JPS6343470B2 - - Google Patents

Info

Publication number
JPS6343470B2
JPS6343470B2 JP56004321A JP432181A JPS6343470B2 JP S6343470 B2 JPS6343470 B2 JP S6343470B2 JP 56004321 A JP56004321 A JP 56004321A JP 432181 A JP432181 A JP 432181A JP S6343470 B2 JPS6343470 B2 JP S6343470B2
Authority
JP
Japan
Prior art keywords
nickel
etching solution
etching
chemical nickel
plating
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
JP56004321A
Other languages
Japanese (ja)
Other versions
JPS57116775A (en
Inventor
Kazuhiko Nakamura
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toshiba Corp
Original Assignee
Toshiba Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Toshiba Corp filed Critical Toshiba Corp
Priority to JP56004321A priority Critical patent/JPS57116775A/en
Publication of JPS57116775A publication Critical patent/JPS57116775A/en
Publication of JPS6343470B2 publication Critical patent/JPS6343470B2/ja
Granted legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23FNON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00Etching metallic material by chemical means
    • C23F1/10Etching compositions
    • C23F1/14Aqueous compositions
    • C23F1/16Acidic compositions
    • C23F1/28Acidic compositions for etching iron group metals
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23FNON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00Etching metallic material by chemical means
    • C23F1/44Compositions for etching metallic material from a metallic material substrate of different composition
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00Apparatus or processes for manufacturing printed circuits
    • H05K3/02Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/06Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
    • H05K3/067Etchants

Description

【発明の詳細な説明】 本発明は2種以上の金属のうち、ニツケルのみ
を選択的に除去するのに適したエツチング液に関
し、特に銅,錫,ニツケルのうちのニツケルのみ
を除去する場合に有効なエツチング液に係る。
[Detailed Description of the Invention] The present invention relates to an etching solution suitable for selectively removing only nickel among two or more metals, particularly when removing only nickel among copper, tin, and nickel. Concerning an effective etching solution.

例えば、印刷配線板の製造においては、セミア
デイテイブ法という新しい方法が開発され、本出
願人は次に示すセミアデイテイブ法の改良方法を
既に提案している。即ち、この方法は絶縁板の両
面にアクリロニトルゴムと熱硬化性樹脂を主成分
とする化学メツキ用接着剤を塗布し、熱硬化せし
めて接着剤層を形成した後、ドリル等でスルホー
ル孔をあけた後、親水化、活性化し、ひきつづき
化学ニツケルメツキ処理を施してスルホール孔を
含む絶縁板全面に化学ニツケルメツキ層を形成す
る。次いで、スルホール孔及び形成すべき回路パ
ターンを除く化学ニツケルメツキ層全面にメツキ
レジスト膜を被覆した後、電気銅メツキ処理を施
してスルホール孔内壁及び所定の回路パターンに
電気銅メツキ膜を形成する。その後、メツキレジ
スト膜を除去し、露出した化学ニツケルメツキ層
部分をエツチング液で溶解除去して化学ニツケル
メツキ層と電気銅メツキ膜からなる二層構造のス
ルホール、回路パターンを有する印刷配線板を造
る。この化学ニツケルメツキ層の溶解除去にあた
つては、電気銅メツキ膜もエツチング液に接触
し、電気銅メツキ膜をもエツチングされ電気抵抗
変化、場合によつては短絡を招く恐れがあるた
め、化学ニツケルメツキ層のみを選択的にエツチ
ングし得るエツチング液を用いることが印刷配線
板の信頼性向上の点で重要である。
For example, in the production of printed wiring boards, a new method called a semi-additive method has been developed, and the applicant has already proposed the following improved method of the semi-additive method. That is, in this method, a chemical plating adhesive mainly composed of acrylonitrile rubber and a thermosetting resin is applied to both sides of an insulating board, and after being thermosetted to form an adhesive layer, through holes are drilled with a drill or the like. After opening, the insulating plate is made hydrophilic and activated, followed by chemical nickel plating treatment to form a chemical nickel plating layer on the entire surface of the insulating board including the through holes. Next, a plating resist film is applied to the entire surface of the chemical nickel plating layer except for the through holes and the circuit pattern to be formed, and then an electrolytic copper plating process is performed to form an electrolytic copper plating film on the inner walls of the through holes and a predetermined circuit pattern. Thereafter, the plating resist film is removed, and the exposed chemical nickel plating layer portion is dissolved and removed using an etching solution to produce a printed wiring board having a two-layer structure consisting of a chemical nickel plating layer and an electrolytic copper plating film, and having through-holes and a circuit pattern. When dissolving and removing this chemical nickel plating layer, the electrolytic copper plating film also comes into contact with the etching solution, and the electrolytic copper plating film may also be etched, resulting in a change in electrical resistance and, in some cases, a short circuit. From the viewpoint of improving the reliability of printed wiring boards, it is important to use an etching solution that can selectively etch only the nickel plating layer.

