JPS5974281A - Removing solution for tin or tin alloy - Google Patents
Removing solution for tin or tin alloyInfo
- Publication number
- JPS5974281A JPS5974281A JP18298082A JP18298082A JPS5974281A JP S5974281 A JPS5974281 A JP S5974281A JP 18298082 A JP18298082 A JP 18298082A JP 18298082 A JP18298082 A JP 18298082A JP S5974281 A JPS5974281 A JP S5974281A
- Authority
- JP
- Japan
- Prior art keywords
- tin
- fluorine
- contg
- ion
- stripping 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
-
- C—CHEMISTRY; METALLURGY
- C23—COATING 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
- C23F—NON-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
- C23F1/00—Etching metallic material by chemical means
- C23F1/44—Compositions for etching metallic material from a metallic material substrate of different composition
-
- 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
- H05K3/02—Apparatus 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
- H05K3/06—Apparatus 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
- H05K3/067—Etchants
Abstract
Description
【発明の詳細な説明】
本発明は錫又は錫合金の剥離液に関するものであり、更
に詳細に述べれば銅基質からその基質を損傷する事なし
に浸漬溶解法又はスプレィ溶解法で錫又は錫合金を選択
的に短時間で剥離し、且つ。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a stripping solution for tin or tin alloys, and more particularly, the present invention relates to a stripping solution for tin or tin alloys, and more particularly, to remove tin or tin alloys from a copper substrate by an immersion melting method or a spray melting method without damaging the substrate. selectively peels off in a short time, and.
白色沈澱物の生成を極力防止した錫又は錫合金の剥離液
である。This is a tin or tin alloy stripping solution that prevents the formation of white precipitates as much as possible.
従来、銅基質に付着した半田は例えば硼フッ化水素酸と
過酸化水素とを含む水溶液を用いて、これに銅基質を浸
漬する事により除去されるが、このような剥離液では酸
の作用にまり鋼の溶解量も少なくない。又過酸化水素と
酸との混合水溶液は銅基質から錫又は錫合金を剥離する
事に利用されているが、この剥離液で処理すると錫又は
錫合金が剥離された後、錫が再び鋼上に析出する傾向が
ある。このため、再付着した被膜状の白色沈澱物を除去
するにはゾラシかげ等の追加的剥離操作な要し、剥離工
程が煩雑になる。又、長期間にわたる操業では多量の白
色沈澱物を生成する。Conventionally, solder attached to a copper substrate is removed by immersing the copper substrate in an aqueous solution containing, for example, borofluoric acid and hydrogen peroxide; The amount of melted steel is also not small. Also, a mixed aqueous solution of hydrogen peroxide and acid is used to strip tin or tin alloy from a copper substrate, but when treated with this stripping solution, after the tin or tin alloy is stripped, the tin is returned to the steel. tends to precipitate. Therefore, in order to remove the re-deposited film-like white precipitate, an additional peeling operation such as shading is required, making the peeling process complicated. In addition, a large amount of white precipitate is produced during long-term operation.
その他の剥離液成分にはクロム酸等も使用されているが
、有毒物質を発生し、公害防止に多大の設備と費用を要
し、又、環境衛生上好ましくない。Chromic acid and the like are also used as other stripping solution components, but they generate toxic substances, require a large amount of equipment and expense to prevent pollution, and are unfavorable in terms of environmental hygiene.
本発明による剥離液は通常の無機酸及び／又は゛有機酸
を主成分としているので長期の操業により発生する沈澱
生成を防止し、錫又は錫合金の溶解が迅速に行なわれる
。又、イオウ原子を含有しておらず環溝成員として＝Ｎ
Ｈ又は三Ｎの形で窒素原子を含有している複素環式化合
物が含まれていて、この化合物が銅表面に吸着されて銅
の溶解と錫イオンの銅表面への再付着を防止する事がで
き又。Since the stripping solution according to the present invention mainly contains ordinary inorganic acids and/or organic acids, it prevents the formation of precipitates that occur during long-term operation, and quickly dissolves tin or tin alloy. Also, it does not contain a sulfur atom and as a ring groove member =N
Contains a heterocyclic compound containing nitrogen atoms in the form of H or 3N, which is adsorbed on the copper surface and prevents the dissolution of copper and the redeposition of tin ions to the copper surface. I can do it again.
銅の酸化が防止される効果が得られる。The effect of preventing copper oxidation can be obtained.
本発明は以上の９口＜、従来の欠点を改善し、＠基質か
らその基質を損傷する事なしに錫又は錫合金を剥離する
のに適した酸性剥離液である。The present invention is an acidic stripping solution that improves the above-mentioned drawbacks of the prior art and is suitable for stripping tin or tin alloys from a substrate without damaging the substrate.
