WO2000075404A1 - Decapant electrolytique de l'argent et procede de decapage electrolytique - Google Patents

Decapant electrolytique de l'argent et procede de decapage electrolytique Download PDF

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Publication number
WO2000075404A1
WO2000075404A1 PCT/JP2000/002364 JP0002364W WO0075404A1 WO 2000075404 A1 WO2000075404 A1 WO 2000075404A1 JP 0002364 W JP0002364 W JP 0002364W WO 0075404 A1 WO0075404 A1 WO 0075404A1
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WO
WIPO (PCT)
Prior art keywords
acid
silver
electrolytic stripping
electrolytic
stripping agent
Prior art date
Application number
PCT/JP2000/002364
Other languages
English (en)
Japanese (ja)
Inventor
Akihiro Aiba
Original Assignee
Japan Energy Corporation
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 Japan Energy Corporation filed Critical Japan Energy Corporation
Publication of WO2000075404A1 publication Critical patent/WO2000075404A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F5/00—Electrolytic stripping of metallic layers or coatings

Definitions

  • the present invention relates to a silver electrolytic stripping agent and a silver electrolytic stripping method suitable for electrolytically stripping all or unnecessary portions of a plating film from silver-coated parts such as lead frames and connectors, and particularly to copper or copper.
  • the present invention relates to a silver electrolytic stripping agent and a silver stripping method which have a good appearance of a silver-coated film and a residual silver-plated film when the metal is processed (material) such as a copper alloy and has no resist attack.
  • Silver is often applied to electronic components such as semiconductor lead frames and connector pins.
  • plating is usually performed after masking is applied to the unnecessary portion, but not all masking is performed completely, and the silver plating film may protrude to the unnecessary portion. In such a case, it is necessary to remove the protruding silver coating.
  • an electrolytic peeling method As a method for removing the silver-coated film at an unnecessary portion, an electrolytic peeling method is known.
  • a silver-coated material to be treated is immersed in a bath of a stripping agent (stripping solution), and the silver-coated film is stripped by electrolysis using the material as an anode. It is a method.
  • silver electrolytic strippers have been used in which concentrated nitric acid is added to sodium nitrate, those that contain cyanide, and those that contain sodium thiosulfate as the main component.
  • Metal such as alloys
  • etch corrode
  • wastewater treatment and poison control there were problems such as the need to pay attention to the handling of processing agents such as. Therefore, as a stripping agent that does not use dangerous concentrated sulfuric acid or highly toxic cyanide, succinimide or phthalimide and alkali metal hydroxide are the main components.
  • Japanese Unexamined Patent Publication (Kokai) No. Hei 6-410900 those containing 2-pyrrolidone-15-carboxylic acid and those further containing saccharides in addition thereto.
  • a release agent containing a cyclic acid imide containing one nitrogen atom in the molecule as a main component has been proposed.
  • a 5- or 6-membered ring compound having one NH— such as peracyl barbiturate and dartarimide
  • a hydantoin compound Japanese Patent Application Laid-Open No. — 2 4 3 1 0 0
  • the release agent consisting of a compound mainly composed of a cyclic acid imide containing one nitrogen atom in the molecule is easily hydrolyzed by alkali, and when the decomposed product accumulates in the bath, the surface becomes silvery.
  • the passivation, discoloration, unevenness, etc., of the required part had an adverse effect on the silver-coated surface, the main component was consumed in a large amount, and the bath life was short.
  • the bonding process is performed through die bonding or wire bonding.
  • Die bonding is a process in which the semiconductor chip and the lead frame are bonded with epoxy resin.If epoxy pre-adhesion occurs, the die pad is contaminated with organic substances, resulting in poor ground bonding and loss of electrical connection to the outside. .
  • Wire bonding is a process in which the semiconductor chip and the inner lead of the lead frame are wired with Au, A1, etc. If the inner lead portion Ag surface is contaminated or the surface condition is very rough, Continuity cannot be obtained. Therefore, it is important that as it does not affect the volume bindings Japanese I 1 production after silver peeling. The above described silver release agents did not satisfy these requirements.
  • the main component of the stripping solution is less likely to be hydrated, has a long bath life, enables silver to be stripped at a high current density, and has no adverse effect on the bonding characteristics.
  • the material to be treated such as copper or copper alloy, slightly dissolves and activates the surface of the material.
  • the present inventors first developed a silver electrolytic stripping agent such as hydantoin and a silver electrolytic stripping agent such as hydantoin.
  • An electrolytic peeling method Japanese Patent Application Laid-Open No. 9-149010 was proposed.
  • the silver electrolytic stripping agent and the electrolytic stripping method solve the above problems and have excellent characteristics as compared with the conventional method. However, since they are alkaline, they unfortunately erode the resist (resist attack). Therefore, when the object to be processed has a resist attached when the silver is peeled off, it cannot be used. Disclosure of the invention
  • the present invention provides a stable stripping solution and a long bath life, enables silver to be stripped at a high current density (high speed), and does not adversely affect the bonding characteristics.
  • a silver electrolytic stripping agent that does not discolor or corrode the material to be processed, such as copper or copper alloy, does not particularly cause a resist attack, and does not impair the material and the remaining silver-plated appearance.
  • the subject is an electrolytic stripping method.
  • Silver electrolytic stripping agent characterized by containing a carboxylic acid or its salt as a main component having at least one carboxyl group (-C ⁇ OH) and one hydroxyl group (-OH) in one molecule.
  • One or more acids selected from the group consisting of salicylic acid, gallic acid, mandelic acid, tolovic acid, glycolic acid, lactic acid, hydroacrylic acid, oxybutyric acid, glyceric acid, and dalconic acid, or a salt thereof, as a main component.
  • the silver electrolytic stripping agent according to any one of (1) to (6) above which contains one or more surfactants selected from an anion-based, a cationic-based, and a non-ionic-based surfactant in an amount of 10 gZl to 1 g / 1.
  • Electrolytic stripping method of silver characterized by electrolysis at a bath temperature of 5 to 80 ° C
