EP0907767B1 - Bain galvanoplastique sans cyanure pour depot d'or et d'alliages d'or - Google Patents

Bain galvanoplastique sans cyanure pour depot d'or et d'alliages d'or Download PDF

Info

Publication number
EP0907767B1
EP0907767B1 EP97933686A EP97933686A EP0907767B1 EP 0907767 B1 EP0907767 B1 EP 0907767B1 EP 97933686 A EP97933686 A EP 97933686A EP 97933686 A EP97933686 A EP 97933686A EP 0907767 B1 EP0907767 B1 EP 0907767B1
Authority
EP
European Patent Office
Prior art keywords
gold
cyanide
free
electroplating bath
acid
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 - Lifetime
Application number
EP97933686A
Other languages
German (de)
English (en)
Other versions
EP0907767A1 (fr
Inventor
Werner Kuhn
Wolfgang Zilske
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.)
Umicore Galvanotechnik GmbH
Original Assignee
Degussa Galvanotechnik GmbH
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 Degussa Galvanotechnik GmbH filed Critical Degussa Galvanotechnik GmbH
Publication of EP0907767A1 publication Critical patent/EP0907767A1/fr
Application granted granted Critical
Publication of EP0907767B1 publication Critical patent/EP0907767B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/62—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of gold
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/48—Electroplating: Baths therefor from solutions of gold

Definitions

  • the invention relates to a cyanide-free galvanic bath for the deposition of gold and gold alloy coatings, with 0.5 to 30 g / l gold in the form of a complex one sulfur-containing compound, 0 to 50 g / l of one Alloy metal in the form of water soluble compounds from Silver, copper, indium, cadmium, zinc, tin, bismuth, arsenic and / or antimony, 1 to 200 g / l of the free sulfur-containing Compound, 0 to 200 g / l conductive and buffer salts in the form of alkali borates, phosphates, citrates, tartrates and / or gluconates and optionally wetting agents and Brighteners.
  • Galvanic baths containing the gold in the form of a thiosulfato complex are also not significantly more stable. They decompose, like other well-known gold complexes with sulfur-containing compounds, sometimes when standing for a long time.
  • EP-OS 0 611 840 the gold thiosulfato complexes are therefore stabilized by adding sulfinates.
  • the applicable current density is limited in these baths and decomposition usually occurs at current densities above 1 A / dm 2 . In addition, these baths usually cause unpleasant smells.
  • the Bath as a sulfur-containing compound of the gold complex Mercaptosulfonic acid, a disulfide sulfonic acid, or Contains mixtures of these compounds.
  • salts preferably the alkali salts, of these connections.
  • the baths preferably contain 1 to 200 g / l of the free sulfur-containing compound or its alkali salts in Excess over the stoichiometric composition of the corresponding gold complex.
  • baths 0.01 to 10 g / l wetting agent in the form of surfactants and 0.1 to 1000 mg / l Brightener in the form of selenium and / or tellurium compounds contain.
  • the bath is advantageously at a pH of 7 to 12 operated.
  • the sulfur-containing compounds for the Baths according to the invention are suitable, show a good one Water solubility and great stability associated with a low vapor pressure, so no bad smell is noticeable.
  • the compounds are preferred in the form of their Alkali salts used.
  • the corresponding gold complexes are simple Implementation of soluble gold compounds, e.g. Tetrachloroauric acid, sodium aurate solutions or the like, with the stoichiometric amount or an excess these sulfur-containing compounds in aqueous solution receive. Note that for the reduction to gold (I) required stoichiometric amount of sulfur-containing Links. Should the galvanic bath be free of To be chloride ions, gold is initially with ammonia solution to fall as gold, to wash thoroughly and in one aqueous solution of the sulfur-containing compound dissolve.
  • soluble gold compounds e.g. Tetrachloroauric acid, sodium aurate solutions or the like
  • the solution of the gold complex can be used directly to prepare the galvanic bath can be used.
  • the bath contains preferably an excess of sulfur-containing Compounds of 1-200 g / l.
  • Co-deposition of other metals besides gold from this System for influencing the layer properties is possible.
  • Co-deposition of silver is interesting, Copper, indium, cadmium, tin, zinc, bismuth and the Semi-metals arsenic and antimony.
  • Bismuth is preferred as citrate or EDTA complex, tin preferably as oxalatostannnate (IV) or tin (II) gluconate complex and indium as a gluconate or EDTA complex used.
  • Arsenic and antimony are mainly used for Increased hardness and gloss formation. Arsenic is preferred in Form of alkali arsenite compounds, antimony preferred in Form of alkali monimonyl tartrate used.
  • the Concentration of the alloy metals can vary widely vary between 10 mg / l and 50 g / l.
  • the concentration the free complexing agent in the bath can be between 0.1 and 200 g / l.
  • lead and buffer substances such as borates, Tetraborates, phosphates, citrates, tartrates or gluconates increase the alkali metals in concentrations of 1-200 g / l the conductivity and spreadability of the bath.
  • ionic and nonionic ethylene oxide adduct type surfactants such as Alkyl (fatty acid) or nonylphenol polyglycol ether with End groups as alcohol, sulfate, sulfonate or phosphate as well as perfluorinated compounds, such as Perfluoroalkane carboxylates or sulfonates and cationic Surfactants, e.g. Tetraalkyammonium.

