JPH0870178A - Treatment of copper circuit of internal layer use wiring board - Google Patents
Treatment of copper circuit of internal layer use wiring boardInfo
- Publication number
- JPH0870178A JPH0870178A JP20353394A JP20353394A JPH0870178A JP H0870178 A JPH0870178 A JP H0870178A JP 20353394 A JP20353394 A JP 20353394A JP 20353394 A JP20353394 A JP 20353394A JP H0870178 A JPH0870178 A JP H0870178A
- Authority
- JP
- Japan
- Prior art keywords
- wiring board
- copper circuit
- copper
- inner layer
- chelate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は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
の確保とハローイング現象を防止する必要性から、上記
銅回路に酸化処理を施し、銅酸化膜を形成した後に、希
硫酸、エチレンジアミン四酢酸等のキレート、及び脂肪
族のアルコールを含む酸性溶液に浸漬し、銅酸化膜中の
酸化第二銅の皮膜を除去する処理が知られている。しか
し、この処理を施した銅回路は処理毎に、スジ状や斑点
状の色むらが発生する問題がある。In this multilayer printed wiring board, the copper circuit formed on the wiring board for the inner layer is required to have adhesiveness and to prevent the halo phenomenon from occurring, so that the copper circuit is oxidized. After forming the copper oxide film, dipping sulfuric acid, a chelate such as ethylenediaminetetraacetic acid, and dipping in an acidic solution containing an aliphatic alcohol, the treatment of removing the cupric oxide film in the copper oxide film is known. ing. However, the copper circuit subjected to this treatment has a problem that streaky or spot-like color unevenness occurs in each treatment.
【０００４】[0004]
【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、内層用
配線板の銅回路に酸化処理を施し、銅酸化膜を形成した
後に、希硫酸、及び、キレートを含有する酸性溶液に浸
漬する内層用配線板の銅回路の処理方法であって、外観
が良好な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。SUMMARY OF THE INVENTION The present invention has been made in view of the above facts, and an object of the present invention is to oxidize a copper circuit of an inner layer wiring board to form a copper oxide film. It is an object of the present invention to provide a method for treating a copper circuit of an inner layer wiring board which is immersed in an acidic solution containing dilute sulfuric acid and a chelate and which has a good appearance.
【０００５】[0005]
【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、内層用配線板の銅
回路に酸化処理を施し、銅酸化膜を形成した後に、希硫
酸、及び、キレートを含有する酸性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、上記酸性溶液中
の銅イオン濃度が０．８ｇ／リットル〜１２ｇ／リット
ルの範囲であることを特徴とする。According to a first aspect of the present invention, there is provided a method of treating a copper circuit of an inner layer wiring board, wherein the copper circuit of the inner layer wiring board is oxidized to form a copper oxide film. A method for treating a copper circuit of an inner wiring board, which is immersed in an acidic solution containing dilute sulfuric acid and a chelate, wherein the copper ion concentration in the acidic solution is in the range of 0.8 g / liter to 12 g / liter. It is characterized by
【０００６】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、上記酸性溶液のｐＨが３．０〜
４．０であり、且つ、この酸性溶液に浸漬した後に、ｐ
Ｈ４．５〜５．５の範囲のキレート含有液に浸漬洗浄す
ることを特徴とする。According to a second aspect of the present invention, there is provided a method for treating a copper circuit of an inner layer wiring board according to the first aspect of the present invention, wherein the acidic solution has a pH of 3.0 to 3.0.
4.0, and after soaking in this acidic solution, p
It is characterized in that it is immersed and washed in a chelate-containing liquid having a range of H4.5 to 5.5.
【０００７】本発明の請求項３に係る内層用配線板の銅
回路の処理方法は、請求項１又は請求項２記載の内層用
配線板の銅回路の処理方法において、上記内層用配線板
の銅回路に酸化処理を施す前処理として、この内層用配
線板の銅回路に塩化第二銅含有水溶液で第１のソフトエ
ッチングをした後に、硫酸と硫酸アンモニウムの水溶
液、及び、硫酸と過酸化水素の水溶液のどちらかの液で
第２のソフトエッチングで処理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 third aspect of the present invention is the method for treating a copper circuit of the inner layer wiring board according to claim 1 or 2, wherein: As a pretreatment for oxidizing the copper circuit, the copper circuit of the inner layer wiring board is first soft-etched with an aqueous solution containing cupric chloride, and then an aqueous solution of sulfuric acid and ammonium sulfate and an aqueous solution of sulfuric acid and hydrogen peroxide are added. The second soft etching is performed by using either one of the aqueous solutions.