  • the silver electrolytic stripping agent and the electrolytic stripping agent method of the present invention are characterized in that silver to be treated is formed on various metal base materials such as copper, copper alloy, iron-nickel alloy such as 42 alloy, stainless steel, and nickel alloy. It can be applied to the case where silver or silver-based film is formed by plating or silver brazing, etc., when all or part of the film is peeled off.
  • the main component of the silver electrolytic stripping agent of the present invention is an oxyacid or a salt thereof having one or more carboxyl groups (one CO OH) and one or more hydroxyl groups (—OH) in the molecule, and specifically, salicylic acid and gallic acid.
  • the main component is one or more acids selected from the group consisting of acids, mandelic acid, torovic acid, glycolic acid, lactic acid, hydroacrylic acid, oxybutyric acid, glyceric acid, and dalconic acid, or salts thereof.
  • the chemical formula of these main components is shown in the following chemical formula 1.
  • An oxyacid or a salt thereof which does not have two or more carboxyl groups (-CO OH) or a hydroxyl group (-OH) in a molecule has a slow silver peeling rate, and has poor silver and material appearance after silver peeling. . It is desirable that the concentration of the acid or salt as a main component of the silver electrolytic stripping agent in the bath is 5 to 300 g Z1. If the concentration is too low, the electrolytic stripping rate of silver is low, and if the concentration is high, the electrolytic stripping effect saturates and is not effective.
  • the above bath concentration is set to 5 to 300 g / 1. More preferably, the acid or salt concentration in the bath is preferably from 20 to 120 g Z1.
  • the silver electrolytic stripping agent of the present invention further contains a boric acid-based or phosphate-based pH buffer of 5 to 100 g Zl.
  • the pH buffer include borate compounds such as potassium tetraborate, (ortho) borate, potassium diborate, sodium borate, and sodium pentaborate, such as borate and di, tetra, and pentaborate; Phosphoric acid or its salts, such as acids, orthophosphoric acid, pyrophosphoric acid can be used.
  • copper or a copper alloy When copper or a copper alloy is used as the material to be treated, it is selected from triazole, imidazo mono, pyrro mono, pyrazole, thiazono, thiol, carboxylic acid, and amine.
  • lmgZL to 10gZL of a discoloration preventing agent of at least one kind it is possible to simultaneously perform the peeling treatment of the material at the same time as the silver peeling.
  • the amount is less than 1 mg / L, the effect of preventing discoloration is low, and if it exceeds 10 gZL, the effect is saturated and useless.
  • a more effective range is between 1 Omg / L and 1 gZL.
  • the object having a silver film formed on its surface is immersed in a bath of the electrolytic stripping agent adjusted as described above, and the object is electrolyzed using the object as an anode.
  • the material of the cathode is not particularly limited, but stainless steel is generally used.
  • the current density is from 0.1 to 50 A / dm 2 , preferably from 0.5 to 1 OAZdm 2 , based on the area of the peeled silver. If the current density is too low, the peeling rate is low, while if the current density is too high, passivation of silver tends to occur, which is not preferable.
  • the electrolysis is performed at a bath temperature of 5 to 80 ° C, preferably 10 to 50 ° C. If the temperature of the bath is too low, the stripping rate is low, while if it is too high, the bath becomes unstable, which is not preferable. It is desirable to stir the bath during the electrolysis, and particularly when the current density is high, the stirring speed should be high to suppress the passivation.
  • a silver or silver coating is formed on a copper or copper alloy base material and a silver coating is formed on the copper or copper alloy base material by peeling, immerse in a bath containing the copper discoloration inhibitor (copper inhibitor). Then, electrolysis can be performed using the object to be processed as an anode under the above-described conditions.
  • the whole may be immersed.
  • the silver plating film in the necessary parts such as the pad part usually becomes a low current density part during electrolytic stripping, and the unnecessary part of the silver plating film around it becomes a high current part. Therefore, even if electrolytic peeling is performed without masking the required silver-coated portion, only the silver-coated film at the unnecessary portion can be removed. Examples and comparative examples
  • Release agent baths having the compositions shown in Sample Nos. 1 to 10 in Table 1 were prepared.
  • * 1 indicates polyoxyethylene nonylphenyl ether
  • * 2 indicates peryl betaine.
  • Sample No. 1 contains salicylic acid 25 gZl as the main component, and further contains polyoxyethylenenoylphenyl ether 1 Omg / 1 as a surfactant and benzotriazoyl 5 OmgZ1 as a copper discoloration inhibitor.
  • No. 2 contained gallic acid 10 g / 1
  • sample No. 3 contained mandelic acid 25 g / 1 as the main component, and further contained benzotriazole 5 Omg / 1 as a copper discoloration inhibitor.
  • Sample No. 4 contained 50 g / 1 of toroic acid as the main component, and further contained 15 g / 1 of boric acid as a pH buffer.
  • Sample No. 5 contained 25 g / 1 of glycolic acid as the main component and further contained an interface.
  • Sample No. 6 containing 10 Omg / 1 stearic acid as the activator
  • Sample No. 7 containing 25 g / l of lactic acid
  • Sample No. 7 containing 10 gZl of hydroacrinoleic acid
  • Sample No. 8 containing 50 gZ1 of oxybutyric acid as the main component
  • boric acid 15 g / pH as a pH buffer l 1 O OmgZ of butyric acid as a surfactant and 5 OmgZ 1 of hexadecyl mercuff as a copper discoloration inhibitor
  • Sample No. 9 contains 50 g Zl of glyceric acid as the main component, Laurinobetaine containing 1 OmgZ1 and Sample No. 10 containing 50 g / 1 of gnoreconic acid.
  • the main component of the release agent is an oxyacid or a salt thereof having one or more carboxyl groups (-COOH) and one or more hydroxyl groups (-OH) in the molecule.
  • the electrolytic stripping bath of Comparative Example 1 contains 50 gZ1 of imidized succinate, and the electrolytic stripping bath of Comparative Example 2 contains 50 gZ1 of hydantoin.
  • the pH is alkaline at 9.0 and 10.0, respectively.
  • the silver stripping agent and the stripping method of the present invention are capable of stripping silver at a high current density (high speed) while maintaining a stable stripping solution and a long bath life. It does not adversely affect the characteristics.
  • the electrolytic stripping agent is used, the discoloration or corrosion of the material to be processed, such as copper or copper alloy, does not occur, and in particular, the resist attack does not occur. It has an excellent effect that the remaining silvery appearance is not impaired.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • ing And Chemical Polishing (AREA)

