EP1408141B1 - Methode et électrolyte pour la deposition galvanique des bronzes - Google Patents

Methode et électrolyte pour la deposition galvanique des bronzes Download PDF

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Publication number
EP1408141B1
EP1408141B1 EP02022718.7A EP02022718A EP1408141B1 EP 1408141 B1 EP1408141 B1 EP 1408141B1 EP 02022718 A EP02022718 A EP 02022718A EP 1408141 B1 EP1408141 B1 EP 1408141B1
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EP
European Patent Office
Prior art keywords
electrolyte
tin
copper
deposition
wetting agent
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.)
Revoked
Application number
EP02022718.7A
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German (de)
English (en)
Other versions
EP1408141A1 (fr
Inventor
Katrin Zschintzsch
Joachim Dr. Heyer
Marlies Dr. Kleinfeld
Stefan Schäfer
Ortrud Steinius
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MacDermid Enthone Inc
Original Assignee
Enthone Inc
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Publication date
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Application filed by Enthone Inc filed Critical Enthone Inc
Priority to ES02022718T priority Critical patent/ES2531163T3/es
Priority to EP02022718.7A priority patent/EP1408141B1/fr
Priority to KR1020057004846A priority patent/KR100684818B1/ko
Priority to PCT/EP2003/011229 priority patent/WO2004035875A2/fr
Priority to CN2003801012538A priority patent/CN1703540B/zh
Priority to JP2004544134A priority patent/JP4675626B2/ja
Priority to US10/531,142 priority patent/US20060137991A1/en
Publication of EP1408141A1 publication Critical patent/EP1408141A1/fr
Publication of EP1408141B1 publication Critical patent/EP1408141B1/fr
Application granted granted Critical
Anticipated expiration legal-status Critical
Revoked 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
    • C25D3/58—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of copper
    • 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
    • C25D3/60—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of tin

