CN1461822A - Stripping lqiuid nickel or nickel alloy - Google Patents
Stripping lqiuid nickel or nickel alloy Download PDFInfo
- Publication number
- CN1461822A CN1461822A CN03140715A CN03140715A CN1461822A CN 1461822 A CN1461822 A CN 1461822A CN 03140715 A CN03140715 A CN 03140715A CN 03140715 A CN03140715 A CN 03140715A CN 1461822 A CN1461822 A CN 1461822A
- Authority
- CN
- China
- Prior art keywords
- weight
- nickel
- stripping liquid
- hydrogen peroxide
- ammonium chloride
- 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
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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
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/28—Acidic compositions for etching iron group metals
-
- 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
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- ing And Chemical Polishing (AREA)
Abstract
The object of the invention is to provide an exfoliating solution used for selectively peeling nickel or nickel alloy film in high velocity without peeling metals other than nickel or nickel alloy, particularly copper or copper alloy and tin or tin alloy film. The invention provides an exfoliating solution for nickel or nickel alloy comprising a solution consisting of (a) hydrogen peroxide, (b) an inorganic acid, (c) a quaternary ammonium salt, and (d) a fatty group alcohol having carbon of number from 3 to 7.
Description
Invention field
The present invention relates to dissolve the stripping liquid of nickel and nickelalloy from the material selectivity that contains nickel or nickelalloy and other metals.Stripping liquid of the present invention can be used for the manufacturing of electronic units such as semiconductor product, printed circuit board (PCB).
Background technology
In the operation of the copper wiring of making printed circuit board (PCB), adopt the nickel plating film in order to shelter the copper wiring temporarily, but nickel plating Film Fractionation is the most at last removed.At this moment, because nearest printed circuit board (PCB) precise treatment more and more, so need to dissolve metal beyond the nickel plating film.
As the nickel stripping liquid, known have hydrogen peroxide-nitric acid system, hydrogen peroxide-fluoridize system, but all there is the problem of dissolved copper or copper alloy and tin or tin alloy (scolding tin) in arbitrary stripping liquid.And hydrogen peroxide-sulfuric acid-organic acid system exists the slow problem of the dissolution rate of nickel.Thereby, need realize the practicability of stripping liquid early, with nickel or optionally dissolving at a high speed of nickel alloy film.
Summary of the invention
The objective of the invention is to, be provided at the metal that does not dissolve beyond nickel or the nickelalloy, particularly not under the condition of dissolved copper or copper alloy thin films and tin or tin alloy film, nickel or nickel alloy film selectivity high speed dissolved stripping liquid.
The present inventor concentrates on studies, it found that, by in hydrogen peroxide-mineral acid system, adding nickel dissolution accelerator and dissolving metal inhibitor, can be under the condition of not dissolved copper or copper alloy thin films and tin or tin alloy film, nickel or nickel alloy film selectivity are dissolved at a high speed, thereby finished the present invention.
That is, the present invention relates to contain (a) hydrogen peroxide, (b) mineral acid, (c) quaternary amine and (d) carbon number be the aqueous solution of 3～7 fatty alcohol, promptly to the stripping liquid of nickel or nickelalloy.
Embodiment
Concentration of hydrogen peroxide of the present invention is 1～30 weight %, preferred 5～20 weight %.Concentration is during less than 1 weight %, and oxidation effectiveness is insufficient and can not get sufficient dissolution rate, and addition can not get better oxidation effectiveness when surpassing 30 weight %, and considering from economic angle can not be preferred.
Mineral acid can exemplify sulfuric acid, nitric acid, phosphoric acid, boric acid etc., wherein preferably sulfuric acid, nitric acid.The concentration of mineral acid is 1～30 weight %, preferred 10～25 weight %.Concentration can not get sufficient dissolution rate during less than 1 weight %, and addition can not get higher dissolution rate when surpassing 30 weight %, and considering from economic angle can not be preferred.