Abstract

L'invention porte sur un décapant électrolytique de l'argent dont le composant principal est un acide oxo présentant un groupe carboxyle (-COOH) et un ou plusieurs groupes hydroxyles (-OH) ou l'un de ses sels, en particulier un ou plusieurs acides choisis parmi les acides salicylique, gallique, mandélique, tropique, glycolique, lactique, hydroacrylique, oxybutyrique, glycérique, et gluconique ou l'un de leurs sels, et sur un procédé de décapage électrolytique l'utilisant. Ledit décapant est avantageux car sa préparation liquide est stable, d'où la longue durée de vie d'un bain l'utilisant. En outre: l'argent peut s'éliminer avec un courant de densité élevée (à grande vitesse), les propriétés des liaisons ne sont pas affectées, et le substrat traité, par exemple de cuivre ou d'alliage de cuivre, ne subit ni variation de couleur, ni corrosion, ni surtout d'attaque des résines, et reste exempt d'altérations d'aspect et de couche résiduelle d'argent.
PCT/JP2000/002364 1999-06-03 2000-04-12 Decapant electrolytique de l'argent et procede de decapage electrolytique WO2000075404A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP11/155975 1999-06-03
JP11155975A JP2000345400A (ja) 1999-06-03 1999-06-03 銀の電解剥離剤及び電解剥離方法

Publications (1)

Publication Number Publication Date
WO2000075404A1 true WO2000075404A1 (fr) 2000-12-14

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI755229B (zh) * 2020-12-30 2022-02-11 力橋國際有限公司 無氰之電解剝銀劑及電解剝銀方法

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011021232A (ja) * 2009-07-15 2011-02-03 Mitsubishi Shindoh Co Ltd 銀めっきが施された銅又は銅合金屑のリサイクル方法
JP2011149037A (ja) * 2010-01-19 2011-08-04 Mitsubishi Shindoh Co Ltd 銀めっきが施された銅又は銅合金屑のリサイクル方法
US9587208B2 (en) 2012-06-13 2017-03-07 Mitsubishi Gas Chemical Company, Inc. Cleaning liquid composition, method for cleaning semiconductor element, and method for manufacturing semiconductor element

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1088400A (ja) * 1996-09-12 1998-04-07 Okuno Chem Ind Co Ltd 銀の電解剥離剤及び剥離液並びに電解剥離方法

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1088400A (ja) * 1996-09-12 1998-04-07 Okuno Chem Ind Co Ltd 銀の電解剥離剤及び剥離液並びに電解剥離方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI755229B (zh) * 2020-12-30 2022-02-11 力橋國際有限公司 無氰之電解剝銀劑及電解剝銀方法

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