JPH0738254A - Treatment of inner layer copper foil - Google Patents
Treatment of inner layer copper foilInfo
- Publication number
- JPH0738254A JPH0738254A JP18134593A JP18134593A JPH0738254A JP H0738254 A JPH0738254 A JP H0738254A JP 18134593 A JP18134593 A JP 18134593A JP 18134593 A JP18134593 A JP 18134593A JP H0738254 A JPH0738254 A JP H0738254A
- Authority
- JP
- Japan
- Prior art keywords
- copper
- treatment
- inner layer
- copper foil
- 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
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/382—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/46—Manufacturing multilayer circuits
- H05K3/4611—Manufacturing multilayer circuits by laminating two or more circuit boards
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、電子機器、電気機器、
コンピューター、通信機器等に利用される多層プリント
配線板の製造に用いる、内層回路用の銅箔処理方法に関
するものである。特に、「ハロー」或いは「ピンクリン
グ」の発生を完全に防止する、多層プリント配線板の製
造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to electronic equipment, electric equipment,
The present invention relates to a copper foil processing method for an inner layer circuit, which is used for manufacturing a multilayer printed wiring board used for computers, communication devices and the like. In particular, the present invention relates to a method for manufacturing a multilayer printed wiring board, which completely prevents the occurrence of "halo" or "pink ring".
【０００２】[0002]
【従来の技術】多層プリント板において、プリント回路
を形成した内層板の、多層化接着力を向上させる方法と
しては、予め両面に微細凸凹を形成した銅箔を用いる方
法，内層用のプリント回路を形成した後、ａ．酸化処理
水溶液により、銅箔表面に酸化銅微細凸凹を形成する方
法、ｂ．銅箔面をシラン系や有機チタネート系のカップ
リング剤で処理する方法等が知られている。接着性と経
済性の点から通常、光沢面を有する銅張積層板に内層用
のプリント回路を形成した後、酸化性のアルカリ水溶液
で処理して、褐色或いは黒色の酸化銅微細凸凹膜を形成
したものが用いられている。2. Description of the Related Art In a multilayer printed circuit board, as a method for improving the multilayer adhesive strength of an inner layer board on which a printed circuit is formed, a method of using a copper foil having fine irregularities formed on both sides in advance and a printed circuit for the inner layer After formation, a. A method of forming copper oxide fine irregularities on the surface of a copper foil with an oxidizing treatment aqueous solution, b. A method of treating a copper foil surface with a silane-based or organic titanate-based coupling agent is known. From the viewpoint of adhesiveness and economical efficiency, a printed circuit for the inner layer is usually formed on a copper clad laminate with a glossy surface, and then treated with an oxidizing alkaline aqueous solution to form a brown or black copper oxide fine uneven film. What has been used is used.
【０００３】ところが、この酸化銅微細凸凹膜を形成し
た内層板を用いて、無電解メッキ、その後の電気メッキ
を施したものには、いわゆるハロー或いはピンクリング
が発生し易く、絶縁性などのプリント配線板の信頼性の
低下の原因となる欠点があった。However, so-called halos or pink rings are apt to occur in those subjected to electroless plating and subsequent electroplating using the inner layer plate on which the copper oxide fine uneven film is formed, and printing such as insulation is performed. There is a drawback that causes a reduction in the reliability of the wiring board.
【０００４】この褐色或いは黒色の酸化銅微細凸凹膜を
用いた場合に発生するハロー或いはピンクリングを防止
する方法として、最近、ｃ．ａで得られた、銅箔表面の
酸化銅微細凸凹膜を還元剤水溶液で還元して、亜酸化銅
或いは、金属銅の微細凸凹膜に変更する方法（特開昭５
６−１５３７９７号等）が開示されるに至っている。こ
れらの方法は、ハローの発生防止の為には有効な方法で
あるが、亜酸化銅若しくは金属銅の表面は不安定で変化
し易く、処理後に出来る限り早急に次の工程を行う必要
がある。また、還元処理を行う際に、一般的には水素ガ
スが発生し、その対策を行わないと爆発等の危険を伴
う。更に、還元処理条件が難しく、処理液の厳密な液管
理を必要とする。また、処理板の積層プレス条件に制限
があったりする。Recently, as a method for preventing the halo or pink ring which occurs when this brown or black copper oxide fine uneven film is used, c. A method of reducing the copper oxide fine uneven film on the surface of the copper foil obtained in a with an aqueous reducing agent solution to change it to a fine uneven film of cuprous oxide or metallic copper (Japanese Patent Laid-open No. Sho 5).