【０００８】以下、本発明を詳細に説明する。本発明は
内層用配線板の銅回路に酸化処理を施し、銅酸化膜を形
成した後に、希硫酸、及び、キレートを含有する酸性溶
液に浸漬す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。The present invention will be described in detail below. The present invention relates to a method for treating a copper circuit of an inner layer wiring board, which comprises subjecting an inner layer wiring board to a copper circuit oxidation treatment to form a copper oxide film, and then dipping it in an acidic solution containing dilute sulfuric acid and a chelate. Is.
【０００９】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 inner layer wiring board used in the present invention has a copper circuit formed on the surface thereof. Examples of the inner layer wiring board, for example, epoxy resin laminated board of glass base material stretched copper foil,
Glass-polyimide resin laminates, unsaturated polyester resin laminates, fluororesin laminates, and modified resin laminates of these resins are used. When copper foil of the laminates is etched, a copper circuit is formed on one side or both sides. To be done.
【００１０】上記内層用配線板は、銅酸化膜の密着を良
くするために、酸化処理をする前処理としてソフトエッ
チングを行い、銅回路を粗化する。上記ソフトエッチン
グは、塩化第二銅含有水溶液等によるソフトエッチング
が挙げられるが、塩化第二銅含有水溶液で第１のソフト
エッチングをした後に、硫酸と硫酸アンモニウムの水溶
液、及び、硫酸と過酸化水素の水溶液のどちらかの水溶
液で第２のソフトエッチングで処理することが好まし
い。上記第１のソフトエッチング液の塩化第二銅含有水
溶液は銅回路を強力に表面粗化し、第２のソフトエッチ
ングは銅回路の表面粗化の度合いを均一にする働きをす
るため、銅回路に色むらが発生しにくい。上記ソフトエ
ッチング後は、酸洗いが行われる。酸洗いの酸の種類は
ソフトエッチングの成分により適宜決定され、塩化第二
銅含有水溶液を用いた場合は塩酸液、硫酸の水溶液を用
いた場合は硫酸で行われる。In order to improve the adhesion of the copper oxide film, the inner layer wiring board is subjected to soft etching as a pretreatment for the oxidation treatment to roughen the copper circuit. Examples of the soft etching include soft etching with an aqueous solution containing cupric chloride. After the first soft etching with an aqueous solution containing cupric chloride, an aqueous solution of sulfuric acid and ammonium sulfate, and an aqueous solution of sulfuric acid and hydrogen peroxide. It is preferred to treat with either of the aqueous solutions in the second soft etching. The cupric chloride-containing aqueous solution of the first soft etching solution strongly roughens the surface of the copper circuit, and the second soft etching functions to make the degree of surface roughening of the copper circuit uniform. Color unevenness is less likely to occur. After the soft etching, pickling is performed. The type of acid used for pickling is appropriately determined depending on the component of soft etching. When a cupric chloride-containing aqueous solution is used, a hydrochloric acid solution is used, and when an aqueous solution of sulfuric acid is used, sulfuric acid is used.