ところで、上記化学ニツケルメツキ層の選択エ
ツチング液には、過酸化水素,燐酸,ベンゾトリ
アゾール,メタニトロベンゼンスルホン酸ソーダ
の組成からなるベンゾトリアゾール系溶液を用い
ていた。かかる組成のエツチング液は化学ニツケ
ルのように純度の低い(92〜98%)のニツケルで
も選択的にエツチングできる特長を有する。しか
しながら、このエツチング液は、組成中にメタニ
トロベンゼンスルホン酸ソーダを用いるために高
価格となること、短期間のエツチングで選択エツ
チング能力が低下しエツチング液を頻繁に交換し
なければならず、大量の使用済エツチング液が排
出されること、等の問題があつた。
By the way, as the selective etching solution for the chemical nickel plating layer, a benzotriazole solution consisting of hydrogen peroxide, phosphoric acid, benzotriazole, and sodium metanitrobenzenesulfonate was used. An etching solution having such a composition has the feature that it can selectively etch even nickel of low purity (92 to 98%), such as chemical nickel. However, this etching solution is expensive because it uses sodium metanitrobenzene sulfonate in its composition, and the selective etching ability decreases after short-term etching, requiring frequent replacement of the etching solution. There were problems such as the used etching solution being discharged.

これに対し、本発明者は上記問題点を克服すべ
く鋭意研究を重ねた結果、硫酸,過酸化水素水,
燐酸及びベンゾトリアゾールに塩化アンモニウム
を配合し、かつ各成分を所定の配合範囲に規定す
ることによつて、ニツケルを含む2種以上の金属
のうちのニツケルのみの選択エツチングに用いた
場合、該ニツケルの純度に影響されることなく、
かつ他の金属の変色、酸化などを招くことなくニ
ツケルを選択エツチングできると共に、その選択
エツチング能力を長期間持続できる安価なニツケ
ル用エツチング液を見い出した。
On the other hand, as a result of intensive research to overcome the above-mentioned problems, the present inventor has found that sulfuric acid, hydrogen peroxide solution,
When used for selective etching of only nickel among two or more metals including nickel by blending ammonium chloride with phosphoric acid and benzotriazole and specifying each component within a predetermined blending range, the nickel without being affected by the purity of
We have also discovered an inexpensive etching solution for nickel that can selectively etch nickel without causing discoloration or oxidation of other metals, and can maintain its selective etching ability for a long period of time.

すなわち、本発明は硫酸100〜200g/、過酸
化水素水50〜150g/、燐酸10〜30g/、ベ
ンゾトリアゾール1〜3g/及び塩化アンモニ
ウム0.05〜1g/の組成からなるものである。
That is, the composition of the present invention is 100 to 200 g of sulfuric acid, 50 to 150 g of hydrogen peroxide, 10 to 30 g of phosphoric acid, 1 to 3 g of benzotriazole, and 0.05 to 1 g of ammonium chloride.

本発明に係るニツケル用エツチング液中の各成
分割合を限定した理由は、各成分割合が上記範囲
を逸脱すると、ニツケルの選択エツチング性、そ
のエツチング能力が著しく損なわれるからであ
る。
The reason why the proportions of each component in the etching solution for nickel according to the present invention are limited is that if the proportion of each component deviates from the above range, the selective etching properties of nickel and its etching ability will be significantly impaired.

次に、本発明をセミアデイテイブ法による印刷
配線板の製造工程での化学ニツケルメツキ層の選
択エツチングに適用した例について説明する。
Next, an example in which the present invention is applied to selective etching of a chemical nickel plating layer in the manufacturing process of a printed wiring board by a semi-additive method will be described.