No. 6-153797) has been disclosed. These methods are effective methods for preventing the occurrence of halo, but the surface of cuprous oxide or metallic copper is unstable and easily changed, and it is necessary to perform the next step as soon as possible after the treatment. . In addition, hydrogen gas is generally generated during the reduction process, and unless measures are taken, there is a risk of explosion or the like. Furthermore, reduction treatment conditions are difficult, and strict liquid management of the processing liquid is required. In addition, there are restrictions on the laminating press conditions for the treated plate.
【０００５】これに対して、ｄ．ａで得られた銅箔表面
の酸化銅の微細凸凹膜を、ｐＨ３．５〜４．０の酸性キ
レート溶液で、溶解除去する方法（PRINTED CIRCUITFAB
RICATION , AUGUST , 1984)が開示され、マクダーミッ
ド社より処理液が市販されている。この方法はｃ．の還
元法と比較し、安全性、積層プレス条件の広いことで有
利であるが、安定的に完全なノンハロー処理ができな
く、内層接着力の低下が見られるなどの欠点を有してい
た。On the other hand, d. A method for dissolving and removing the fine uneven film of copper oxide on the surface of the copper foil obtained in a by using an acidic chelate solution having a pH of 3.5 to 4.0 (PRINTED CIRCUITFAB
RICATION, AUGUST, 1984) is disclosed, and a treatment liquid is marketed by MacDermid. This method is c. Compared with the reduction method of No. 1, it is advantageous in terms of safety and a wide range of laminating press conditions, but it has drawbacks such that stable complete non-halo treatment cannot be performed and the adhesive strength of the inner layer is reduced.
【０００６】[0006]
【発明が解決しようとする課題】本発明は、マクダーミ
ッド社の市販している内層銅箔処理液を用いて、安定的
に、完全にハローの発生を抑制し、接着力低下を許容レ
ベルに抑制する、簡便な方法を提供することを目的とす
るものである。その結果、本発明者らは、酸化処理する
前に、ソフトエッチングを一定量以上行い、酸化処理
後、酸化銅膜を溶解処理し、さらにその表面を防錆処理
する方法を見いだし、本発明を完成するに至った。さら
に、本発明により、マクダーミッド社の市販している内
層銅箔処理方法の標準的な処理時間を、大幅に短縮する
事ができることも見いだした。DISCLOSURE OF THE INVENTION The present invention stably and completely suppresses the generation of halos and suppresses the decrease in adhesive strength to an acceptable level by using a commercially available inner layer copper foil treatment liquid of McDermid Co., Ltd. The purpose is to provide a simple method. As a result, the present inventors have found that before the oxidation treatment, a certain amount or more of soft etching is performed, after the oxidation treatment, the copper oxide film is subjected to a dissolution treatment, and the surface thereof is subjected to rust-prevention treatment. It came to completion. Further, it was also found that the present invention can significantly reduce the standard processing time of the commercially available inner layer copper foil processing method of MacDermid.
【０００７】[0007]
【課題を解決するための手段】本発明は、中間層として
プリント回路を形成した内層板の銅箔面を、まずエッチ
ング剤を用いて１．０μｍ〜３．０μｍソフトエッチン
グして、微細な粗化処理を行った後、アルカリ性水溶液
で表面処理（プレディップ）し、さらにアルカリ性亜塩
素酸ナトリウム水溶液で酸化処理し、３０〜６０ｍｇ／
ｄｍ2 の酸化銅微細凸凹膜 (ブラックオキサイド) を形
成した後、酸性キレート水溶液で酸化銅膜を９０〜９９
％溶解除去（ポストディップ）した後に、ベンゾトリア
ゾール等の銅の防錆処理液に浸漬処理し、防錆皮膜を形
成することを特徴とする、完全なノンハローを達成でき
る、多層プリント配線板用の内層銅箔処理方法である。According to the present invention, a copper foil surface of an inner layer plate having a printed circuit formed as an intermediate layer is first soft-etched with an etching agent to a fine roughness of 1.0 μm to 3.0 μm. After chemical treatment, surface treatment (pre-dip) with an alkaline aqueous solution, further oxidation treatment with an alkaline sodium chlorite aqueous solution, 30-60 mg /
After forming a copper oxide fine uneven film (black oxide) of dm 2, the copper oxide film is washed with an acidic chelate aqueous solution at 90-99.