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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)
  • Electroplating And Plating Baths Therefor (AREA)

Claims (6)

  1. Bain galvanoplastique sans cyanure pour le dépôt de revêtements d'or ou d'alliages d'or avec de 0,5 à 30 g/l d'or sous la forme d'un complexe d'un composé contenant du soufre, de 0 à 50 g/l d'un métal d'alliage sous la forme de composés solubles dans l'eau, de l'argent, du cuivre, de l'indium, du cadmium, du zinc, de l'étain, du bismuth, de l'arsenic et/ou de l'antimoine, de 1 à 200 g/l d'un composé contenant du soufre libre, de 0 à 200 g/l de sels conducteurs et tampon sous forme de borates, de phosphates, de citrates, de tartrates et/ou de gluconates de métal alcalin,
    caractérisé en ce qu'
    il contient en tant que composé contenant du soufre, du complexe d'or, un acide mercaptosulfonique, un acide disulfuresulfonique, leurs sels ou des mélanges de ces composés.
  2. Bain galvanoplastique sans cyanure, selon la revendication 1,
    caractérisé en ce qu'
    il contient un composé de formule générale (I) X-S-CHR-(CR'R")n-SO3H dans laquelle
    X, représente H, ou le reste -S-CHR-(CR'R")n-SO3H
    R, représente H, un alkyle ou un aryle ayant jusqu'à 12 atomes de carbone et SO3H et
    R', R", R ou OH ou SH ou NH2
    n : nombres de 0 à 6.
  3. Bain galvanoplastique sans cyanure, selon les revendications 1 ou 2,
    caractérisé en ce qu'
    il contient de l'acide 2-mercaptoéthanesulfonique, de l'acide 3-mercaptopropanesulfonique, de l'acide 2,3-dimercaptopropane-sulfonique, du disulfure de bis-(2-sulfopropyle) ou leurs sels de métal alcalin.
  4. Bain galvanoplastique sans cyanure selon les revendications 1 à 3,
    caractérisé en ce qu'
    il contient de 0,01 à 10 g/l d'agent mouillant sous la forme d'un agent tensioactif et de 0,1 à 1000 mg/l d'un agent de brillance sous la forme de composés du sélénium et/ou du tellure.
  5. Procédé de formation de dépôts gavanoplastiques d'or et d'alliages d'or à partir d'un bain galvanoplastique sans cyanure,
    caractérisé en ce que
    le dépôt s'effectue à partir d'un bain selon les revendications 1 à 4.
  6. Procédé selon la revendication 5,
    caractérisé en ce que
    le bain est utilisé à une valeur de pH de 7 à 12.
EP97933686A 1996-07-23 1997-07-21 Bain galvanoplastique sans cyanure pour depot d'or et d'alliages d'or Expired - Lifetime EP0907767B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19629658A DE19629658C2 (de) 1996-07-23 1996-07-23 Cyanidfreies galvanisches Bad zur Abscheidung von Gold und Goldlegierungen
DE19629658 1996-07-23
PCT/EP1997/003903 WO1998003700A1 (fr) 1996-07-23 1997-07-21 Bain galvanoplastique sans cyanure pour depot d'or et d'alliages d'or

Publications (2)

Publication Number Publication Date
EP0907767A1 EP0907767A1 (fr) 1999-04-14
EP0907767B1 true EP0907767B1 (fr) 2002-02-13

Family

ID=7800576

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97933686A Expired - Lifetime EP0907767B1 (fr) 1996-07-23 1997-07-21 Bain galvanoplastique sans cyanure pour depot d'or et d'alliages d'or

Country Status (6)

Country Link
US (1) US6165342A (fr)
EP (1) EP0907767B1 (fr)
JP (1) JPH11513078A (fr)
KR (1) KR20000064256A (fr)
DE (2) DE19629658C2 (fr)
WO (1) WO1998003700A1 (fr)