実施例 まず、積層板の両面にアクリロニトリルゴム40
重量部、レゾール型フエノール樹脂20重量部、ビ
スフエノール型エポキシ樹脂20重量部、シリカゲ
ル10重量部及び硬化剤10重量部をメチルエチルケ
トン―ブチロセロソルブ混合溶剤で溶解した化学
メツキ用接着剤をデイツプ方式で塗布し、風乾後
160℃で40分間乾燥し厚さ約30μmの接着剤層を
形成した。つづいて、この積層板の所定箇所をド
リルでスルホールをあけた後、接着剤層をクロム
酸―硫酸混液で親水化処理し、常法に従つて活性
化処理し、ひきつづき化学ニツケルメツキ浴に浸
漬し、厚さ1.0μmの化学ニツケルメツキ層を全面
に形成した。その後、スルホール孔内壁及び形成
すべき回路パターンを除く化学ニツケルメツキ層
全面にシルク印刷法によりメツキレジスト膜を被
覆し、乾燥後5〜20%硫酸溶液で活性化し、化学
ニツケルメツキ層を陰極として電気銅メツキ処理
を施してスルホール孔内壁及び回路パターンに厚
さ35μmの電気銅メツキ膜を形し、更に回路パタ
ーンの電気銅メツキ膜上にメツキレジスト膜をマ
スクとして錫メツキ膜を選択的に形成した。
Example First, acrylonitrile rubber 40% was applied to both sides of the laminate.
A chemical plating adhesive prepared by dissolving 20 parts by weight of a resol type phenolic resin, 20 parts by weight of a bisphenol type epoxy resin, 10 parts by weight of silica gel and 10 parts by weight of a hardening agent in a mixed solvent of methyl ethyl ketone and butyrocellosolve is prepared using a dip method. After applying and air drying
It was dried at 160° C. for 40 minutes to form an adhesive layer with a thickness of about 30 μm. Next, after drilling through holes in predetermined locations on the laminate, the adhesive layer was made hydrophilic with a chromic acid-sulfuric acid mixture, activated in a conventional manner, and then immersed in a chemical nickel plating bath. A chemical nickel plating layer with a thickness of 1.0 μm was formed on the entire surface. After that, a plating resist film is coated on the entire surface of the chemical nickel plating layer except for the inner walls of the through-holes and the circuit pattern to be formed by silk printing, and after drying, it is activated with a 5-20% sulfuric acid solution, and electrolytic copper plating is applied using the chemical nickel plating layer as a cathode. A 35 μm thick electrolytic copper plating film was formed on the inner wall of the through hole and the circuit pattern, and a tin plating film was selectively formed on the electrolytic copper plating film of the circuit pattern using the plating resist film as a mask.

次いで、メツキレジスト膜を剥離、除去した
後、非回路パターン部分である露出した化学ニツ
ケルメツキ層部分を下記組成のニツケル用エツチ
ング液(液温;30℃)で溶解除去して化学ニツケ
ルメツキ層と電気銅メツキ膜の二層構造のスルホ
ール、回路パターンを有し、さらに同パターンの
一部に錫メツキ膜が形成された印刷配線板を製造
した。
Next, after peeling off and removing the plating resist film, the exposed chemical nickel plating layer portion, which is a non-circuit pattern part, is dissolved and removed using an etching solution for nickel having the following composition (liquid temperature: 30°C), and the chemical nickel plating layer and electrolytic copper are removed. A printed wiring board was manufactured that had a two-layer plating film structure of through-holes and a circuit pattern, and further had a tin plating film formed on a part of the pattern.

(ニツケル用エツチング液) Γ 硫酸 150g/ Γ 過酸化水素水 100g/ Γ 燐酸 16g/ Γ ベンゾトリアゾール 1.5g/ Γ 塩化アンモニウム 0.2g/ しかして、本実施例において化学ニツケルメツ
キ層を上記組成のエツチング液で選択エツチング
する際、厚さ1.0μmの化学ニツケルメツキ層を約
6分間で溶解除去でき、かつこの時、電気銅メツ
キ膜、錫メツキ膜の変色、酸化は全く起きなかつ
た。その結果、スルホール、回路パターンの抵抗
が所期の値を有し、しかもエツチング液が溜り易
いスルホールでの断線がなく、更に錫メツキ膜上
に部品の端子等を良好に接続できる高信頼性の印
刷配線板を得ることができた。
(Etching solution for nickel) Γ Sulfuric acid 150g / Γ Hydrogen peroxide solution 100g / Γ Phosphoric acid 16g / Γ Benzotriazole 1.5g / Γ Ammonium chloride 0.2g / Therefore, in this example, the chemical nickel plating layer was etched with the etching solution having the above composition. During selective etching, a 1.0 μm thick chemical nickel plating layer could be dissolved and removed in about 6 minutes, and at this time, no discoloration or oxidation of the electrolytic copper plating film or tin plating film occurred. As a result, the resistance of the through-holes and circuit patterns has the desired value, there is no disconnection in the through-holes where etching solution tends to accumulate, and the terminals of components can be connected well on the tin-plated film with high reliability. We were able to obtain a printed wiring board.