【００１１】上記銅回路を粗化した後に、内層用配線板
の銅回路に酸化処理を施し、銅酸化膜を形成する。上記
酸化処理の方法としては、例えば、亜塩素酸ナトリウム
水溶液、過硫酸カリウム等の過硫酸塩水溶液が挙げら
れ、なかでも亜塩素酸ナトリウム水溶液が汎用される。
この亜塩素酸ナトリウム水溶液として、具体的には、亜
塩素酸ナトリウム（ＮａＣｌＯ2 ）、水酸化ナトリウム
（ＮａＯＨ）、及び、緩衝液としてリン酸・１２水和物
（Ｈ3 ＰＯ4 ・１２Ｈ2 Ｏ）を成分とした水溶液が挙げ
られる。上記酸化処理を施した後に、水洗を行い、充分
に乾燥させた後に、酸性溶液に内層用配線板を浸漬する
ことが好ましい。上記乾燥は１００〜１５０℃で３〜６
０分が適当である。充分に乾燥することにより、銅回路
に均一な酸化第一銅の皮膜を得ることができる。After roughening the copper circuit, the copper circuit of the inner layer wiring board is subjected to oxidation treatment to form a copper oxide film. Examples of the oxidation treatment method include an aqueous solution of sodium chlorite and an aqueous solution of persulfate such as potassium persulfate. Among them, an aqueous solution of sodium chlorite is generally used.
The sodium chlorite aqueous solution is specifically sodium chlorite (NaClO 2 ), sodium hydroxide (NaOH), and phosphoric acid dodecahydrate (H 3 PO 4 12H 2 O) as a buffer solution. ) As an ingredient. It is preferable that the inner layer wiring board is immersed in an acidic solution after the above oxidation treatment, followed by washing with water and sufficient drying. The above drying is 3 to 6 at 100 to 150 ° C.
0 minutes is appropriate. By sufficiently drying, a uniform cuprous oxide film can be obtained on the copper circuit.
【００１２】さらに、希硫酸、及びキレートを含有する
酸性溶液に浸漬すると、酸化第二銅の皮膜を除去する処
理を均一に施すことができる。上記酸性溶液としては、
希硫酸、及びエチレンジアミン四酢酸等のキレートを含
有し、さらに必要により、脂肪族のアルコール、ほう
酸、ぎ酸、カルボン酸等の有機酸を含む水溶液であり、
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。上記酸性溶液のｐＨは３．０〜４．
０が適している。[0012] Furthermore, by immersing in an acidic solution containing dilute sulfuric acid and a chelate, the treatment for removing the cupric oxide film can be uniformly performed. As the acidic solution,
Dilute sulfuric acid, and an aqueous solution containing a chelate such as ethylenediaminetetraacetic acid and, if necessary, an aliphatic alcohol, boric acid, formic acid, an organic acid such as carboxylic acid,
The inclusion of the chelate, boric acid, formic acid, and carboxylic acid has an effect of preventing the copper ions of the removed cupric acid from reattaching to the copper circuit. The acidic solution has a pH of 3.0 to 4.
0 is suitable.
【００１３】本発明においては、上記酸性溶液中の銅イ
オン濃度が０．８ｇ／リットル〜１２ｇ／リットルの範
囲である。上記酸性溶液中の銅イオン濃度が０．８ｇ／
リットル未満であると、上記銅回路面上での反応速度に
ばらつきを生じ、色むらが発生し易く、銅イオン濃度が
１２ｇ／リットルを超えると、上記銅酸化膜中の酸化第
二銅が充分に除去されなくなる恐れがあり、銅回路に色
むらが発生し易い。In the present invention, the copper ion concentration in the acidic solution is in the range of 0.8 g / liter to 12 g / liter. Copper ion concentration in the acidic solution is 0.8 g /
If it is less than 1 liter, the reaction rate on the copper circuit surface varies, and color unevenness is likely to occur. If the copper ion concentration exceeds 12 g / liter, cupric oxide in the copper oxide film is sufficient. There is a risk that it will not be removed, and color unevenness is likely to occur in the copper circuit.
【００１４】上記酸性溶液に浸漬した後、水洗が施され
るが、この水洗の前にｐＨ４．５〜５．５の範囲のキレ
ート含有液に浸漬洗浄することが好ましい。上記キレー
ト含有液の浸漬洗浄は、上記銅回路からの残留した銅イ
オンの除去に有効である。上記キレート含有液のｐＨは
４．５〜５．５が最適である。上記キレートとしては、
エチレンジアミン四酢酸等が挙げられ、ｐＨの調製に希
硫酸が用いられる。さらに、しゅう酸、グルコン酸等の
カルボン酸を含有すると、より残留した銅イオンの除去
に有効である。After dipping in the above acidic solution, washing with water is carried out. Before washing with water, dipping and washing with a chelate-containing solution having a pH range of 4.5 to 5.5 is preferable. Immersion cleaning of the chelate-containing liquid is effective for removing residual copper ions from the copper circuit. The pH of the chelate-containing liquid is optimally 4.5 to 5.5. As the chelate,
Examples thereof include ethylenediaminetetraacetic acid, and dilute sulfuric acid is used to adjust the pH. Furthermore, the inclusion of a carboxylic acid such as oxalic acid or gluconic acid is effective in removing more residual copper ions.