Quaternary amine has the effect as the dissolving metal inhibitor.As main material, can exemplify tetramethyl ammonium chloride (Tetramethyl ammonium chloride), Three methyl Benzene ammonio methacrylate (Trimethyl benzil ammonium chloride), triethylbenzene ammonio methacrylate (Triethyl benzil ammonium chloride), tributyl phenmethyl ammonium chloride (Tributylbenzil ammonium chloride), tri-n-octyl methyl ammonium chloride (Trioctyl methylammonium chloride), trimethyldodecane ammonium chloride (Trimethyl dodecylammonium chloride), trimethylammonium lauryl chlorination ammonium (Trimethyl lauryl ammoniumchloride), N-lauryl chloride pyridine (N-lauryl pyridium chloride), dimethyl chlorination tetramethyleneimine (Dimethyl pyrrolidinium chloride), trimethylphenyl amine bromide (Trimethyl phenyl ammonium bromide), triethylbenzene methyl brometo de amonio (Triethylbenzil ammonium bromide), 4 bromide (tetramethyl ammoniumbromide), tetraethylammonium bromide (tetraethyl ammonium bromide), four n normal-butyl bromination ammoniums (tetra-n-butyl ammonium bromide), dimethyl bromination tetramethyleneimine (dimethyl pyrrolidinium bromide), Tetramethylammonium iodide (tetramethylammonium iodide), tetrabutylammonium iodide (tetra-n-butyl ammonium iodide) etc.Wherein, preferred tetramethyl ammonium chloride, 4 bromide, trimethyldodecane ammonium chloride, trimethylammonium lauryl chlorination ammonium, dimethyl chlorination tetramethyleneimine are more preferably trimethyldodecane ammonium chloride, trimethylammonium lauryl chlorination ammonium, dimethyl chlorination tetramethyleneimine.
The concentration of quaternary amine is 0.01～1 weight %, and preferred 0.01～0.5 weight % is more preferably 0.05～0.5 weight %.Concentration can not get sufficient dissolving metal and suppresses effect during less than 0.01 weight %, and addition is when surpassing 1 weight %, and the dissolution rate of nickel descends and can not be preferred.
Carbon number is 3～7 fatty alcohol, has the effect as the nickel dissolution accelerator.As main material, can exemplify 1-propyl alcohol, 2-propyl alcohol, 1-butanols, 2-butanols, 3-butanols, isopropylcarbinol, 1-amylalcohol, 2-amylalcohol, 3-amylalcohol, primary isoamyl alcohol, 1-hexanol, 2-hexanol, 3-hexanol, 1-enanthol, 2-enanthol, 3-enanthol, 4-enanthol etc., wherein, preferred 1-propyl alcohol, 1-butanols, 2-butanols, 1-amylalcohol, 1-hexanol are more preferably 1-propyl alcohol, 1-butanols, 2-butanols.
The concentration of fatty alcohol is 0.1～10 weight %, and preferred 0.5～5 weight % is more preferably 0.5～3 weight %.Addition can not get the effect of sufficient as the nickel dissolution accelerator during less than 0.1 weight %, and addition is when surpassing 10 weight %, can not get better as the effect of nickel dissolution accelerator, and considering from economic angle can not be preferred.Fatty alcohol can add a kind ofly, also can add two or more.
For the use temperature of stripping liquid of the present invention, there is no particular limitation, but preferred 20～50 ℃.Use temperature is high more, and the dissolution rate of nickel is fast more, but when surpassing 50 ℃, and the decomposition of hydrogen peroxide is fierce and can not be preferred.
For the treatment process of utilizing stripping liquid of the present invention, there is no particular limitation, can utilize means such as dipping, spraying.In addition, for the treatment time, can suitably select according to the thickness of dissolved nickel film.
Embodiment
Utilize embodiment and comparative example below, describe the present invention in detail, but the present invention is not limited to following embodiment.