% Multi-layered printed wiring board that can achieve a complete non-halo, characterized by forming a rust-preventive film by dipping in copper anti-rust treatment solution such as benzotriazole after post-dip It is an inner layer copper foil processing method.
【０００８】本発明による、ハローの発生を完全に防止
するための、内層銅箔処理工程の概略は、(1).ソフトエ
ッチング → (2). 水洗 → (3). 酸洗 → (4). 水洗
→(5).プレデッップ → (6). ブラックオキサイド
→ (7). 水洗 → (8). ポストディップ → (9). 水洗
→ (10).防錆処理 → (11).水洗 → (12).乾燥から
なるものである。The outline of the inner layer copper foil treatment step for completely preventing the generation of halo according to the present invention is as follows: (1). Soft etching → (2). Water washing → (3). Pickling → (4) Wash with water → (5). Predep → (6). Black oxide
→ (7). Washing with water → (8). Post dip → (9). Washing with water → (10). Rust prevention treatment → (11). Washing with water → (12). Drying.
【０００９】本発明の多層プリント板とは、中間層に使
用する内層用プリント回路を形成した内層板として、銅
箔面を化学的に酸化し、黒色或いは褐色の酸化銅微細凸
凹膜を形成した内層板、多層化接着に使用するプリプレ
グ、外層を形成する為のプリプレグ及び銅箔或いは片面
銅張り積層板などの積層材料、並びに積層成形の方法に
よって製造した、両外表面銅箔の多層プリント配線板に
スルーホール穴あけし、デスミア処理、ついで無電解メ
ッキしてなるものであり、従来もっとも汎用的に製造さ
れているものである。The multilayer printed board of the present invention is an inner layer board having an inner layer printed circuit used as an intermediate layer, in which a copper foil surface is chemically oxidized to form a black or brown copper oxide fine uneven film. Inner layer board, prepreg used for multi-layer adhesion, prepreg for forming outer layer and laminated material such as copper foil or single-sided copper clad laminate, and multilayer printed wiring of both outer surface copper foil manufactured by lamination molding method It is a through-hole drilled in a plate, desmeared, and then electroless plated.
【００１０】本発明で用いる、ソフトエッチング処理液
としては、塩化銅、塩化鉄、過硫酸ナトリウム、過硫酸
カリウム、過酸化水素−硫酸等、公知の物が使用でき
る。このなかで特に好ましいのは、過硫酸ナトリウム１
００ｇ／１(リットル)の水溶液で、３０〜４０℃で、１〜４
分処理する方法であり、エッチング量は１．０μｍ以
上、好ましくは１．５〜３．０μｍである。As the soft etching treatment liquid used in the present invention, known substances such as copper chloride, iron chloride, sodium persulfate, potassium persulfate and hydrogen peroxide-sulfuric acid can be used. Of these, sodium persulfate 1 is particularly preferable.
00 g / 1 (liter) aqueous solution at 30-40 ° C for 1-4
In this method, the amount of etching is 1.0 μm or more, preferably 1.5 to 3.0 μm.
【００１１】ここで酸洗は、硫酸、塩酸、リン酸、酢
酸、等の１〜２０ｗ／ｗ％溶液が用いられる。特に好ま
しくは、硫酸の１０ｗ／ｗ％水溶液で、処理温度２０〜
３５℃、処理時間１〜２分である。For the pickling, a 1 to 20 w / w% solution of sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid or the like is used. Particularly preferably, a 10 w / w% aqueous solution of sulfuric acid is used at a treatment temperature of 20 to
The temperature is 35 ° C. and the treatment time is 1 to 2 minutes.