本発明の剥離液は以下の成分から構成される。The stripping solution of the present invention is composed of the following components.
本発明の第一成分はフッ素含有錯イオンであり。The first component of the present invention is a fluorine-containing complex ion.
例えば硼フッ化水素酸イオン（ＢＦ４−）、 フッ化
チタン酸イオン（ＴｉＦ”−）、フッ化硅酸イオン（Ｓ
正、２′″）、フッ化アルミン酸イオン（ＡｌＦ２）、
等である。For example, borohydrofluoride ion (BF4-), fluorotitanate ion (TiF"-), fluorosilicate ion (S
Positive, 2′″), fluoroaluminate ion (AlF2),
etc.
フッ素含有錯イオンは溶解錫イオンを安定化し。Fluorine-containing complex ions stabilize dissolved tin ions.
酸及び促進剤との共存で酸化作用を促進し、その相剰作
用により錫又は錫合金を迅速に剥離する。。Coexistence with an acid and an accelerator promotes oxidation, and their mutual action quickly strips tin or tin alloy. .
錫又は錫合金は酸性溶液のみでも溶解するがその反応は
極めて遅く、実用にはならない。Tin or tin alloys can be dissolved in acidic solutions alone, but the reaction is extremely slow and is not of practical use.
フッ素含有錯イオンの濃度はフッ素量にして。The concentration of fluorine-containing complex ions is expressed as the amount of fluorine.
好ましくは０．１〜３５０ Ｖｌ、より好ましくは３〜
２５０ Ｖｌの濃度範囲で使用する。フッ素含有錯イオ
ンを０．１ ｖｌ以下で使用した場合には上記の効果が
期待できず、又、５５０ ｖ１以上ではそれ以上の大ぎ
な効果が期待できない。Preferably 0.1-350 Vl, more preferably 3-350 Vl
Used in a concentration range of 250 Vl. If the fluorine-containing complex ion is used at 0.1 vl or less, the above effect cannot be expected, and if it is 550 v1 or more, no greater effect can be expected.
本発明に於ける第二成分は沈澱防止添加剤としてのフッ
化物或いは、その塩である。フッ素含有錯イオンのみで
も沈澱防止効果は多少あるが、その効果は充分満足でき
るものではない。The second component in the present invention is a fluoride or a salt thereof as an anti-settling additive. Although fluorine-containing complex ions alone have some effect on preventing precipitation, the effect is not fully satisfactory.
添加剤濃度の効果はフッ素量にして０．０５〜１５０ｙ
−／ｌで白色沈澱の生成を著しく防止する事がわかった
。０．０５ｖｌ以下では白色沈澱防止効果か認められず
、又、１５０ｔ／Ａ！以上ではそれ以上の大きな効果が
期待できず実用上不経済でもあり、設備・装置などの腐
蝕、或いは作業環境の悪化等の問題も生じる。従って、
沈澱防止添加剤であるフッ化物或いはその塩の濃度は、
０．０５〜１５０ ＰＩ３が好ましい。The effect of additive concentration is 0.05 to 150y in terms of fluorine amount.
-/l was found to significantly prevent the formation of white precipitate. At 0.05vl or less, no white precipitation prevention effect was observed, and at 150t/A! The above methods cannot be expected to produce any greater effects and are uneconomical in practice, and also cause problems such as corrosion of equipment and devices and deterioration of the working environment. Therefore,
The concentration of fluoride or its salt, which is an anti-settling additive, is
0.05-150 PI3 is preferred.
本発明に於ける酸としては、例えば塩酸、硝酸。Examples of acids in the present invention include hydrochloric acid and nitric acid.
硫酸等の無機酸及び蓚酸、スルファミノ酸、クエン酸等
の有機酸が挙げられるが、錫又は錫合金を溶解して溶液
を作る酸か、又は一旦溶液を形成した後、沈澱を生じる
ような酸のいづれかであれば良い。Examples include inorganic acids such as sulfuric acid, and organic acids such as oxalic acid, sulfamino acid, and citric acid. Any one of these is fine.
又、酸の濃度は０．１規定以下では錫又は錫合金の溶解
力が実用的に期待できず１０規定を越えると逆に溶解が
減じてくる。Furthermore, if the concentration of acid is less than 0.1N, it cannot be expected to have a practical ability to dissolve tin or a tin alloy, and if it exceeds 10N, the dissolution will decrease.