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WO2001027354A1 (fr) * 1999-10-07 2001-04-19 Tanaka Kikinzoku Kogyo K.K. Liquide de dorure et procede de dorure par ce liquide
EP1162289A1 (fr) * 2000-06-08 2001-12-12 Lucent Technologies Inc. Bain pour l'electrodeposition de palladium et processus pour l'electrodeposition
JP4183240B2 (ja) * 2001-02-28 2008-11-19 ヴィーラント デンタル ウント テクニーク ゲーエムベーハー ウント コー カーゲー 金および金合金の電着浴とその用法
DE10110743A1 (de) * 2001-02-28 2002-09-05 Wieland Dental & Technik Gmbh Bad zur galvanischen Abscheidung von Gold und Goldlegierungen sowie dessen Verwendung
US6736954B2 (en) * 2001-10-02 2004-05-18 Shipley Company, L.L.C. Plating bath and method for depositing a metal layer on a substrate
JP3985220B2 (ja) * 2001-12-06 2007-10-03 石原薬品株式会社 非シアン系の金−スズ合金メッキ浴
CA2365749A1 (fr) 2001-12-20 2003-06-20 The Governors Of The University Of Alberta Un procede d'electrodeposition et un materiau composite multicouche ainsi obtenu
JP2006111960A (ja) * 2004-09-17 2006-04-27 Shinko Electric Ind Co Ltd 非シアン無電解金めっき液及び無電解金めっき方法
JP4759416B2 (ja) * 2006-03-20 2011-08-31 新光電気工業株式会社 非シアン無電解金めっき液及び無電解金めっき方法
CH710184B1 (fr) 2007-09-21 2016-03-31 Aliprandini Laboratoires G Procédé d'obtention d'un dépôt d'alliage d'or jaune par galvanoplastie sans utilisation de métaux ou métalloïdes toxiques.
DE102009024396A1 (de) * 2009-06-09 2010-12-16 Coventya Spa Cyanid-freier Elektrolyt zur galvanischen Abscheidung von Gold oder dessen Legierungen
EP2312021B1 (fr) 2009-10-15 2020-03-18 The Swatch Group Research and Development Ltd. Procédé d'obtention d'un dépôt d'alliage d'or jaune par galvanoplastie sans utilisation de métaux toxiques
JP5529497B2 (ja) * 2009-11-05 2014-06-25 三菱重工印刷紙工機械株式会社 フレキソ印刷機のインキ洗浄方法及び装置
DE102010053676A1 (de) 2010-12-07 2012-06-14 Coventya Spa Elektrolyt für die galvanische Abscheidung von Gold-Legierungen und Verfahren zu dessen Herstellung
DE102012004348B4 (de) 2012-03-07 2014-01-09 Umicore Galvanotechnik Gmbh Verwendung von organischen Thioharnstoffverbindungen zur Erhöhung der galvanischen Abscheiderate von Gold und Goldlegierungen
ITFI20120103A1 (it) * 2012-06-01 2013-12-02 Bluclad Srl Bagni galvanici per l'ottenimento di una lega di oro a bassa caratura e processo galvanico che utilizza detti bagni.
CN102731536A (zh) * 2012-06-29 2012-10-17 长沙铂鲨环保设备有限公司 一种阴离子型金络合物及其应用
JP6254942B2 (ja) * 2012-07-13 2017-12-27 東洋鋼鈑株式会社 燃料電池用セパレータ、燃料電池セル、燃料電池スタック、および燃料電池用セパレータの製造方法
CN103741180B (zh) * 2014-01-10 2015-11-25 哈尔滨工业大学 无氰光亮电镀金添加剂及其应用
CN104233385A (zh) * 2014-10-22 2014-12-24 华文蔚 一种噻唑无氰镀金的电镀液及其电镀方法
JP6207655B1 (ja) * 2016-04-12 2017-10-04 日本エレクトロプレイテイング・エンジニヤース株式会社 非シアン系Ａｕ−Ｓｎ合金めっき液
CN106757201B (zh) * 2016-12-29 2019-01-15 三门峡恒生科技研发有限公司 一种无氰弱酸性电镀液、及其制备方法和使用方法

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US35513A (en) * 1862-06-10 Improvement in window-sash
US3057789A (en) * 1959-02-26 1962-10-09 Paul T Smith Gold plating bath and process
DE2355581C3 (de) * 1973-11-07 1979-07-12 Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler, 6000 Frankfurt Galvanisches Glanzgoldbad mit hoher Abscheidungsgeschwindigkeit
DE2445538C2 (de) * 1974-09-20 1984-05-30 Schering AG, 1000 Berlin und 4709 Bergkamen Cyanidfreies Bad und Verfahren zur galvanischen Abscheidung von Edelmetall - Legierungen
JPS5337149A (en) * 1976-09-20 1978-04-06 Toho Kasei Kougiyou Kk Gold plating method
JPS5384829A (en) * 1976-12-30 1978-07-26 Seiko Instr & Electronics Nonncyanogen gold alloy plating liquid
CH622829A5 (fr) * 1977-08-29 1981-04-30 Systemes Traitements Surfaces
US5302278A (en) * 1993-02-19 1994-04-12 Learonal, Inc. Cyanide-free plating solutions for monovalent metals
EP0693579B1 (fr) * 1994-07-21 1997-08-27 W.C. Heraeus GmbH Bain pour le dépÔt électrolytique d'alliages Palladium-Argent
JP3365866B2 (ja) * 1994-08-01 2003-01-14 荏原ユージライト株式会社 非シアン性貴金属めっき浴

Also Published As

Publication number Publication date
EP0907767A1 (fr) 1999-04-14
DE19629658A1 (de) 1998-01-29
US6165342A (en) 2000-12-26
KR20000064256A (ko) 2000-11-06
WO1998003700A1 (fr) 1998-01-29
JPH11513078A (ja) 1999-11-09
DE59706393D1 (de) 2002-03-21
DE19629658C2 (de) 1999-01-14

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