【００１５】上記酸性溶液に浸漬した後、又は、酸性溶
液に浸漬し、さらにｐＨ４．５〜５．５の範囲のキレー
ト含有液に浸漬洗浄した後に、上記内層用配線板は水洗
が行われる。この水洗の方法は、多段式が望ましく、ｐ
Ｈの変化による衝撃を緩和するために、最初の水洗はｐ
Ｈ４．５〜７．５の範囲で水洗することが好ましい。After immersing in the acidic solution, or after immersing in the acidic solution and further immersing in the chelate-containing solution having a pH of 4.5 to 5.5, the inner layer wiring board is washed with water. This washing method is preferably a multi-stage method,
In order to mitigate the impact due to the change in H, the first water wash is p
It is preferable to wash with water in the range of H4.5 to 7.5.
【００１６】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.
【００１７】[0017]
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。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.
【００１８】この内層用配線板の銅回路にソフトエッチ
ングを施した。ソフトエッチング液に塩酸が１６０ｇ／
リットル、Ｃｕ2+が１３ｇ／リットル、Ｃｕ+ が２ｇ／
リットル含有した塩化第二銅含有水溶液を用い、上記内
層用配線板を温度３０℃のソフトエッチング液に１分３
０秒浸漬し、２回水洗した。その後、塩酸の濃度が１４
０ｇ／リットル含有した３０℃の液で１分３０秒酸洗い
をした。The copper circuit of the inner layer wiring board was soft-etched. Hydrochloric acid 160g / in soft etching liquid
Liter, Cu 2+ is 13 g / liter, Cu + is 2 g /
Using an aqueous solution containing cupric chloride containing 1 liter, the inner layer wiring board was immersed in a soft etching solution at a temperature of 30 ° C. for 1 minute 3
It was immersed for 0 seconds and washed twice with water. After that, the concentration of hydrochloric acid is 14
Pickling was carried out for 1 minute and 30 seconds with a liquid of 0 g / liter at 30 ° C.
【００１９】その後、１５℃の亜塩素酸ナトリウム水溶
液に５分浸漬し、酸化処理を施した。亜塩素酸ナトリウ
ム水溶液は、亜塩素酸ナトリウム（ＮａＣｌＯ2 ）の濃
度が１００ｇ／リットル、水酸化ナトリウム（ＮａＯ
Ｈ）の濃度が４３ｇ／リットル、リン酸・１２水和物
（Ｈ3 ＰＯ4 ・１２Ｈ2 Ｏ）の濃度が１５ｇ／リットル
であった。酸化処理後、水洗し、１３０℃で２０分乾燥
した。After that, it was immersed in an aqueous solution of sodium chlorite at 15 ° C. for 5 minutes for oxidation treatment. The sodium chlorite aqueous solution has a sodium chlorite (NaClO 2 ) concentration of 100 g / liter and sodium hydroxide (NaO 2 ).
The concentration of H) was 43 g / liter, and the concentration of phosphoric acid dodecahydrate (H 3 PO 4 12H 2 O) was 15 g / liter. After the oxidation treatment, it was washed with water and dried at 130 ° C. for 20 minutes.
【００２０】次に、酸性溶液として、銅イオン濃度が
６．０ｇ／リットル、エチレンジアミン四酢酸を０．１
４モル／リットル含有するｐＨ３．７の希硫酸の水溶液
を用いた。上記内層用配線板を５５℃の酸性溶液に５分
浸漬した。Next, as an acidic solution, a copper ion concentration of 6.0 g / liter and ethylenediaminetetraacetic acid of 0.1
An aqueous solution of dilute sulfuric acid having a pH of 3.7 and containing 4 mol / liter was used. The inner layer wiring board was immersed in an acidic solution at 55 ° C. for 5 minutes.