【００１２】プレディップは、水酸化ナトリウム、水酸
化カリウム等のアルカリ水溶液を使用する。このなかで
特に好ましいものは、水酸化ナトリウムであり、濃度３
０〜５０ｇ／ｌになるように調整した液を用いる。好ま
しい処理条件は、温度４５〜５５℃、時間１〜２分であ
る。For the pre-dip, an alkaline aqueous solution such as sodium hydroxide or potassium hydroxide is used. Of these, sodium hydroxide is particularly preferred, with a concentration of 3
A liquid adjusted to 0 to 50 g / l is used. Preferable processing conditions are a temperature of 45 to 55 ° C. and a time of 1 to 2 minutes.
【００１３】ブラックオキサイドは、塩素酸ナトリウ
ム、亜塩素酸ナトリウム、過硫酸ナトリウム、過硫酸カ
リウム等のアルカリ性水溶液を使用する。この中で好ま
しいのは亜塩素酸ナトリウムで、濃度１００〜１４０ｇ
／１(リットル)、水酸化ナトリウム濃度３０〜５０ｇ／１で
アルカリ性に調整した液を用いる。好ましい処理条件
は、温度７０〜８０℃、時間３〜６分である。As the black oxide, an alkaline aqueous solution of sodium chlorate, sodium chlorite, sodium persulfate, potassium persulfate or the like is used. Among these, sodium chlorite is preferable, and the concentration is 100 to 140 g.
A liquid adjusted to have an alkalinity of 1 (liter) and a sodium hydroxide concentration of 30 to 50 g / 1 is used. Preferred processing conditions are a temperature of 70 to 80 ° C. and a time of 3 to 6 minutes.
【００１４】ポストディップは、エチレンジアミン四酢
酸塩（ＥＤＴＡ）水溶液に、硫酸、燐酸、硝酸、酢酸等
の鉱酸もしくは有機酸を加え、ＥＤＴＡ濃度０．０５〜
０．２０Ｍ、ｐＨ３．５〜４．０になるように調整した
液を用いる。好ましい条件は、温度５０〜６０℃、時間
３〜６分である。The post-dip is prepared by adding a mineral acid or organic acid such as sulfuric acid, phosphoric acid, nitric acid or acetic acid to an aqueous solution of ethylenediaminetetraacetic acid salt (EDTA) to obtain an EDTA concentration of 0.05 to
A liquid adjusted to have a pH of 0.20M and a pH of 3.5 to 4.0 is used. Preferred conditions are a temperature of 50 to 60 ° C. and a time of 3 to 6 minutes.
【００１５】本発明で用いる、銅系の防錆剤としては、
ベンゾトリアゾール、ベンゾチアゾール、トリルトリア
ゾール、アルキルイミダゾール、ベンジルイミダゾール
等の公知のものを使用することができる。この中で特に
好ましいのは、ベンゾトリアゾール０．５〜５ｇ／ｌ(リ
ットル)、好ましくは１〜３ｇ／ｌの水溶液で、３０〜８０
℃、好ましくは５０〜７０℃で、０．５〜５分、好まし
くは１〜３分浸漬処理する方法である。As the copper-based rust preventive used in the present invention,
Known compounds such as benzotriazole, benzothiazole, tolyltriazole, alkylimidazole, and benzylimidazole can be used. Among these, particularly preferred is an aqueous solution of benzotriazole 0.5 to 5 g / l (liter), preferably 1 to 3 g / l, and 30 to 80
This is a method of immersion treatment at 0.5 ° C., preferably 50 to 70 ° C. for 0.5 to 5 minutes, preferably 1 to 3 minutes.
【００１６】乾燥条件としては、プリント回路を形成し
た内層板の水分を、十分に除去できるものであれば特に
限定されるものではない。好ましい乾燥条件は、９０℃
で３０〜６０分の乾燥をすることである。The drying conditions are not particularly limited as long as the water content of the inner layer plate on which the printed circuit is formed can be sufficiently removed. Preferred drying conditions are 90 ° C
It is to dry for 30 to 60 minutes.