また、従来のベンゾトリアゾール、燐酸、過酸
化水素水及びメタニトロベンゼンスルホン酸ソー
ダからなるエツチング液は前記膜厚の化学ニツケ
ルメツキ層を0.5程度エツチングすると、その
選択エツチング能力が喪失するのに対し、上記組
成のエツチング液では1〜2の面積の化学ニツ
ケルメツキ層を選択エツチングしても十分な選択
エツチング能力を有し、2倍以上の寿命をもつも
のであつた。
In addition, the conventional etching solution consisting of benzotriazole, phosphoric acid, hydrogen peroxide solution, and sodium metanitrobenzene sulfonate loses its selective etching ability after etching a chemical nickel plating layer of the above-mentioned thickness by about 0.5%, whereas the above-mentioned composition The etching solution had sufficient selective etching ability even when selectively etching a chemical nickel plating layer with an area of 1 to 2, and had a lifetime more than twice as long.

以上詳述した如く、本発明によればニツケルを
含む2種以上の金属のうちのニツケルのみの選択
エツチングに際し、該ニツケルの純度に影響され
ることなく、かつ他の金属の変色、酸化などを招
くことなくニツケルを選択エツチングできると共
に、その選択エツチング能力を長期間持続でき、
もつてセミアデイテイブ法により化学ニツケルメ
ツキ層と電気銅メツキ膜からなるスルホール及び
回路パターン、更には該パターン上に錫メツキ膜
を有する印刷配線板を製造する場合の化学ニツケ
ルメツキ層の選択エツチング等に有効である安価
なニツケル用エツチング液を提供できるものであ
る。
As described in detail above, according to the present invention, when selectively etching only nickel among two or more metals including nickel, it is possible to selectively etch only nickel without being affected by the purity of the nickel, and to prevent discoloration, oxidation, etc. of other metals. It is possible to selectively etch nickel without causing damage, and the selective etching ability can be maintained for a long period of time.
It is effective for selective etching of chemical nickel plating layers when producing through holes and circuit patterns made of chemical nickel plating layers and electrolytic copper plating films by semi-additive methods, and furthermore, printed wiring boards having tin plating films on the patterns. It is possible to provide an inexpensive etching solution for nickel.

Claims (1)

【特許請求の範囲】[Claims] 1 硫酸100〜200g/、過酸化水素水50〜150
g/、燐酸10〜30g/、ベンゾトリアゾール
1〜3g/及び塩化アンモニウム0.05〜1.0
g/の組成からなるニツケル用エツチング液。
1 Sulfuric acid 100-200g/, hydrogen peroxide solution 50-150g
g/, phosphoric acid 10-30 g/, benzotriazole 1-3 g/, and ammonium chloride 0.05-1.0
An etching liquid for nickel having a composition of g/g/g.
JP56004321A 1981-01-14 1981-01-14 Etching solution for nickel Granted JPS57116775A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP56004321A JPS57116775A (en) 1981-01-14 1981-01-14 Etching solution for nickel

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP56004321A JPS57116775A (en) 1981-01-14 1981-01-14 Etching solution for nickel

Publications (2)

Publication Number Publication Date
JPS57116775A JPS57116775A (en) 1982-07-20
JPS6343470B2 true JPS6343470B2 (en) 1988-08-30

Family

ID=11581191

Family Applications (1)

Application Number Title Priority Date Filing Date
JP56004321A Granted JPS57116775A (en) 1981-01-14 1981-01-14 Etching solution for nickel

Country Status (1)

Country Link
JP (1) JPS57116775A (en)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5869130A (en) * 1997-06-12 1999-02-09 Mac Dermid, Incorporated Process for improving the adhesion of polymeric materials to metal surfaces
US6146701A (en) * 1997-06-12 2000-11-14 Macdermid, Incorporated Process for improving the adhension of polymeric materials to metal surfaces
US6162503A (en) * 1997-06-12 2000-12-19 Macdermid, Incorporated Process for improving the adhesion of polymeric materials to metal surfaces
US6383272B1 (en) 2000-06-08 2002-05-07 Donald Ferrier Process for improving the adhesion of polymeric materials to metal surfaces
US6419784B1 (en) 2000-06-21 2002-07-16 Donald Ferrier Process for improving the adhesion of polymeric materials to metal surfaces
US6554948B1 (en) 2000-08-22 2003-04-29 Donald Ferrier Process for improving the adhesion of polymeric materials to metal surfaces
US7591956B2 (en) * 2006-05-03 2009-09-22 OMG Electronic Chemicals, Inc. Method and composition for selectively stripping nickel from a substrate
CN113265660B (en) * 2021-04-30 2023-03-17 光华科学技术研究院(广东)有限公司 Etching solution and application thereof

Also Published As

Publication number Publication date
JPS57116775A (en) 1982-07-20

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