【００２１】その後、先ずｐＨ４．５〜７．５の範囲
で、徐々にｐＨを上げながら、３回水洗を繰り返し、乾
燥を行った。Then, first, in the range of pH 4.5 to 7.5, washing with water was repeated three times while gradually raising the pH, and drying was performed.
【００２２】実施例２ 実施例１の酸性溶液として、銅イオン濃度が０．８ｇ／
リットルであった以外は実施例１と同様にして内層用配
線板の銅回路に処理を施した。Example 2 The acidic solution of Example 1 had a copper ion concentration of 0.8 g /
The copper circuit of the inner layer wiring board was treated in the same manner as in Example 1 except that the amount was 1 liter.
【００２３】実施例３ 実施例１の酸性溶液として、銅イオン濃度が１２．０ｇ
／リットルであった以外は実施例１と同様にして内層用
配線板の銅回路に処理を施した。Example 3 As the acidic solution of Example 1, the copper ion concentration was 12.0 g.
The copper circuit of the wiring board for inner layer was treated in the same manner as in Example 1 except that the amount was 1 / liter.
【００２４】比較例１ 実施例１の酸性溶液として、銅イオン濃度が１８．０ｇ
／リットルであった以外は実施例１と同様にして内層用
配線板の銅回路に処理を施した。Comparative Example 1 The acidic solution of Example 1 had a copper ion concentration of 18.0 g.
The copper circuit of the wiring board for inner layer was treated in the same manner as in Example 1 except that the amount was 1 / liter.
【００２５】比較例２ 実施例１の酸性溶液として、銅イオン濃度が０．１ｇ／
リットルであった以外は実施例１と同様にして内層用配
線板の銅回路に処理を施した。Comparative Example 2 The acidic solution of Example 1 had a copper ion concentration of 0.1 g /
The copper circuit of the inner layer wiring board was treated in the same manner as in Example 1 except that the amount was 1 liter.
【００２６】得られた実施例１〜３、及び、比較例１〜
２の内層用配線板の外観を目視で評価した。５００枚の
内層用配線板の銅回路２０カ所、計１万カ所について、
スジ状や斑点状の色むらが発生しているかを検査し、少
しでも色むらの生じている個所を数えた。結果は表１に
示すとおり実施例１〜３は比較例に比べ色むらが非常に
少なかった。The obtained Examples 1 to 3 and Comparative Examples 1 to 1
The appearance of the inner layer wiring board 2 was visually evaluated. About 20 copper circuits of 500 inner wiring boards, 10,000 in total,
It was inspected whether streak-like or spot-like color unevenness had occurred, and the number of points where color unevenness had occurred was counted. As shown in Table 1, in Examples 1 to 3, the color unevenness was much smaller than that in Comparative Example.
【００２７】[0027]
【表１】 [Table 1]
【００２８】実施例４ 実施例１と同様に銅回路を作製した内層用配線板を用い
た。Example 4 An inner layer wiring board having a copper circuit produced in the same manner as in Example 1 was used.
【００２９】この内層用配線板の銅回路にソフトエッチ
ングを施した。塩酸が１６０ｇ／リットル、Ｃｕ2+が１
３ｇ／リットル、Ｃｕ+ が２ｇ／リットル含有した塩化
第二銅含有水溶液を第１のソフトエッチング液とし、硫
酸が４０ｇ／リットル、過酸化水素が２０ｇ／リット
ル、Ｃｕ2+が５ｇ／リットル含有した水溶液を第２のソ
フトエッチング液とした。温度３０℃の第１のソフトエ
ッチング液に１分３０秒浸漬し、２回水洗した後に、温
度３０℃の第２のソフトエッチング液に１分３０秒浸漬
し、２回水洗した。その後、硫酸の濃度が４２０ｇ／リ
ットル含有した２５℃の液で１分３０秒酸洗いをした。The copper circuit of this inner layer wiring board was soft-etched. Hydrochloric acid is 160 g / liter, Cu 2+ is 1
An aqueous solution containing cupric chloride containing 3 g / liter of Cu + and 2 g / liter of Cu + was used as the first soft etching solution, containing 40 g / liter of sulfuric acid, 20 g / liter of hydrogen peroxide, and 5 g / liter of Cu 2+ . The aqueous solution was used as the second soft etching solution. After being immersed in the first soft etching solution at a temperature of 30 ° C. for 1 minute 30 seconds and washed twice with water, it was immersed in the second soft etching solution at a temperature of 30 ° C. for 1 minute 30 seconds and washed twice with water. Then, it was pickled for 1 minute and 30 seconds with a 25 ° C. liquid containing a sulfuric acid concentration of 420 g / liter.