本発明に於ける銅インヒビターとしては＝ＮＨ又は＝Ｎ
の形で窒素原子を含有している複素環式化合物で、イオ
ウ原子を含有せず酸性溶液に溶解可能なものであり１例
えばピラゾール、イミダゾール、トリアゾール及びこれ
らの誘導体が挙げられる。The copper inhibitor in the present invention is =NH or =N
It is a heterocyclic compound containing a nitrogen atom in the form of a sulfur atom and is soluble in an acidic solution. Examples include pyrazoles, imidazoles, triazoles, and derivatives thereof.
本発明の剥離液は以上の成分を組み合わせた液組成であ
るが上記の成分のほかに他の物質を添加する事ができる
。例えば過酸化水素や過酸イオン及びこれらの安定化剤
として尿素、アルコール等を添加する事ができる。The stripping solution of the present invention has a liquid composition that combines the above-mentioned components, but other substances can be added in addition to the above-mentioned components. For example, hydrogen peroxide, peroxide ions, and their stabilizers such as urea and alcohol can be added.
以上１本発明では沈澱の生成を防止するために錫又は錫
合金の剥離を長期にわたって円滑に行なえるようにした
ものである。As mentioned above, in the present invention, tin or a tin alloy can be peeled off smoothly over a long period of time in order to prevent the formation of precipitates.
又１本発明に於ける剥離液は錫又は錫合金な除去できる
ならばどのような方法で使用しても良く。Furthermore, the stripping solution in the present invention may be used in any manner as long as it can remove tin or tin alloys.
例えば従来から一般的に用いられている浸漬法の他にス
プレィ法などの方法を用いる事ができる。For example, in addition to the conventionally commonly used dipping method, a spray method can be used.
次に本発明の実施例を示す。Next, examples of the present invention will be shown.
実施例 １
硝酸 １００ Ｖ１硼フ
ッ化水素酸 ６００インヒビター（
例えばイミダゾール）１０過酸化水素
１０フツ化アンモン １
００水 総量が１１になるまで添加する。Example 1 Nitric acid 100 V1 borohydrofluoric acid 600 inhibitor (
(e.g. imidazole) 10 hydrogen peroxide
10 ammonium fluoride 1
00 water Add until the total amount reaches 11.
５０Ｘ５０ｉｍの大きさの銅で被覆したフェノール板に
錫６０チ及び鉛４０％を含む半田でメッキした板（半田
厚１０μ）を室温で上記の組成からなる剥離液に浸漬し
たところ、半田が６分間で板から完全に除去された。半
田を板から除去した後、この銅で被覆された板を剥離液
に更に６０分間浸漬し続けた。剥離液から板をとりだし
、その銅表面を検査した結果、光沢があり、銅表面には
何ら異状が認められなかった。更に半田メッキした板を
上記の組成からなる剥離液に溶解し続け、半田溶解量が
８０ Ｖ′ｌになるまで溶解後１日放置して、沈澱の有
無を調べたが白色沈澱物は生成しなかった。When a plate (solder thickness: 10μ) plated with a solder containing 60% tin and 40% lead on a copper-coated phenol plate measuring 50×50im was immersed in a stripping solution having the above composition at room temperature, the solder was removed for 6 minutes. completely removed from the board. After the solder was removed from the board, the copper coated board was kept immersed in the stripping solution for an additional 60 minutes. The board was removed from the stripping solution and its copper surface was inspected. As a result, it was found to be shiny and no abnormality was observed on the copper surface. Furthermore, the solder-plated plate was continued to be dissolved in a stripping solution having the above composition, and after dissolving it was left for one day until the solder dissolution amount reached 80 V'l, and the presence or absence of precipitate was examined, but no white precipitate was formed. There wasn't.
これに対し、フッ化アンモン無添加の時は半田溶解量が
４０ ｖｌ で沈澱が認められた。On the other hand, when ammonium fluoride was not added, precipitation was observed when the amount of solder melted was 40 vl.
実施例 ２
硝酸 ３０ｕＰ／ｌ硼フツ化
水素酸 ２００ Ｖｌインヒビター（例
えばイミダゾール） １０ＶＩＪ過酸化水素
１０ ｔ／１４０チフツ化水素
５０ ｔ／１水 総量が１１になるま
で添加する。Example 2 Nitric acid 30 uP/l borofluoric acid 200 Vl inhibitor (e.g. imidazole) 10 VIJ Hydrogen peroxide
10 t/140 hydrogen thiefide
50 t/1 water Add until the total amount becomes 11.