Definitions

  • the present invention relates to a process for the electrodeposition of bronzes, with which the substrate to be coated in an acidic electrolyte, which comprises at least tin and copper ions, an alkyl sulfonic acid and a wetting agent is metallized, and the representation of such an electrolyte.
  • an acidic electrolyte which comprises at least tin and copper ions, an alkyl sulfonic acid and a wetting agent is metallized
  • the European patent application EP 1 091 023 discloses a method for depositing tin-copper alloys for electrical engineering applications.
  • the electrolytes known from said patent application may contain between 5 and 100 g / l of tin, 0.01 and 10 g / l of copper and an aromatic nonionic surfactant and an alkylsulfonic acid.
  • an electrolyte for depositing tin-copper alloys which contains water-soluble tin salts, water-soluble copper salts, inorganic or organic acids or their water-soluble salts, and one or more compounds selected from the group consisting of thioamides and thiols.
  • the thus deposited tin-copper alloys can serve as a replacement for lead-containing tin solders.
  • an electrolyte for the deposition of specularly lustrous tin-copper alloys, wherein the electrolyte is an aqueous cyanide-free solution comprising organosulfonic acids, bivalent tin and copper salt and a brightener.
  • an alkaline cyanide bath for depositing copper-tin alloys containing as organo-constituents either a fatty acid amidoalkyldialkylamine oxide, a fatty acid amidoalkyldialkylamine betaine or an ethoxylated naphthol.
  • a solution for the deposition of tin alloys and a corresponding deposition method comprises an organic sulfonic acid, tin salts of organic sulfonic acid and sulfonates of metals of the group consisting of zinc, bismuth, silver, indium and copper.
  • an electrolyte for depositing low-melting tin alloys is known, wherein the electrolyte may comprise tin as methanesulfonates or isopropanol sulfonates. As further alloying metals to be deposited.
  • the electrolyte may contain copper, silver, indium, zinc or thallium.
  • the US patent US 6,176,996 discloses an electrolyte for depositing a tin-based binary alloy, wherein the electrolyte is 20 to 500 g / L of a tin salt, 1 to 100 g / L of a metal salt selected from the group consisting of zinc, cobalt, bismuth and copper, 20 to 200 g / L a methanesulfonic acid, 10 to 300 g / l of a lead compound and 0.5 to 50 g / l of a complexing agent.
  • the oxidation to tetravalent tin is associated with a strong sludge formation, which can prevent a stable operation and a long life of the acidic electrolyte.
  • the formation of an adherent and non-porous coating is no longer guaranteed by such impurities.
  • the invention is therefore based on the object of specifying a method for the deposition of bronzes, which allows a uniform deposition of at least tin and copper next to each other from an acidic electrolyte at much higher deposition rates over the methods known in the art.
  • adherent and non-porous bronze coatings with high copper contents and different decorative and mechanical properties should be deposited.
  • an acidic electrolyte is to be provided for the deposition of such bronze coatings, which may have a high content of bivalent copper ions, is stable to oxidation-induced sludge formation, is ready for use over a prolonged period and is economical and environmentally friendly.
  • the object is achieved by a process for the electrodeposition of bronzes with a copper content of> 10 wt .-%, wherein a substrate to be coated is metallized in an acidic electrolyte at a set current density between 0.1 to 120 A / dm 2 , wherein the electrolyte has at least tin and copper ions, an aromatic nonionic surfactant and methanesulfonic acid dissolved, characterized in that the electrolyte has a tin ion concentration of 2 to 75 g / l, a copper ion concentration of 2 to 70 g / l and a methanesulfonic acid concentration of at least 238 g / l is adjusted and bismuth and / or zinc is added to the electrolyte.
  • the present invention provides a process for the electrodeposition of bronzes, wherein, using an electrolyte, an anode of a copper-tin alloy and a cathode connected to the substrate to be coated, the coating is carried out while passing through direct current. Furthermore, the invention provides an electrolyte which can be used in particular for this process and also the coatings obtainable by this process.
  • the disadvantages known in the prior art become available with the provision of a novel composition of the electrolyte eliminated and achieved in this way significantly better deposition results.
  • the implementation is simplified and made more economical. This too is mainly due to the advantageous composition of the electrolyte.
  • the process is carried out at room temperature or between 17 to 25 ° C and to be coated Substrate metallized in a strongly acidic medium at a pH of ⁇ 1. In this temperature range, the electrolyte is particularly stable.
  • there are no costs for heating the electrolyte and also the metallized substrates need not be cooled down in a time and cost intensive manner.
  • deposition rates of 0.25 ⁇ m / min are achieved at a current density of 1 A / dm 2 , inter alia due to the pH value and the advantageous addition of at least one aromatic, nonionic wetting agent.
  • This can be increased by the increase of the metal content up to 7 A / dm 2 in the rack application and for pass-through systems even up to 120 A / dm 2 .
  • applicable current densities in a range of 0.1 to 120 A / dm 2 are achieved depending on the type of system.
  • the wetting of the surfaces to be metallized, especially of more complex substrates is surprisingly improved considerably.
  • This advantageously has the consequence that not only significantly higher deposition rates are achieved by the use of the method according to the invention, but also that the coatings obtained by the process are uniform and of high quality, have a very good adhesion and are completely non-porous.
  • Another advantage of the aromatic, nonionic wetting agent used is that due to the advantageous wetting properties during the process, the electrolyte and / or the substrate in the electrolyte has little or no need to be moved in order to achieve the desired deposition results, so that the use of additional devices for moving the electrolyte can be dispensed with.
  • the aromatic, nonionic wetting agent when removing the metallized substrates from the electrolyte, the electrolyte residues run better from the substrates, which leads to reduced carry-over losses and thus to lower process costs.
  • Particularly advantageous is the addition of 2 to 40 g / l of one or more aromatic, nonionic wetting agents, particular preference being given to using ⁇ -naphthol ethoxylate and / or nonylphenol ethoxylate.
