなく、銅回路の剥離
強度は１．０８ｋｇ／ｃｍ2 と良好であった。The halo phenomenon of the obtained inner layer wiring board and the adhesion of the copper circuit were evaluated in the same manner as in Example 1. Result is,
As shown in Table 2, the halo phenomenon did not occur and the peel strength of the copper circuit was good at 1.08 kg / cm 2 .
【００３９】比較例３ 実施例１と同様にして亜塩素酸ナトリウム水溶液に浸漬
し、銅回路に１００ｍｇ／ｄｍ2 の銅酸化膜を形成し
た。Comparative Example 3 In the same manner as in Example 1, the copper circuit was dipped in an aqueous solution of sodium chlorite to form a 100 mg / dm 2 copper oxide film on the copper circuit.
【００４０】次に、実施例１と同様の弱酸性水溶液に浸
漬し、銅回路に２ｍｇ／ｄｍ2 の膜厚を形成した。Next, it was dipped in the same weakly acidic aqueous solution as in Example 1 to form a film thickness of 2 mg / dm 2 on the copper circuit.
【００４１】得た内層用配線板のハロー現象、及び銅回
路の密着力の評価を実施例１と同様に行った。結果は、
表２のとおり、ハロー現象の発生はなかったが、銅回路
の剥離強度は０．５４ｋｇ／ｃｍ2 と低下していた。The halo phenomenon of the obtained inner layer wiring board and the adhesion of the copper circuit were evaluated in the same manner as in Example 1. Result is,
As shown in Table 2, the halo phenomenon did not occur, but the peel strength of the copper circuit was lowered to 0.54 kg / cm 2 .
【００４２】比較例４ 実施例１と同様にして亜塩素酸ナトリウム水溶液に浸漬
し、銅回路に７０ｍｇ／ｄｍ2 の銅酸化膜を形成した。Comparative Example 4 A copper oxide film of 70 mg / dm 2 was formed on a copper circuit by immersing in a sodium chlorite aqueous solution in the same manner as in Example 1.
【００４３】次に、実施例１と同様の弱酸性水溶液に浸
漬し、銅回路に２ｍｇ／ｄｍ2 の膜厚を形成した。Next, it was dipped in the same weakly acidic aqueous solution as in Example 1 to form a film thickness of 2 mg / dm 2 on the copper circuit.
【００４４】得た内層用配線板のハロー現象、及び銅回
路の密着力の評価を実施例１と同様に行った。結果は、
表２のとおり、ハロー現象の発生はなかったが、銅回路
の剥離強度は０．５６ｋｇ／ｃｍ2 と低下していた。The halo phenomenon of the obtained inner layer wiring board and the adhesion of the copper circuit were evaluated in the same manner as in Example 1. Result is,
As shown in Table 2, the halo phenomenon did not occur, but the peel strength of the copper circuit was lowered to 0.56 kg / cm 2 .
【００４５】比較例５ 実施例１と同様にして亜塩素酸ナトリウム水溶液に浸漬
し、銅回路に１８０ｍｇ／ｄｍ2 の銅酸化膜を形成し
た。Comparative Example 5 In the same manner as in Example 1, it was immersed in an aqueous sodium chlorite solution to form a copper oxide film of 180 mg / dm 2 on the copper circuit.
【００４６】次に、実施例１と同様の弱酸性水溶液に浸
漬し、銅回路に３９ｍｇ／ｄｍ2 の膜厚を形成した。Next, the film was immersed in the same weakly acidic aqueous solution as in Example 1 to form a film thickness of 39 mg / dm 2 on the copper circuit.
【００４７】得た内層用配線板のハロー現象、及び銅回
路の密着力の評価を実施例１と同様に行った。結果は、
表２のとおり、ハロー現象が２０２μｍ発生し、銅回路
の剥離強度は０．５２ｋｇ／ｃｍ2 と低下していた。The halo phenomenon of the obtained inner layer wiring board and the adhesion of the copper circuit were evaluated in the same manner as in Example 1. Result is,
As shown in Table 2, the halo phenomenon occurred at 202 μm and the peel strength of the copper circuit was lowered to 0.52 kg / cm 2 .