Embodiment 1
In stripping liquid as the aqueous solution that contains hydrogen peroxide 5 weight %, nitric acid 10 weight %, trimethyldodecane ammonium chloride 0.1 weight % and 1-propyl alcohol 1 weight %, with nickel plate sample (50 * 30 * 0.3mm), fine copper plate sample (50 * 30 * 0.3mm), implement the gold-plated tin lead of 10 μ m (tin: plumbous=9: 1) plate (50 * 30 * 0.3mm), flooded simultaneously 1 minute at 30 ℃.The dissolution rate of nickel, fine copper, tin alloy is as shown in table 1.
Embodiment 2
Use contains outside the stripping liquid of hydrogen peroxide 7 weight %, sulfuric acid 15 weight %, trimethylammonium lauryl chlorination ammonium 0.2 weight %, 1-butanols 1 weight %, implements and embodiment 1 identical operations.Its result is as shown in table 1.
Embodiment 3
Use contains outside the stripping liquid of hydrogen peroxide 3 weight %, nitric acid 10 weight %, dimethyl chlorination tetramethyleneimine 0.05 weight %, 2-butanols 1 weight %, implements and embodiment 1 identical operations.Its result is as shown in table 1.
Embodiment 4
Use contains outside the stripping liquid of hydrogen peroxide 5 weight %, nitric acid 10 weight %, tetramethyl ammonium chloride 0.05 weight %, 1-propyl alcohol 2 weight %, implements and embodiment 1 identical operations.Its result is as shown in table 1.Comparative example 1
Use contains outside the stripping liquid of nitric acid 10 weight %, trimethyldodecane ammonium chloride 0.1 weight %, 1-propyl alcohol 1 weight %, implements and embodiment 1 identical operations.Its result is as shown in table 1.Comparative example 2
Use contains outside the stripping liquid of hydrogen peroxide 5 weight %, trimethyldodecane ammonium chloride 0.1 weight %, 1-propyl alcohol 1 weight %, implements and embodiment 1 identical operations.Its result is as shown in table 1.Comparative example 3
Use outside the stripping liquid that adds hydrogen peroxide 5 weight %, nitric acid 10 weight %, 1-propyl alcohol 1 weight %, implement and embodiment 1 identical operations.Its result is as shown in table 1.Comparative example 4
Use contains outside the stripping liquid of hydrogen peroxide 5 weight %, nitric acid 10 weight %, trimethyldodecane ammonium chloride 0.1 weight %, implements and embodiment 1 identical operations.Its result is as shown in table 1.Comparative example 5
Use contains outside the stripping liquid of hydrogen peroxide 5 weight %, nitric acid 10 weight %, benzotriazole 0.1 weight %, 1-propyl alcohol 1 weight %, implements and embodiment 1 identical operations.Its result is as shown in table 1.
Table 1
| Dissolution rate (μ m/min) | |||
| ????Ni | ????Cu | ????Sn-Pb | |
| Embodiment 1 | ????5.5 | ????＜0.1 | ????＜0.1 |
| Embodiment 2 | ????3.0 | ????＜0.1 | ????＜0.1 |
| Embodiment 3 | ????5.5 | ????＜0.1 | ????＜0.1 |
| Embodiment 4 | ????6.0 | ????＜0.1 | ????＜0.1 |
| Comparative example 1 | ????＜0.1 | ????＜0.1 | ????＜0.1 |
| Comparative example 2 | ????＜0.1 | ????＜0.1 | ????＜0.1 |
| Comparative example 3 | ????4.5 | ????2.5 | ????＜0.1 |
| Comparative example 4 | ????＜0.1 | ????＜0.1 | ????＜0.1 |
| Comparative example 5 | ????3.0 | ????1.5 | ????＜0.1 |
As shown in table 1, stripping liquid of the present invention, the meltage of nickel is big, and the meltage of copper, tin-lead is few.
The invention effect
By stripper of the present invention, can selectively dissolve at a high speed nickel or nickel alloy film.
Claims (5)
1. the stripping liquid of nickel or nickelalloy, for contain (a) hydrogen peroxide, (b) mineral acid, (c) quaternary amine and (d) carbon number be the aqueous solution of 3～7 fatty alcohol.