【００３０】その後、実施例１と同様に亜塩素酸ナトリ
ウム水溶液に５分浸漬し、酸化処理を施した後、水洗
し、１３０℃で２０分乾燥した。Then, as in Example 1, it was immersed in an aqueous solution of sodium chlorite for 5 minutes, subjected to an oxidation treatment, washed with water, and dried at 130 ° C. for 20 minutes.
【００３１】次に、酸性溶液として、銅イオン濃度が
６．０ｇ／リットル、エチレンジアミン四酢酸を０．１
４モル／リットル含有するｐＨ３．７の希硫酸の水溶液
を用いた。上記内層用配線板を５５℃の酸性溶液に５分
浸漬した。Next, as an acidic solution, a copper ion concentration of 6.0 g / liter and ethylenediaminetetraacetic acid of 0.1 were prepared.
An aqueous solution of dilute sulfuric acid having a pH of 3.7 and containing 4 mol / liter was used. The inner layer wiring board was immersed in an acidic solution at 55 ° C. for 5 minutes.
【００３２】さらに、キレート含有液として、キレート
にエチレンジアミン四酢酸を含有するｐＨ５．０の水溶
液を用い、このキレート含有液で浸漬洗浄した。その
後、実施例１と同様に３回水洗を繰り返し、乾燥を行っ
た。Further, as the chelate-containing solution, an aqueous solution containing ethylenediaminetetraacetic acid as a chelate and having a pH of 5.0 was used, and immersion cleaning was performed with the chelate-containing solution. Then, as in Example 1, washing with water was repeated three times and drying was performed.
【００３３】実施例５ 実施例４と同様に銅回路を作製した内層用配線板を用い
た。Example 5 An inner layer wiring board having a copper circuit produced in the same manner as in Example 4 was used.
【００３４】この内層用配線板の銅回路に実施例４と同
様に２回ソフトエッチングを施し、水洗、酸洗いをし
た。The copper circuit of this wiring board for the inner layer was soft-etched twice as in Example 4, and washed with water and pickled.
【００３５】その後、実施例４と同様の亜塩素酸ナトリ
ウム水溶液に５分浸漬し、酸化処理を施した後、水洗し
た。After that, it was immersed in the same sodium chlorite aqueous solution as in Example 4 for 5 minutes, subjected to an oxidation treatment, and washed with water.
【００３６】次に、実施例４と同様の酸性溶液に５分浸
漬した。その後、実施例４と同様に３回水洗を繰り返
し、乾燥を行った。Next, it was immersed in the same acidic solution as in Example 4 for 5 minutes. After that, washing with water was repeated 3 times and drying was performed in the same manner as in Example 4.
【００３７】実施例６ 実施例１と同様に銅回路を作製した内層用配線板を用い
た。Example 6 An inner layer wiring board having a copper circuit produced in the same manner as in Example 1 was used.
【００３８】この内層用配線板の銅回路に実施例１と同
様に１回ソフトエッチングを施し、水洗、酸洗いをし
た。The copper circuit of this inner layer wiring board was soft-etched once in the same manner as in Example 1, and washed with water and pickled.
【００３９】その後、実施例１と同様の亜塩素酸ナトリ
ウム水溶液に５分浸漬し、酸化処理を施した後、水洗し
た。After that, it was immersed in the same sodium chlorite aqueous solution as in Example 1 for 5 minutes, subjected to an oxidation treatment, and washed with water.