  • the proposed method is thus advantageously economical and environmentally friendly with respect to the cyanidic processes.
  • anionic and / or aliphatic, nonionic wetting agents are possible, provided that they support the advantageous mode of action of the aromatic, nonionic wetting agent or even reinforce.
  • Polyethylene glycols and / or anionic surfactants are preferably added to the electrolyte as anionic and / or aliphatic, nonionic wetting agents in this regard.
  • the method according to the invention is characterized in particular by the particular composition of the electrolyte.
  • This contains essentially tin and copper ions, an alkyl sulfonic acid and an aromatic nonionic wetting agent.
  • stabilizers and / or complexing agents, anionic and / or nonionic, aliphatic wetting agents, antioxidants, brighteners and other metal salts may additionally be present in the electrolyte.
  • the metals introduced mainly for the deposition of bronze according to the invention in the electrolyte - tin and copper - may be present primarily as salts of alkylsulfonic acids, preferably as methanesulfonates or as salts of mineral acids, preferably as sulfates.
  • the tin salt used is particularly preferably the tin methanesulfonate in the electrolyte, which is advantageously added to the electrolyte in an amount of 5 to 195 g / l of electrolyte, preferably 11 to 175 g / l of electrolyte.
  • the copper salt used is particularly preferably the copper methanesulfonate in the electrolyte, which is advantageously added to the electrolyte in an amount of 8 to 280 g / l of electrolyte, preferably 16 to 260 g / l of electrolyte.
  • the electrolyte is an acid, preferably a mineral and / or an alkyl sulfonic acid in Quantities of 140 to 382 g / l electrolyte, preferably 175 to 245 g / l electrolyte added.
  • methanesulphonic acid turned out to be particularly advantageous, since on the one hand it causes advantageous solubility of the metal salts and, on the other hand, prescribes or facilitates the adjustment of the pH required for the process due to its acidity.
  • the methanesulfonic acid has the advantageous property of contributing significantly to the stability of the bath.
  • At least one additional metal and / or chloride is added to the electrolyte.
  • the metals are in the form of their soluble salts.
  • the addition of zinc and / or bismuth influences the properties of the deposited coatings to a particular extent.
  • the zinc and / or bismuth metals introduced into the electrolyte may be predominantly present as salts of alkylsulfonic acids, preferably as methanesulfonates or as salts of mineral acids, preferably as sulfates.
  • the zinc sulfate is particularly preferably used in the electrolyte, which is advantageously added to the electrolyte in an amount of 0 to 25 g / l electrolyte, preferably 15 to 20 g / l electrolyte.
  • the bismuth salt is particularly preferably used in the electrolyte, which is advantageously added in an amount of 0 to 5 g / l electrolyte, preferably 0.05 to 0.2 g / l electrolyte to the electrolyte.
  • additives such as stabilizers and / or complexing agents, antioxidants and brighteners, which are commonly used in acidic electrolytes for the deposition of tin alloys, may be added to the electrolyte.
  • gluconates are added to the electrolyte as stabilizers and / or complexing agents.
  • the concentration of the stabilizers and / or complexing agents is 0 to 50 g / l of electrolyte, preferably 20 to 30 g / l of electrolyte.
  • the antioxidant compounds are preferred from the class of Dihydroxybenzenes, for example, mono- or polyhydroxyphenyl such as catechol or phenolsulfonic acid used.
  • the concentration of the antioxidants is 0 to 5 g / l of electrolyte.
  • the electrolyte contains hydroquinone as an antioxidant.
  • the implementation of the method according to the invention enables the deposition of bronzes on different substrates.
  • all common materials for the production of electronic components can be used.
  • hard and wear-resistant bronze coatings are deposited on materials such as plain bearings etc. by the method according to the invention.
  • the inventive method is advantageously used, which is particularly advantageous in these areas, the deposition of multi-metal alloys containing tin, copper, zinc and bismuth, effects.
  • a very particular advantage is that with the method according to the invention so-called "real" bronzes can be deposited, which have a copper content> 60%, wherein the copper content can be up to 95 wt .-%, depending on the desired property.
  • the ratio of the copper content to the tin content in the electrolyte has a significant influence on the properties such as hardness and color of the bronze coatings.
  • silver-colored coatings, so-called white bronzes are deposited, which are relatively soft.
  • yellow gold-colored coatings so-called yellow bronzes
  • red-gold-colored coatings so-called red bronzes
  • the electrolyte contains brighteners from the class of aromatic carbonyl compounds and / or ⁇ , ⁇ -unsaturated carbonyl compounds.
  • the concentration of the brightener is 0 to 5 g / l electrolyte.
  • Electrolyte composition :
  • the base electrolyte of the strongly acidic electrolyte according to the invention essentially comprises (per liter of the electrolyte) 2 - 75 g divalent tin, 2 - 70 g divalent copper, 2 - 40 g an aromatic, nonionic wetting agent and 140 - 382 g a mineral and / or alkylsulfonic acid
  • further constituents can be added to the electrolyte: 0-10 g an anionic and / or aliphatic, nonionic wetting agent, 0 - 50 g a stabilizer and / or complexing agent, 0 - 5 g an antioxidant, 0 - 5 g a shine agent 0 - 5 g trivalent bismuth 0 - 25 g divalent zinc
  • Example 1 red bronze 4 g / l Sn 2+ 18 g / l Cu 2+ 286 g / l methane 3 g / l aromatic, nonionic wetting agent 0.4 g / l aliphatic, nonionic wetting agent 2 g / l Antioxidant 20 mg / l complexing
  • Example 2a (yellow bronze) 4 g / l Sn 2+ 18 g / l Cu 2+ 240 g / l methane 32.2 g / l aromatic, nonionic wetting agent 2 g / l Antioxidant 25 g / l Stabilizer / complexing agent
  • Example 2b (yellow bronze) 4 g / l Sn 2+ 18 g
  • Example 5 (high ductility) (Example of the invention) 4 g / l Sn 2+ 18 g / l Cu 2+ 238 g / l methane 32.2 g / l aromatic, nonionic wetting agent 3 mg / l brightener 2 g / l Antioxidant 25 g / l Stabilizer / complexing agent 20 g / l ZnSO 4
  • Example 6 (Hardness) (Example of the invention) 4 g / l Sn 2+ 18 g / l Cu 2+ 238 g / l methane 32.2 g / l aromatic, nonionic wetting agent 2 g / l Antioxidant 25 g / l Stabilizer / complexing agent 0.1 g / l Bi 3+
  • Example 7 (Yellow Bronze) (Example of the invention) 14.5 g / l Sn 2+ 65.5 g / l Cu 2+ 382