実施例１と同条件でメッキされた半田板を室温で上記剥
離液に浸漬したところ６分間で板から完全に除去された
。半田を板から除去した後、この鋼で被覆された板を剥
離液に更に６０分間浸漬し続けた。剥離液から板をとり
だし、その銅表面を検査した結果、光沢があり、銅表面
には何ら異状が認められなかった。更に半田メッキした
板を上記の組成からなる剥離液に浴解し続け、半田溶解
量が９０ Ｖｌになるまで溶解した。１日放置しても白
色沈澱物は生成しなかった。When a solder plate plated under the same conditions as in Example 1 was immersed in the stripping solution at room temperature, it was completely removed from the plate in 6 minutes. After the solder was removed from the board, the steel coated board was kept immersed in the stripper solution for an additional 60 minutes. The board was removed from the stripping solution and its copper surface was inspected. As a result, it was found to be shiny and no abnormality was observed on the copper surface. Further, the solder-plated plate was continued to be bath-dissolved in a stripping solution having the above composition until the amount of solder dissolved reached 90 Vl. No white precipitate was formed even after being left for one day.
これに対し、４０チフツ化水素無添加の時は半田溶解量
が４０ Ｆ／／ｌで沈澱の生成が認められた二以上の事
より７ツ化物の添加が沈澱生成を著しく抑制し沈澱防止
に充分効果のある事がわかった。On the other hand, when hydrogen 40 thiefide was not added, the formation of precipitates was observed at a solder dissolution amount of 40 F//l.The addition of 7 thiefide significantly suppressed the formation of precipitates and was effective in preventing precipitation. It turned out to be quite effective.
（ほか３名）(3 others)
Claims (1)
してそれぞれ０．１〜３５０ ｆｌ−／ｌ及び０．０５
〜１５０ Ｖｌ含む錫又は錫合金の酸性剥離液。 ２）フッ素含有錯イオン及びフッ素イオンをフッ素量に
してそれぞれ０．１〜３５０ ｆｉ−／ｌ及び０．０５
〜１５０ Ｖｌを含む酸性溶液にイオウ原子を含有して
おらず環溝成員として−ＮＨ又は＝Ｎの形で窒素原子を
含有している複素環式化合物を添加した錫又は錫合金の
酸性剥離液。[Claims] 1) Fluorine-containing complex ions and fluorine ions have a fluorine content of 0.1 to 350 fl-/l and 0.05, respectively.
Acidic stripper of tin or tin alloy containing ~150 Vl. 2) Fluorine-containing complex ions and fluorine ions have a fluorine content of 0.1 to 350 fi-/l and 0.05, respectively.
An acidic stripping solution for tin or tin alloys in which a heterocyclic compound containing no sulfur atoms and containing a nitrogen atom in the form of -NH or =N as a ring groove member is added to an acidic solution containing ~150 Vl. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18298082A JPS6015707B2 (en) | 1982-10-20 | 1982-10-20 | Tin or tin alloy stripper |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18298082A JPS6015707B2 (en) | 1982-10-20 | 1982-10-20 | Tin or tin alloy stripper |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5974281A true JPS5974281A (en) | 1984-04-26 |
| JPS6015707B2 JPS6015707B2 (en) | 1985-04-20 |
Family
ID=16127657
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18298082A Expired JPS6015707B2 (en) | 1982-10-20 | 1982-10-20 | Tin or tin alloy stripper |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6015707B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000043574A1 (en) * | 1999-01-25 | 2000-07-27 | Alpha Fry Limited | Process for the recovery of tin, tin alloys or lead alloys from printed circuit boards |
| KR100710481B1 (en) | 2004-08-31 | 2007-04-24 | 한국생산기술연구원 | Composition for stripping tin and stripping method using the same |
| EP2196560A2 (en) * | 2008-12-15 | 2010-06-16 | General Electric Company | Methods of manufacturing casted articles, and systems |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0222895Y2 (en) * | 1986-10-16 | 1990-06-21 |
-
1982
- 1982-10-20 JP JP18298082A patent/JPS6015707B2/en not_active Expired
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000043574A1 (en) * | 1999-01-25 | 2000-07-27 | Alpha Fry Limited | Process for the recovery of tin, tin alloys or lead alloys from printed circuit boards |
| JP2003508624A (en) * | 1999-01-25 | 2003-03-04 | アルフア フライ リミテッド | How to recover tin, tin alloy or lead alloy from printed circuit board |
| KR100710481B1 (en) | 2004-08-31 | 2007-04-24 | 한국생산기술연구원 | Composition for stripping tin and stripping method using the same |
| EP2196560A2 (en) * | 2008-12-15 | 2010-06-16 | General Electric Company | Methods of manufacturing casted articles, and systems |
| EP2196560A3 (en) * | 2008-12-15 | 2014-01-22 | General Electric Company | Methods of manufacturing casted articles, and systems |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6015707B2 (en) | 1985-04-20 |
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