【００１７】[0017]
【作用】内層用回路板の銅回路の表面に、十分厚い酸化
皮膜を形成させることができ、酸化皮膜を溶解除去した
後に、十分なアンカー効果を持つ粗化面を残すことがで
きる。これにより、プリプレグ樹脂と銅回路の接着力を
高めることができる。更に、防錆処理することにより、
酸化皮膜のメッキ処理などの酸に対する溶解性を小さく
することができ、完全にハローの発生を抑制することが
できる。更に処理膜の安定化が図れ、放置安定性が増
す。A sufficiently thick oxide film can be formed on the surface of the copper circuit of the inner layer circuit board, and a roughened surface having a sufficient anchoring effect can be left after the oxide film is dissolved and removed. Thereby, the adhesive force between the prepreg resin and the copper circuit can be increased. Furthermore, by rust prevention treatment,
It is possible to reduce the solubility of the oxide film in an acid such as plating treatment, and to completely suppress the generation of halo. Further, the treated film can be stabilized, and the storage stability is increased.
【００１８】[0018]
【実施例】次に本発明を実施例により具体的に説明す
る。 実施例１ 両面に７０μ厚の銅箔を張って形成した、厚み０．８ｍ
ｍのガラス布基材エポキシ樹脂積層板（三菱ガス化学
（株）製ＥＬ−１７０）を用いて、両面に電気回路を形
成した。次に、過硫酸ナトリウム１００ｇ／１(リットル)の
濃度のソフトエッチング水溶液を用いて、３５℃で２分
間浸漬し、約１．５μｍソフトエッチングを行った。EXAMPLES Next, the present invention will be specifically described by way of examples. Example 1 0.8 m thick formed by stretching a 70 μ thick copper foil on both sides
An electric circuit was formed on both sides of the glass cloth-based epoxy resin laminated plate (EL-170 manufactured by Mitsubishi Gas Chemical Co., Inc.) of m. Then, using a soft etching aqueous solution having a concentration of 100 g / 1 (liter) of sodium persulfate, the solution was immersed at 35 ° C. for 2 minutes to perform soft etching of about 1.5 μm.
【００１９】このソフトエッチングした積層板を、濃度
４０ｇ／ｌの水酸化ナトリウム水溶液に５０℃で１分間
浸漬（プレディップ）した。次に、アルカリ性亜塩素酸
ナトリウム水溶液（亜塩素酸ナトリウム１２０ｇ／ｌ、
水酸化ナトリウム４０ｇ／ｌ）に、７５℃で３分間浸漬
することによって、銅の回路表面を酸化処理（黒化処
理）して、回路面をさらに粗化すると共に、酸化第２銅
皮膜を５０ｍｇ／ｄｍ2 形成（ブラックオキサイド）し
た。This soft-etched laminate was immersed (pre-dip) in a sodium hydroxide aqueous solution having a concentration of 40 g / l at 50 ° C. for 1 minute. Next, an alkaline sodium chlorite aqueous solution (sodium chlorite 120 g / l,
By immersing it in sodium hydroxide 40 g / l) at 75 ° C. for 3 minutes, the copper circuit surface is oxidized (blackened) to further roughen the circuit surface and 50 mg of the cupric oxide film. / Dm 2 was formed (black oxide).
【００２０】次に、ＥＤＴＡ水溶液に、硫酸を加えて調
整した溶液（ＥＤＴＡ濃度０．１０Ｍ、ＰＨ３．７）
に、５５℃で３分間浸漬することにより、回路表面の酸
化第２銅皮膜の約９５％を溶解除去（ポストディップ）
した。Next, a solution prepared by adding sulfuric acid to the EDTA aqueous solution (EDTA concentration 0.10 M, PH 3.7)
Approximately 95% of the cupric oxide film on the surface of the circuit is dissolved and removed by immersing it in 55 ° C for 3 minutes (post dip)
did.
【００２１】次に、ベンゾトリアゾールの３ｇ／１の水
溶液を調整し、７０℃で１分間浸漬することにより、回
路表面に防錆皮膜を形成（防錆処理）した。次に、十分
純水で洗浄した後、９０℃で６０分間乾燥した。Next, a 3 g / 1 aqueous solution of benzotriazole was prepared and immersed at 70 ° C. for 1 minute to form an anticorrosion film on the circuit surface (anticorrosion treatment). Then, after sufficiently washing with pure water, the resultant was dried at 90 ° C. for 60 minutes.