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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)
  • Electroplating Methods And Accessories (AREA)
  • Chemically Coating (AREA)

Claims (15)

  1. Procédé pour le dépôt galvanique de bronzes présentant une proportion de cuivre > 10% en poids, un substrat à revêtir étant métallisé dans un électrolyte acide à une densité de courant réglée entre 0,1 à 120 A/dm2, l'électrolyte présentant au moins des ions d'étain et des ions de cuivre, un mouillant aromatique non ionique ainsi que de l'acide méthanesulfonique, caractérisé en ce qu'on règle dans l'électrolyte une concentration en ions d'étain de 2 à 75 g/l, une concentration en ions de cuivre de 2 à 70 g/l et une concentration en acide méthanesulfonique d'au moins 238 g/l et on ajoute du bismuth et/ou du zinc à l'électrolyte.
  2. Procédé selon la revendication 1, caractérisé en ce qu'on ajoute à l'électrolyte, comme mouillant aromatique non ionique, de l'éthoxylate de β-naphtol.
  3. Procédé selon la revendication 2, l'électrolyte étant additionné de 2 à 40 g/l d'éthoxylate de β-naphtol.
  4. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que le dépôt a lieu à une température de 17°C à 25°C.
  5. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce qu'on règle, pour le dépôt, un pH de l'électrolyte < 1.
  6. Électrolyte acide pour le dépôt galvanique de bronzes présentant une proportion de cuivre > 10% en poids, contenant au moins des ions d'étain et des ions de cuivre, de l'acide méthanesulfonique ainsi qu'un mouillant aromatique non ionique, caractérisé en ce que l'électrolyte présente une concentration en ions d'étain entre 2 et 75 g/l, une concentration en ions de cuivre entre 2 et 70 g/l et une concentration en acide méthanesulfonique d'au moins 238 g/l et contient du bismuth et/ou du zinc.
  7. Electrolyte selon la revendication 6, caractérisé en ce que l'électrolyte présente, comme mouillant aromatique non ionique, de l'éthoxylate de ß-naphtol.
  8. Electrolyte selon la revendication 7, caractérisé en ce qu'il présente 2 à 40 g/l d'éthoxylate de β-naphtol.
  9. Electrolyte selon l'une quelconque des revendications 6 à 8, caractérisé en ce qu'il contient de l'étain et du cuivre sous forme d'un sel soluble d'un acide alkylsulfonique.
  10. Electrolyte selon l'une quelconque des revendications 6 à 9, caractérisé en ce qu'il contient du polyéthylèneglycol et/ou des tensioactifs anioniques comme autre mouillant.
  11. Electrolyte selon l'une quelconque des revendications 6 à 10, caractérisé en ce qu'il contient du chlorure.
  12. Electrolyte selon l'une quelconque des revendications 6 à 11, caractérisé en ce qu'il contient, comme complexant, du gluconate.
  13. Electrolyte selon l'une quelconque des revendications 6 à 12, caractérisé en ce qu'il contient un antioxydant de la classe des dihydroxybenzènes.
  14. Electrolyte selon l'une quelconque des revendications 6 à 13, caractérisé en ce qu'il contient un brillanteur de la classe des composés carbonyle aromatiques et/ou des composés carbonyle α,β-insaturés.
  15. Electrolyte selon l'une quelconque des revendications 6 à 14, caractérisé en ce qu'il présente un pH < 1.
EP02022718.7A 2002-10-11 2002-10-11 Methode et électrolyte pour la deposition galvanique des bronzes Revoked EP1408141B1 (fr)