【００４８】[0048]
【表２】 [Table 2]
【００４９】[0049]
【発明の効果】本発明の請求項１又は請求項２の内層用
配線板の銅回路の処理方法を用いるとハロー現象が起き
ず、内層用配線板の銅回路の密着性の良好な多層プリン
ト配線板を得ることができる。EFFECTS OF THE INVENTION When the method for treating a copper circuit of an inner layer wiring board according to claim 1 or 2 of the present invention is used, a halo phenomenon does not occur, and a multilayer print having good adhesion of the copper circuit of the inner layer wiring board. A wiring board can be obtained.
Claims (2)
液に浸漬して、内層用配線板の銅回路に銅酸化膜を形成
し、その後弱酸性水溶液に浸漬する内層用配線板の銅回
路の処理方法であって、 亜塩素酸ナトリウムの濃度が９２〜１１２ｇ／リット
ル、水酸化ナトリウムの濃度が３５〜４５ｇ／リット
ル、水酸化ナトリウムに対する亜塩素酸ナトリウムの重
量比が２．０〜３．２の配合からなる亜塩素酸ナトリウ
ム水溶液に内層用配線板を浸漬し、 上記内層用配線板の金属銅からなる銅回路に銅酸化膜
を８０〜１６０ｍｇ／ｄｍ2 形成した後に、 弱酸性水溶液に浸漬して、内層用配線板の金属銅から
なる銅回路の膜厚を３．２〜３３．６ｍｇ／ｄｍ2 と
し、且つ、上記亜塩素酸ナトリウム水溶液浸漬後の銅酸
化膜に対し、上記弱酸性水溶液浸漬後の上記膜厚が重量
比で０．０４〜０．２１の範囲とすることを特徴とする
内層用配線板の銅回路の処理方法。1. A copper circuit for an inner layer wiring board is formed by immersing the inner layer wiring board in an aqueous sodium chlorite solution to form a copper oxide film on the copper circuit of the inner layer wiring board, and then immersing it in a weakly acidic aqueous solution. A treatment method, wherein the concentration of sodium chlorite is 92 to 112 g / liter, the concentration of sodium hydroxide is 35 to 45 g / liter, and the weight ratio of sodium chlorite to sodium hydroxide is 2.0 to 3.2. After immersing the inner layer wiring board in the sodium chlorite aqueous solution consisting of the above composition, forming a copper oxide film of 80 to 160 mg / dm 2 on the copper circuit made of metallic copper of the inner layer wiring board, and immersing it in the weakly acidic aqueous solution. Then, the film thickness of the copper circuit made of metallic copper of the wiring board for the inner layer is set to 3.2 to 33.6 mg / dm 2 , and the weak acidity against the copper oxide film after immersion in the aqueous sodium chlorite solution is set. After immersion in aqueous solution 2. The method for treating a copper circuit of a wiring board for an inner layer, wherein the above-mentioned film thickness is in the range of 0.04 to 0.21 in weight ratio.
配線板を浸漬した際に亜塩素酸ナトリウム水溶液中に蓄
積される塩化ナトリウムの濃度を４０ｇ／リットル以
下、酸化第二銅の濃度を６ｇ／リットル以下、炭酸ナト
リウムの濃度を４０ｇ／リットル以下に保持することを
特徴とする請求項１記載の内層用配線板の銅回路の処理
方法。2. The concentration of sodium chloride accumulated in the aqueous solution of sodium chlorite when the wiring board for the inner layer is immersed in the aqueous solution of sodium chlorite is 40 g / liter or less, and the concentration of cupric oxide is 6 g / liter. The method for treating a copper circuit of a wiring board for an inner layer according to claim 1, characterized in that the concentration of sodium carbonate is kept at liter or less and the sodium carbonate concentration is kept at 40 g / liter or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2564794A JP3367189B2 (en) | 1994-02-23 | 1994-02-23 | Processing method of copper circuit of wiring board for inner layer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2564794A JP3367189B2 (en) | 1994-02-23 | 1994-02-23 | Processing method of copper circuit of wiring board for inner layer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07235766A true JPH07235766A (en) | 1995-09-05 |
| JP3367189B2 JP3367189B2 (en) | 2003-01-14 |
Family
ID=12171627
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2564794A Expired - Fee Related JP3367189B2 (en) | 1994-02-23 | 1994-02-23 | Processing method of copper circuit of wiring board for inner layer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3367189B2 (en) |
-
1994
- 1994-02-23 JP JP2564794A patent/JP3367189B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP3367189B2 (en) | 2003-01-14 |
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