【００２２】このようにして製造した、中間層の両面
に、ガラス布基材にエポキシ樹脂を含浸乾燥して製造し
た、厚み０．１ｍｍのプリプレグ（三菱ガス化学（株）
製ＧＥＰＬ−１７０）を、３枚づつ重ねると共に、さら
にその外側に厚み１８μの銅箔を重ね、３０ｋｇ／ｃｍ
2 、１７０℃、６０分間積層成形することにより、４層
プリント配線板を得た。この積層成形は中間層の処理後
１日以内に行った。A prepreg having a thickness of 0.1 mm (manufactured by Mitsubishi Gas Chemical Co., Inc.) manufactured by impregnating and drying an epoxy resin on a glass cloth base material on both surfaces of the intermediate layer thus manufactured.
GEPL-170) made by 3 sheets, and a copper foil having a thickness of 18μ is further placed on the outer side thereof, and 30 kg / cm.
2 , 4-layer printed wiring board was obtained by laminating and molding at 170 ° C. for 60 minutes. The lamination molding was performed within 1 day after the treatment of the intermediate layer.
【００２３】次に、４層プリント配線板に０．４ｍｍφ
のドリルビットを用いて、回転数８０，０００ｒｐｍ、
送り速度１．６ｍ／ｍｉｎ（２０μ／ｒｅｖ）のドリル
条件で穴あけした。次にデスミア処理、無電解メッキ処
理、電気メッキ処理（硫酸銅浴）をした。Next, 0.4 mmφ is formed on the four-layer printed wiring board.
With a drill bit of 80,000 rpm,
Drilling was performed under a drill condition of a feed rate of 1.6 m / min (20 μ / rev). Next, desmear treatment, electroless plating treatment, and electroplating treatment (copper sulfate bath) were performed.
【００２４】こうして処理した、プリント配線板のスル
ーホール部を、中間層が十分良く観察できるまで水平研
磨して、ハローの発生状況を顕微鏡で観察した。観察場
所は、穴あけ初期（１〜５００穴）とそれ以後（１００
１〜１５００穴）の２箇所とした。４層プリント配線板
における内層銅箔と樹脂との層間接着力を測定した。表
１に処理条件、ハロー大きさ、内層接着力を示した。The through hole portion of the printed wiring board thus treated was horizontally polished until the intermediate layer could be observed sufficiently well, and the state of halo generation was observed with a microscope. The observation place is at the beginning of drilling (1 to 500 holes) and thereafter (100 holes).
1 to 1500 holes). The interlayer adhesive force between the inner layer copper foil and the resin in the four-layer printed wiring board was measured. Table 1 shows the treatment conditions, halo size, and inner layer adhesive strength.
【００２５】実施例２ 処理工程の条件を、プレディップ２分、ブラックオキサ
イド４分、ポストディップ６分、防錆処理２分に変化さ
せたことを除いて、実施例１と全く同様にして行った。 実施例３ 処理工程の条件を、ソフトエッチング３μｍに変化させ
たことを除いて、実施例１と全く同様にして行った。Example 2 The same procedure as in Example 1 was carried out except that the treatment conditions were changed to 2 minutes for pre-dip, 4 minutes for black oxide, 6 minutes for post-dip, and 2 minutes for anticorrosion treatment. It was Example 3 The procedure of Example 1 was repeated, except that the condition of the treatment process was changed to 3 μm of soft etching.
【００２６】実施例４ 処理工程の条件を、ソフトエッチング３μｍ、ブラック
オキサイド２分、ポストディップ２分、防錆処理１分に
変化させたことを除いて、実施例１と全く同様にして行
った。 実施例５ 積層成形を、中間層処理後７日間放置した後に行った他
は実施例１と全く同様にして行った。Example 4 Except that the treatment conditions were changed to 3 μm for soft etching, 2 minutes for black oxide, 2 minutes for post-dip, and 1 minute for rust-prevention treatment, the same procedure as in Example 1 was carried out. . Example 5 Laminate molding was carried out in exactly the same manner as in Example 1 except that the molding was carried out after standing for 7 days after the intermediate layer treatment.