2. stripping liquid according to claim 1 contains (a) hydrogen peroxide 1～30 weight %, (b) mineral acid 1～30 weight %, (c) quaternary amine 0.01～1 weight % and (d) fatty alcohol 0.1～10 weight %.
3. stripping liquid according to claim 1, mineral acid are be selected from sulfuric acid or nitric acid at least a.
4. stripping liquid according to claim 1, quaternary amine is for being selected from least a in trimethyldodecane ammonium chloride (trimethyl dodecyl ammonium chloride), trimethylammonium lauryl chlorination ammonium (trimethyl lauryl ammonium chloride) and the dimethyl chlorination tetramethyleneimine (dimethylpyrrolidinium chloride).
5. stripping liquid according to claim 1, fatty alcohol are to be selected from least a in 1-propyl alcohol, 1-butanols and the 2-butanols.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002157954A JP4019256B2 (en) | 2002-05-30 | 2002-05-30 | Nickel or nickel alloy stripper |
| JP157954/2002 | 2002-05-30 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1461822A true CN1461822A (en) | 2003-12-17 |
| CN1274880C CN1274880C (en) | 2006-09-13 |
Family
ID=29773555
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB031407153A Expired - Lifetime CN1274880C (en) | 2002-05-30 | 2003-05-30 | Stripping lqiuid nickel or nickel alloy |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP4019256B2 (en) |
| KR (1) | KR100938735B1 (en) |
| CN (1) | CN1274880C (en) |
| TW (1) | TW589402B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018232873A1 (en) * | 2017-06-22 | 2018-12-27 | 韦荣群 | Selective etching liquid for nickel |
| CN114156099A (en) * | 2021-12-06 | 2022-03-08 | 北京七星飞行电子有限公司 | Method for processing capacitor lead |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006286371A (en) * | 2005-03-31 | 2006-10-19 | Ngk Spark Plug Co Ltd | Method for manufacturing sparking plug |
| KR101298766B1 (en) | 2011-05-20 | 2013-08-21 | 주식회사 익스톨 | Etching solution composites for nickel, chrome, and/or nickel-chrome alloy and etching method using the etching solution composites |
| KR101495421B1 (en) * | 2013-05-03 | 2015-02-24 | 주식회사 포스코 | Gas detector, solution for quantitative analysis of nikel about nickel coated steel sheet and method using the same |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06322560A (en) * | 1993-05-07 | 1994-11-22 | Okuno Chem Ind Co Ltd | Nickel or nickel alloy coating film remover |
| JPH08311663A (en) * | 1995-05-18 | 1996-11-26 | Merutetsukusu Kk | Release liquid for nickel coating film or nickel alloy coating film |
| JPH10158869A (en) * | 1996-11-27 | 1998-06-16 | Nippon Hyomen Kagaku Kk | Chemical polishing liquid for iron-nickel alloy or iron-nickel-cobalt alloy and chemical polishing method therefor |
-
2002
- 2002-05-30 JP JP2002157954A patent/JP4019256B2/en not_active Expired - Lifetime
-
2003
- 2003-05-23 TW TW092113984A patent/TW589402B/en not_active IP Right Cessation
- 2003-05-29 KR KR1020030034323A patent/KR100938735B1/en active IP Right Grant
- 2003-05-30 CN CNB031407153A patent/CN1274880C/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018232873A1 (en) * | 2017-06-22 | 2018-12-27 | 韦荣群 | Selective etching liquid for nickel |
| CN114156099A (en) * | 2021-12-06 | 2022-03-08 | 北京七星飞行电子有限公司 | Method for processing capacitor lead |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4019256B2 (en) | 2007-12-12 |
| KR100938735B1 (en) | 2010-01-26 |
| CN1274880C (en) | 2006-09-13 |
| TW589402B (en) | 2004-06-01 |
| TW200401050A (en) | 2004-01-16 |
| KR20030094014A (en) | 2003-12-11 |
| JP2003342756A (en) | 2003-12-03 |
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Granted publication date: 20060913 |
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