Priority Applications (7)

Application Number Priority Date Filing Date Title
ES02022718T ES2531163T3 (es) 2002-10-11 2002-10-11 Procedimiento y electrolito para la deposición galvánica de bronces
EP02022718.7A EP1408141B1 (fr) 2002-10-11 2002-10-11 Methode et électrolyte pour la deposition galvanique des bronzes
CN2003801012538A CN1703540B (zh) 2002-10-11 2003-10-10 电沉积青铜的方法
PCT/EP2003/011229 WO2004035875A2 (fr) 2002-10-11 2003-10-10 Procede de depot galvanique de bronzes
KR1020057004846A KR100684818B1 (ko) 2002-10-11 2003-10-10 청동의 전해석출 방법
JP2004544134A JP4675626B2 (ja) 2002-10-11 2003-10-10 ブロンズ電析法及び電解質
US10/531,142 US20060137991A1 (en) 2002-10-11 2003-10-10 Method for bronze galvanic coating

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP02022718.7A EP1408141B1 (fr) 2002-10-11 2002-10-11 Methode et électrolyte pour la deposition galvanique des bronzes

Publications (2)

Publication Number Publication Date
EP1408141A1 EP1408141A1 (fr) 2004-04-14
EP1408141B1 true EP1408141B1 (fr) 2014-12-17

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EP02022718.7A Revoked EP1408141B1 (fr) 2002-10-11 2002-10-11 Methode et électrolyte pour la deposition galvanique des bronzes

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US (1) US20060137991A1 (fr)
EP (1) EP1408141B1 (fr)
JP (1) JP4675626B2 (fr)
KR (1) KR100684818B1 (fr)
CN (1) CN1703540B (fr)
ES (1) ES2531163T3 (fr)
WO (1) WO2004035875A2 (fr)

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JP5642928B2 (ja) 2007-12-12 2014-12-17 ローム・アンド・ハース・エレクトロニック・マテリアルズ，エル．エル．シー． 青銅の電気めっき
ATE486157T1 (de) 2008-05-08 2010-11-15 Umicore Galvanotechnik Gmbh Modifizierter kupfer-zinn-elektrolyt und verfahren zur abscheidung von bronzeschichten
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DE102011008836B4 (de) 2010-08-17 2013-01-10 Umicore Galvanotechnik Gmbh Elektrolyt und Verfahren zur Abscheidung von Kupfer-Zinn-Legierungsschichten
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CN102605394B (zh) * 2012-03-07 2015-02-18 深圳市华傲创表面技术有限公司 一种无氰酸性白铜锡电镀液
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EP3540097A1 (fr) 2018-03-13 2019-09-18 COVENTYA S.p.A. Produits galvanisés et bain électrolytique approprié pour fournir de tels produits
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CN1703540A (zh) 2005-11-30
JP2005537394A (ja) 2005-12-08
US20060137991A1 (en) 2006-06-29
KR100684818B1 (ko) 2007-02-22
KR20050059174A (ko) 2005-06-17
JP4675626B2 (ja) 2011-04-27
WO2004035875A3 (fr) 2005-04-14
WO2004035875A2 (fr) 2004-04-29
CN1703540B (zh) 2010-10-06
ES2531163T3 (es) 2015-03-11
EP1408141A1 (fr) 2004-04-14

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