【００２７】比較例１ ポストディップ処理、防錆処理を行わないことを除い
て、実施例１と全く同様にして行った。 比較例２ 防錆処理を行わないことを除いて、実施例１と全く同様
にして行った。 比較例３ 防錆処理を行わないことを除いて、実施例５と全く同様
にして行った。 比較例４ ソフトエッチング量を、０．５μｍとしたことを除い
て、実施例１と全く同様にして行った。Comparative Example 1 The same procedure as in Example 1 was carried out except that post dip treatment and rust prevention treatment were not performed. Comparative Example 2 The procedure of Example 1 was repeated, except that no rust-proofing treatment was performed. Comparative Example 3 The same procedure as in Example 5 was carried out except that no antirust treatment was performed. Comparative Example 4 The procedure of Example 1 was repeated, except that the soft etching amount was 0.5 μm.
【００２８】[0028]
【表１】 実施例 比較例 処理条件、測定項目＆単位 1 2 3 4 5 * 1 2 3 * 4 ソフトエッチング量 (μｍ) 1.5 1.5 3 3 1.5 1.5 1.5 1.5 0.5 プレディップ (分) 1 2 1 1 1 1 1 1 1 ブラックオキサイド (分) 3 4 3 2 3 3 3 3 3 ポストディップ (分) 3 6 3 2 3 - 3 3 3防錆処理 (分) 1 2 1 1 1 - - - 1 ハロー大きさ 1-500 穴 0 0 0 0 0 250 60 40 100 (μｍ) 1001-1500穴 0 0 0 0 0 200 40 40 80 内層接着力 (kg/cm) 1.3 1.2 1.4 1.4 1.4 0.3 1.2 1.2 1.0 ＊ 実施例５、比較例３は処理後７日間放置してから積層成形を行った。[Table 1]Example Comparative example Processing conditions, measurement items & units 1 2 3 4 5 * 1 2 3 * 4 Soft etching amount (μm) 1.5 1.5 3 3 1.5 1.5 1.5 1.5 0.5 Predip (min) 1 2 1 1 1 1 1 1 1 Black oxide (min) 3 4 3 2 3 3 3 3 3 Post dip (min) 3 6 3 2 3-3 3 3Rust prevention treatment (min) 1 2 1 1 1---1 Halo size 1-500 hole 0 0 0 0 0 250 60 40 100 (μm) 1001-1500 hole 0 0 0 0 0 200 40 40 80 Inner layer adhesive strength (kg / cm) 1.3 1.2 1.4 1.4 1.4 0.3 1.2 1.2 1.0 * In Example 5 and Comparative Example 3, after the treatment, the laminate was left for 7 days and then laminated.
【００２９】[0029]
【発明の効果】以上、詳細な説明及び、実施例から本発
明の処理方法による多層プリント配線板は、ハロー或い
はピンクリングの発生を完全に防止できることが明瞭で
ある。本発明のソフトエッチング処理は、ソフトエッチ
ング条件の選択で容易に達成され、防錆処理も既存の工
程に追加するのみである。きわめて簡単な変更で、信頼
性の向上した多層プリント配線板を生産性良く、製造可
能とするものであり、工業的な意義はきわめて高いもの
である。As described above, from the detailed description and the examples, it is apparent that the multilayer printed wiring board according to the processing method of the present invention can completely prevent the occurrence of halo or pink ring. The soft etching treatment of the present invention is easily achieved by selecting the soft etching conditions, and the rust prevention treatment is only added to the existing process. The multilayer printed wiring board with improved reliability can be manufactured with high productivity by a very simple change, and has an extremely high industrial significance.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 田中 恭夫 東京都葛飾区新宿６丁目１番１号 三菱瓦 斯化学株式会社東京工場内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yasuo Tanaka 6-1, 1-1 Shinjuku, Katsushika-ku, Tokyo Mitsubishi Gas Chemical Co., Ltd. Tokyo factory
Claims (5)
性のアルカリ水溶液で処理し、３０〜６０ｍｇ／ｄｍ2
の酸化銅の皮膜を形成した後、この銅の回路の表面の酸
化物皮膜を、ｐＨ３．５〜４．０に調整した酸性キレー
ト溶液により９０〜９９％溶解除去し、更に防錆処理液
で銅の回路表面に防錆皮膜を形成することを特徴とする
内層銅箔の処理方法。1. A copper circuit provided on an inner layer circuit board is treated with an oxidizing aqueous alkaline solution to obtain 30 to 60 mg / dm 2.