【００４０】次に、実施例１と同様の酸性溶液に５分浸
漬し、さらに、キレート含有液として、キレートにエチ
レンジアミン四酢酸を含有するｐＨ４．５の水溶液を用
い、このキレート含有液で浸漬洗浄した。その後、実施
例１と同様に３回水洗を繰り返し、乾燥を行った。Next, it was immersed in the same acidic solution as in Example 1 for 5 minutes, and as the chelate-containing solution, an aqueous solution having a pH of 4.5 containing ethylenediaminetetraacetic acid as a chelate was used. did. Then, as in Example 1, washing with water was repeated three times and drying was performed.
【００４１】実施例７ 実施例６のキレート含有液として、キレートにエチレン
ジアミン四酢酸、カルボン酸としてしゅう酸を含有する
ｐＨ５．５の水溶液を用いた以外は実施例６と同様にし
て、内層用配線板の銅回路に処理を施した。Example 7 Wiring for inner layer was carried out in the same manner as in Example 6 except that as the chelate-containing solution of Example 6, an aqueous solution having a pH of 5.5 containing ethylenediaminetetraacetic acid as a chelate and oxalic acid as a carboxylic acid was used. The copper circuit of the board was treated.
【００４２】実施例８ 実施例６のキレート含有液として、キレートにエチレン
ジアミン四酢酸を含有するｐＨが３．５の水溶液を用い
た以外は実施例６と同様にして、内層用配線板の銅回路
に処理を施した。Example 8 A copper circuit for an inner layer wiring board was prepared in the same manner as in Example 6 except that an aqueous solution containing ethylenediaminetetraacetic acid as a chelate and having a pH of 3.5 was used as the chelate-containing solution of Example 6. Was processed.
【００４３】得られた実施例４〜８の内層用配線板の外
観を上述と同様に評価した。結果は表２に示すとおりで
あった。第１のソフトエッチングと第２のソフトエッチ
ングの処理と酸性溶液に浸漬した後、ｐＨ４．５〜５．
５の範囲のキレート含有液に浸漬洗浄した実施例４の色
むらの発生は他の実施例より優れていた。酸性溶液に浸
漬した後、ｐＨ４．５〜５．５の範囲のキレート含有液
に浸漬洗浄した実施例６、７は実施例１〜３より良好で
あった。また、キレート含有液のｐＨの範囲が外れてい
た実施例８は、比較例１、２よりは良好であったが、他
の実施例ほどは低下しなかった。The appearance of the obtained inner layer wiring boards of Examples 4 to 8 was evaluated in the same manner as described above. The results are shown in Table 2. After the treatment of the first soft etching and the second soft etching and the immersion in the acidic solution, the pH is 4.5 to 5.
The occurrence of color unevenness in Example 4, which was immersed and washed in the chelate-containing solution in the range of 5, was superior to the other Examples. Examples 6 and 7, which were dipped in an acidic solution and then dipped and washed in a chelate-containing liquid having a pH range of 4.5 to 5.5, were better than Examples 1 to 3. In addition, Example 8 in which the pH range of the chelate-containing liquid was out of the range was better than Comparative Examples 1 and 2, but did not decrease as much as the other Examples.
【００４４】[0044]
【表２】 [Table 2]
【００４５】[0045]
【発明の効果】本発明の請求項１乃至請求項３いずれか
記載の内層用配線板の銅回路の処理方法を用いると、ス
ジ状や斑点状の色むらが発生しない、外観の良好な内層
用配線板を得ることができる。EFFECT OF THE INVENTION When the method for treating a copper circuit of an inner layer wiring board according to any one of claims 1 to 3 of the present invention is used, an inner layer having a good appearance in which no stripe-like or spot-like color unevenness occurs The wiring board can be obtained.