After forming the copper oxide film of, the oxide film on the surface of the copper circuit is dissolved and removed by 90 to 99% with an acidic chelate solution adjusted to pH 3.5 to 4.0, and further with a rust preventive treatment liquid. A method for treating an inner copper foil, which comprises forming an anticorrosive film on a copper circuit surface.
理する前に、銅の回路表面を１．０〜３．０μｍソフト
エッチングする請求項１に記載の内層銅箔処理方法。2. The inner layer copper foil treating method according to claim 1, wherein the copper circuit surface is soft-etched by 1.0 to 3.0 μm before the copper circuit provided on the inner layer circuit board is oxidized.
が、アルカリ性水溶液と、アルカリ性の亜塩素酸ナトリ
ウム水溶液の２段処理である事を特徴とする請求項１に
記載の内層銅箔の処理方法。3. The method for treating an inner layer copper foil according to claim 1, wherein the treatment with the oxidizing alkaline aqueous solution is a two-step treatment of an alkaline aqueous solution and an alkaline sodium chlorite aqueous solution.
四酢酸塩と、鉱酸もしくは有機酸からなる溶液である請
求項１に記載の内層銅箔の処理方法。4. The method for treating an inner copper foil according to claim 1, wherein the acidic chelate solution is a solution containing ethylene dian tetraacetate and a mineral acid or an organic acid.
のベンゾトリアゾール水溶液であり、処理温度３０〜８
０℃で、０．５〜５分間浸漬処理する請求項１に記載の
内層銅箔処理方法。5. The anticorrosion treatment liquid is 0.5 to 5 g / 1 (liter).
Benzotriazole aqueous solution of 30 to 8
The inner layer copper foil treatment method according to claim 1, wherein the immersion treatment is performed at 0 ° C. for 0.5 to 5 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18134593A JP3332047B2 (en) | 1993-07-22 | 1993-07-22 | Processing method of inner layer copper foil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18134593A JP3332047B2 (en) | 1993-07-22 | 1993-07-22 | Processing method of inner layer copper foil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0738254A true JPH0738254A (en) | 1995-02-07 |
| JP3332047B2 JP3332047B2 (en) | 2002-10-07 |
Family
ID=16099083
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18134593A Expired - Lifetime JP3332047B2 (en) | 1993-07-22 | 1993-07-22 | Processing method of inner layer copper foil |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3332047B2 (en) |
Cited By (7)
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|---|---|---|---|---|
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| JP2002503041A (en) * | 1998-02-03 | 2002-01-29 | アトーテヒ ドイッチュラント ゲゼルシャフト ミット ベシュレンクテル ハフツング | Method for pretreatment of copper surfaces |
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1993
- 1993-07-22 JP JP18134593A patent/JP3332047B2/en not_active Expired - Lifetime
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002503040A (en) * | 1998-02-03 | 2002-01-29 | アトーテヒ ドイッチュラント ゲゼルシャフト ミット ベシュレンクテル ハフツング | Solutions and methods for pretreating copper surfaces |
| JP2002503041A (en) * | 1998-02-03 | 2002-01-29 | アトーテヒ ドイッチュラント ゲゼルシャフト ミット ベシュレンクテル ハフツング | Method for pretreatment of copper surfaces |
| JP2005306023A (en) * | 2004-03-25 | 2005-11-04 | Nippon Steel Chem Co Ltd | Method for surface treating of copper foil and for manufacturing copper-clad laminated board |
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| WO2010050266A1 (en) * | 2008-10-27 | 2010-05-06 | 日立化成工業株式会社 | Method for surface treatment of copper and copper |
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| JP2018016886A (en) * | 2016-07-15 | 2018-02-01 | ナミックス株式会社 | Production method of copper foil used for printed wiring board |
| WO2019093077A1 (en) * | 2017-11-10 | 2019-05-16 | ナミックス株式会社 | Object having roughening-treated copper surface |
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