Claims (3)
し、銅酸化膜を形成した後に、希硫酸、及び、キレート
を含有する酸性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、上記酸性溶液中の銅イオン濃度が
０．８ｇ／リットル〜１２ｇ／リットルの範囲であるこ
とを特徴とする内層用配線板の銅回路の処理方法。1. A method of treating a copper circuit of an inner layer wiring board, which comprises subjecting a copper circuit of the inner layer wiring board to oxidation treatment to form a copper oxide film, and then immersing the copper circuit in an inner layer wiring board in an acidic solution containing dilute sulfuric acid and a chelate. The method for treating a copper circuit of a wiring board for an inner layer, wherein the copper ion concentration in the acidic solution is in the range of 0.8 g / liter to 12 g / liter.
あり、且つ、この酸性溶液に浸漬した後に、ｐＨ４．５
〜５．５の範囲のキレート含有液に浸漬洗浄することを
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 acidic solution has a pH of 3.0 to 4.0, and has a pH of 4.5 after being immersed in the acidic solution.
The method for treating a copper circuit of a wiring board for an inner layer according to claim 1, wherein the washing is performed by immersion in a chelate-containing solution in the range of to 5.5.
施す前処理として、この内層用配線板の銅回路に塩化第
二銅含有水溶液で第１のソフトエッチングをした後に、
硫酸と硫酸アンモニウムの水溶液、及び、硫酸と過酸化
水素の水溶液のどちらかの液で第２のソフトエッチング
で処理することを特徴とする請求項１又は請求項２記載
の内層用配線板の銅回路の処理方法。3. As a pretreatment for subjecting the copper circuit of the inner layer wiring board to an oxidation treatment, after the copper circuit of the inner layer wiring board is first soft-etched with an aqueous solution containing cupric chloride,
The copper circuit of the inner layer wiring board according to claim 1 or 2, which is treated by the second soft etching with one of an aqueous solution of sulfuric acid and ammonium sulfate and an aqueous solution of sulfuric acid and hydrogen peroxide. Processing method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20353394A JP3237410B2 (en) | 1994-08-29 | 1994-08-29 | Processing method of copper circuit of wiring board for inner layer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20353394A JP3237410B2 (en) | 1994-08-29 | 1994-08-29 | Processing method of copper circuit of wiring board for inner layer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0870178A true JPH0870178A (en) | 1996-03-12 |
| JP3237410B2 JP3237410B2 (en) | 2001-12-10 |
Family
ID=16475734
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20353394A Expired - Fee Related JP3237410B2 (en) | 1994-08-29 | 1994-08-29 | Processing method of copper circuit of wiring board for inner layer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3237410B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6261953B1 (en) * | 2000-01-25 | 2001-07-17 | Kabushiki Kaisha Toshiba | Method of forming a copper oxide film to etch a copper surface evenly |
| JP2006019655A (en) * | 2004-07-05 | 2006-01-19 | Hitachi Chem Co Ltd | Multilayer printed circuit board, manufacturing method thereof, and chemical roughening solution |
-
1994
- 1994-08-29 JP JP20353394A patent/JP3237410B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6261953B1 (en) * | 2000-01-25 | 2001-07-17 | Kabushiki Kaisha Toshiba | Method of forming a copper oxide film to etch a copper surface evenly |
| US6475909B2 (en) | 2000-01-25 | 2002-11-05 | Kabushiki Kaisha Toshiba | Method of fabricating metal wiring on a semiconductor substrate using ammonia-containing plating and etching solutions |
| KR100426554B1 (en) * | 2000-01-25 | 2004-04-08 | 가부시끼가이샤 도시바 | Method of forming copper oxide film, method and apparatus of fabricating a semeconductor device, and a semiconductor device |
| US6818556B2 (en) | 2000-01-25 | 2004-11-16 | Kabushiki Kaisha Toshiba | Method of plating a metal or metal compound on a semiconductor substrate that includes using the same main component in both plating and etching solutions |
| US7183203B2 (en) | 2000-01-25 | 2007-02-27 | Kabushiki Kaisha Toshiba | Method of plating a metal or metal compound on a semiconductor substrate that includes using the same main component in both plating and etching solutions |
| JP2006019655A (en) * | 2004-07-05 | 2006-01-19 | Hitachi Chem Co Ltd | Multilayer printed circuit board, manufacturing method thereof, and chemical roughening solution |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3237410B2 (en) | 2001-12-10 |
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